CN102504054B - 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
- Publication number
- CN102504054B CN102504054B CN201110338097.3A CN201110338097A CN102504054B CN 102504054 B CN102504054 B CN 102504054B CN 201110338097 A CN201110338097 A CN 201110338097A CN 102504054 B CN102504054 B CN 102504054B
- Authority
- CN
- China
- Prior art keywords
- ketone
- phenyl
- hydroxyl
- methylpropane
- bis
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
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
Structure and the preparation method, particularly one that the present invention relates to the novel photoinitiator in ultraviolet light polymerization (UV solidifies) field can reduce until eliminate structure of the polyfunctional group alcohol ketone photoinitiator of volatile organic compounds (VOC) discharge and preparation method thereof.
Background technology
One, about alcohol ketone photoinitiator
Hydroxyalkyl aryl ketones light trigger refers to the general name containing 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 aryl, and opposite side is the alkyl for containing a α position hydroxyl.
It is fast that hydroxyalkyl aryl ketones light trigger has velocity of initiation, and efficiency of initiation is high, and the persistence xanthochromia of product is affected to the good characteristics such as little, has therefore been subject to very early showing great attention to of academia and industry member.For many years, many about patent and research paper 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 the hydroxyalkyl aryl ketones light trigger of, having obtained important commercial applications has following representational kinds.
As far back as 1978, Merck company has applied for the product patent of Section 1 hydroxyalkyl aryl ketones light trigger, and this patent is bought by Ciba-Geigy company of Switzerland (existing purchased by BASF AG, below identical), commodity are called Darocur 1173, and structural formula is as follows:
Nineteen eighty-three, Ciba-Geigy company of Switzerland applies for and has obtained another hydroxyalkyl aryl ketones light trigger patent, the commodity Irgacure 184 by name of this product, and structural formula is as follows:
Structure, above the two difference is: the hydroxyalkyl of Darocur 1173 is hydroxyl sec.-propyl, and the hydroxyalkyl of Irgacure 184 is hydroxy-cyclohexyl.
Above-mentioned binomial product has been obtained the large business success of tool at present.According to statistics, the consumption of the annual Darocur 1173 in the whole world and Irgacure 184 single products has just exceeded 6000 tons at present.
US Patent No. 4672079 has been described the important hydroxyalkyl aryl ketones light trigger patent on the eighties application in last century another market of having by Italian Lamberti company, and its commodity are called KIP150, and structural formula is as follows:
Structure, this product is equivalent to Darocur 1173 to couple together by the Alpha-Methyl methylene radical of phenyl ring contraposition.In actual fabrication process, first this product carries out oligomerization by alpha-methyl styrene, it is said that the product polymerization degree is between 4-6, is then connected hydroxyalkyl by the synthetic method similar with Darocur 1173 in the contraposition of phenyl ring.This is unique hydroxyalkyl aryl ketones light trigger kind of patenting and obtaining important commercial applications except Ciba company of Switzerland up to now.
US Patent No. 4861919 has been introduced by Ciba-Geigy company of Switzerland in the eighties application in last century and has been had another important hydroxyalkyl aryl ketones light trigger patent and obtained practical, commercial, and its commodity are called Darocur2959:
This product, among the structure of Darocur 1173, has increased hydroxyl ethoxy substituting group in the contraposition of phenyl, and 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 in order further to develop, new texture provides the foundation and possibility in the hydroxy ethoxy functional group, newly increasing.
Chinese patent CN1249009C has introduced west bar special chemical (the Ciba Special Chemical by Switzerland, formed by Ciba-Geigy restructuring, now purchased by BASF AG) another hydroxyalkyl aryl ketones light trigger patent of obtaining the authorization in 2006 and announcing, its structural formula is as follows:
This product is named as Irgacure 127.Structure, this product is equivalent to two Darocur 1173 molecules to couple together by a methylene radical in the contraposition of phenyl ring.Although this time to market (TTM) is not long, due to the new features that this product has, manifest important commercial application prospect at present.
The product patent of the hydroxyalkyl aryl ketones light trigger relating to both at home and abroad recent decades also has a lot, but except above-mentioned kind, great majority there is no and obtain commercial applications.
Two, discharge about VOC
VOC (english abbreviation of volatile organic compounds volatile organic compounds) is one of important root causing environmental air pollution.Modern society is more and more higher for eco-friendly requirement, therefore also more and more stricter to the requirement of VOC discharge.
Countries in the world and all kinds of mechanism are for VOC still without unified definition at present, and the requirement that therefore limits VOC discharge is also not quite similar.When how discussion reduces and eliminate VOC discharge, different definition and requirement can cause there is incomplete same result.
Chinese tobacco monopoly bureau has promulgated industry standard YC/T 207-2006 " the mensuration Headspace-Gas Chromatography Analysis of volatile organic compounds in tobacco shred and box packaging paper " on October 13rd, 2006, this is domestic the clearest and the most definite also the severeest professional VOC emission standard up to now, and this standard has proposed 16 concrete VOC test items and these individual project examination criterias and the comprehensive judging criterion of VOC total amount (in table one):
Table one individual event examination criteria and the comprehensive judging criterion 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.
VOC is defined as any organic compound that can participate in atmospheric photochemical reaction by U.S. ASTM D3960-98 standard; The World Health Organization is defined as the general name of fusing point boiling point volatile organic compounds between 50～250 DEG C lower than room temperature to total volatile organic compound (TVOC); International standard ISO 4618/1-1998 and German DIN55649-2000 standard to the definition of VOC are: at normal temperatures and pressures, and organic liquid and/or the solid of the spontaneous volatilization of any energy.In addition, German DIN 55649-2000 standard has a restriction in the time measuring VOC content, and under pressure condition conventionally, boiling point or initial boiling point are less than or equal to any organic compound of 250 DEG C.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 to participate in the prerequisite of atmospheric photochemical reaction, therefore, World Health Organization and European standard are more severe to the restriction of VOC, related material is more extensive.Generally speaking, under normal pressure, boiling point can be got rid of outside VOC substantially higher than 250 DEG C of above organic compound.Can find out easily according to this principle, China Tobacco Corporation limits 16 kinds of materials to tobacco bale printing-ink VOC, and its atmospheric boiling point is all well below below 250 DEG C, but still has the volatile organic matter of One's name is legion not among this standard limits.
Three, the relation of hydroxyalkyl aryl ketones light trigger and VOC
Examine or check the atmospheric boiling point of five kinds of hydroxyalkyl aryl ketones light triggers listed above, except the atmospheric boiling point of Darocur 1173 and Irgacure184 approaches 250 DEG C, the atmospheric boiling point of its excess-three kind is all far above 250 DEG C, therefore these five kinds of light triggers self all do not belong to 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 occurs under ultraviolet radiation can represent with figure below:
Hydroxyalkyl aryl ketones belongs to crack type photoinitiator.From then in figure, can find out, under ultraviolet radiation, the molecule of hydroxyalkyl aryl ketones is accepted photon energy, is cracked into two free radicals, and one of them is aroyl free radical, and another is hydroxyalkyl radical.These free 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 free radical that our unwanted side reaction has occurred, such as aroyl free radical generation hydrogen abstraction reaction generates aromatic aldehyde, hydroxyalkyl radical generation hydrogen transfer reactions generates alkyl ketone.Previously described five kinds of hydroxyalkyl aryl ketones light triggers after reaction the by product that generates and boiling point list thereof in table two:
Table two: the atmospheric boiling point list of five kinds of conventional hydroxyalkyl aryl ketones light trigger cleaved fragment by products
As can be seen from Table II, 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 meet the emission request of VOC after optical radiation.It needs to be noted, also all can not meet 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 the polyfunctional group alcohol ketone photoinitiator that a class is new, 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 when more than 200 DEG C, can significantly reduce the discharge of this light trigger VOC after photochemical reaction, when the boiling point of aromatic aldehyde by product and alkyl ketone by product is when more than 250 DEG C, can eliminate the VOC discharge of this light trigger completely.The invention provides a class reduces until eliminate polyfunctional group alcohol ketone photoinitiator of VOC discharge and preparation method thereof.
For achieving the above object, technical scheme of the present invention is:
Reduce until eliminate the polyfunctional group alcohol ketone photoinitiator of VOC discharge, the chemical structure of this light trigger is suc as formula shown in I or II:
Wherein, I or II must meet following five conditions simultaneously:
(1) n is integer 2,3 or 4;
(2) Ar is substituted or non-substituted aryl, Ar
1for containing the polyaromatic of 2-4 phenyl ring; The feature of above-mentioned substituted or non-substituted aryl and polyaromatic is that formed its atmospheric boiling point of aromatic aldehyde is greater than 179 DEG C;
Described non-substituted aryl is including but not limited to eight yuan or eight yuan of above monocyclic aryl, fused ring aryl, assorted monocyclic aryl and assorted polyaromatics;
Described substituted aryl is including but not limited to all kinds of monosubstituted and/or polysubstituted phenyl; Substituted radical is any one of following group: phenyl, halogen, C
1-C
12alkyl, C
5-C
6cycloalkyl ,-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); Wherein M
1, M
2and M
3for C
1-C
12hydrocarbyl group;
(3) R, R ' are independent is separately the C of straight or branched
1-C
12alkyl, this alkyl be not substituted or 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 after the polynary halides dehalogenation of one of following structure;
(5), while being constructed as follows the compound of alkyl ketone structure by R, R ', Z, its atmospheric boiling point is greater than 155 DEG C:
Preferably naphthyl, fluorenyl or carbazyl of wherein said non-substituted aryl.
Described substituted aryl is preferably the phenyl being replaced by following group: phenyl, halogen, C
1-C
12alkyl, OM
1,-SM
1,-NM
2m
3.
Described Ar
1be preferably one of following polyaromatic:
When being substituted alkyl, described R, R ' replaced by following group: C
1-C
4alkoxyl group, C
5-C
6cycloalkyl, heterocyclic radical, phenoxy group, halogen or benzene.
Light trigger of the present invention preferably includes following compound:
1,10-dibiphenylyl-2,9-dihydroxyl-2,9-dimethyl nonane-1,10-diketone,
2,9-dihydroxyl-1,10-bis-(1,3,5-trimethylammonium) phenyl-2,9-dimethyl decane-1,10-diketone,
2,9-dihydroxyl-1,10-docosyl phenyl-2,9-dimethyl decane-1,10-diketone,
2,9-dihydroxyl-1,10-bis-(4-methoxyl group) phenyl-2,9-dimethyl decane-1,10-diketone,
2,9-dihydroxyl-1,10-bis-(2,4-dichloro) phenyl-2,9-dimethyl decane-1,10-diketone,
2,9-dihydroxyl-1,10-bis-(4-hydroxy ethoxy) phenyl-2,9-dimethyl decane-1,10-diketone,
3,3 '-(Isosorbide-5-Nitrae-phenylene) two (2-hydroxyl-1-xenyl-2-methylpropane-1-ketone),
3,3 '-(hexanaphthene-Isosorbide-5-Nitrae-bis-base) 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 " (1,3,5-phenylene) three (2-hydroxyl-1-xenyl-2-methylpropane-1-ketone),
2,6-dihydroxyl-4,4-bis-(2-hydroxyl-1-xenyl-2-methylpropane-1-ketone)-2,6-dimethyl-1,7-dibiphenylyl heptane-1,7-diketone,
2-hydroxyl-1-(4-(4-(2-hydroxy-2-methyl myristoyl) phenmethyl) phenyl)-2-methyl pentadecane-1-ketone,
3,3 '-(Isosorbide-5-Nitrae-phenylene) two (2-hydroxyl-1-(1，3，5-trimethyl-benzene base)-2-methylpropane-1-ketone),
3,3 '-(Isosorbide-5-Nitrae-phenylene) two (2-hydroxyl-1-(4-dodecylphenyl)-2-methylpropane-1-ketone),
3,3 '-(Isosorbide-5-Nitrae-phenylene) two (2-hydroxyl-1-(4-methoxyphenyl)-2-methylpropane-1-ketone),
3,3 '-(Isosorbide-5-Nitrae-phenylene) two (2-hydroxyl-1-(2,4 dichloro benzene base)-2-methylpropane-1-ketone),
3,3 '-(Isosorbide-5-Nitrae-phenylene) two (2-hydroxyl-1-(4-hydroxy ethoxy phenyl)-2-methylpropane-1-ketone),
3,3 '-(hexanaphthene-Isosorbide-5-Nitrae-bis-base) two (2-hydroxyl-1-(1,3,5-trimethylammonium) phenyl-2-methylpropane-1-ketone),
3,3 '-(hexanaphthene-Isosorbide-5-Nitrae-bis-base) two (2-hydroxyl-1-(4-dodecyl) phenyl-2-methylpropane-1-ketone),
3,3 '-(hexanaphthene-Isosorbide-5-Nitrae-bis-base) two (2-hydroxyl-1-(4-methoxyl group) phenyl-2-methylpropane-1-ketone),
3,3 '-(hexanaphthene-Isosorbide-5-Nitrae-bis-base) two (2-hydroxyl-1-(2,4-dichloro) phenyl-2-methylpropane-1-ketone),
3,3 '-(hexanaphthene-Isosorbide-5-Nitrae-bis-base) 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-(1,3,5-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-(2,4-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 " (1,3,5-phenylene) three (2-hydroxyl-1-(1,3,5-trimethylammonium) phenyl-2-methylpropane-1-ketone),
3,3 ', 3 " (1,3,5-phenylene) three (2-hydroxyl-1-(4-dodecyl) phenyl-2-methylpropane-1-ketone),
3,3 ', 3 " (1,3,5-phenylene) three (2-hydroxyl-1-(4-methoxyl group) phenyl-2-methylpropane-1-ketone),
3,3 ', 3 " (1,3,5-phenylene) three (2-hydroxyl-1-(2,4-dichloro) phenyl-2-methylpropane-1-ketone),
3,3 ', 3 " (1,3,5-phenylene) three (2-hydroxyl-1-(4-hydroxy ethoxy) phenyl-2-methylpropane-1-ketone),
2,6-dihydroxyl-4,4-bis-(2-hydroxyl-1-mesitylene base-2-methylpropane-1-ketone)-2,6-dimethyl-1,7-dibiphenylyl heptane-1,7-diketone,
2,6-dihydroxyl-4,4-bis-(2-hydroxyl-1-(4-dodecyl) phenyl-2-methylpropane-1-ketone)-2,6-dimethyl-1,7-dibiphenylyl heptane-1,7-diketone,
2,6-dihydroxyl-4,4-bis-(2-hydroxyl-1-(4-methoxyl group) phenyl-2-methylpropane-1-ketone)-2,6-dimethyl-1,7-dibiphenylyl heptane-1,7-diketone,
2,6-dihydroxyl-4,4-bis-(2-hydroxyl-1-(2,4-dichloro) phenyl-2-methylpropane-1-ketone)-2,6-dimethyl-1,7-dibiphenylyl heptane-1,7-diketone,
2,6-dihydroxyl-4,4-bis-(2-hydroxyl-1-(4-hydroxy ethoxy) phenyl-2-methylpropane-1-ketone)-2,6-dimethyl-1,7-dibiphenylyl heptane-1,7-diketone,
2-hydroxyl-1-(4-(4-(2-hydroxy-2-methyl myristoyl) phenoxy group) the phenyl)-2-methyl tetradecane-1-ketone,
1,1 '-(sulfo-two (4,1-phenylene)) two (the 2-hydroxy-2-methyl tetradecane-1-ketone),
1,1 '-((methyl azane two bases) two (4,1-phenylene)) two (the 2-hydroxy-2-methyl tetradecane-1-ketone),
1,1 '-(9-ethyl-9H-carbazole-3,6-bis-bases) two (the 2-hydroxy-2-methyl tetradecane-1-ketone),
1,1 '-(carbonyl diurethane (3,1-phenylene)) two (the 2-hydroxy-2-methyl tetradecane-1-ketone),
1,1 ', 1 " (first three bases three (benzene-4,1-bis-bases)) three (the 2-hydroxy-2-methyl tetradecane-1-ketone).
Shown in formula I of the present invention, reducing until eliminate the preparation method of the polyfunctional group alcohol ketone photoinitiator of VOC discharge divides five steps to complete conventionally:
A: intermediate (I) synthetic: prepare polycarboxylic acid taking diethyl malonate as raw material.
In A step, alkali used comprises sodium ethylate, sodium hydride, sodium hydroxide, potassium hydroxide, cesium hydroxide, salt of wormwood, sodium carbonate, potassiumphosphate; Preferred alcohol sodium, sodium hydride, salt of wormwood.In reaction, the consumption of alkali is excessive, deal based on diethyl malonate (molar equivalent, below ketone), preferred excessive 0.5-5 part, preferably preferred excessive 0.5-2 part.
Polynary halides described in A step can be fluorine, chlorine, bromine, idohydrocarbon, preferably hydrochloric ether, hydrobromic ether; The concrete structure of polynary halides is described above.
In A step, hydrocarbylation useable solvents also can not used solvent, as used solvent can select acetone, ethanol, benzene, DMF, tetrahydrofuran (THF), preferred alcohol, DMF; Hydrolysis and decarboxylic reaction can be with also can not using solvent, as used solvent can select hydrocarbon or the aromatic hydrocarbon that boiling point is higher, and as dodecane, toluene, dimethylbenzene, sym-trimethylbenzene, ethylbenzene, diethylbenzene, isopropyl benzene, preferably dodecane, diethylbenzene.
In A step, hydrocarbyl reaction temperature range is between-10 DEG C-60 DEG C, preferably 20 DEG C-45 DEG C; Hydrolysis temperature variation range between 50 DEG C-100 DEG C, preferably 50 DEG C-80 DEG C; Decarboxylic reaction temperature range is 100 DEG C-150 DEG C, preferably 120 DEG C-140 DEG C.
B: intermediate (II) synthetic: polynary carboxylic acid halides is prepared in polycarboxylic acid and halogenating agent effect;
In B step, halide reagent used comprises halogenation sulfoxide, phosphorus trihalide, phosphorus pentahalides, oxalyl halogen, phosgene; Preferably sulfur oxychloride and phosphorus trichloride.In reaction, halide reagent is excessive, based on the deal of diethyl malonate, and the excessive 0.3-5 part of halide reagent, preferred excessive 0.3-1.5 part.
In B step, reaction can also can be without solvent with solvent, preferably directly taking halogenating agent as the no longer another solubilizing agent of solvent, and as selected halogenated alkane with solvent, for example methylene dichloride, ethylene dichloride, chloroform, tetracol phenixin; Also can select aromatic hydrocarbon, for example benzene,toluene,xylene.
In B step, temperature of reaction span of control is 0 DEG C-100 DEG C, preferably 50 DEG C-80 DEG C.
C: intermediate (III) synthetic: polynary carboxylic acid halides makes polynary aromatic ketone with the electrophilic substitution reaction that aromatic hydrocarbons carries out on aromatic nucleus under a kind of Lewis acid (Lewis) catalysis.
In C step, lewis acid catalyst used comprises aluminum trichloride (anhydrous), FERRIC CHLORIDE ANHYDROUS, Zinc Chloride Anhydrous, anhydrous alchlor etc.; Preferably aluminum trichloride (anhydrous), the 1.0-1.5 that its proportioning is acyl chlorides times molar equivalent, preferably 1.05-1.2 times of molar equivalent.
In C step, reaction both can also can be selected other solvent as solvent with aromatic hydrocarbons itself, and other solvent can select halohydrocarbon, inertia aromatic hydrocarbons as methylene dichloride, ethylene dichloride, chloroform, tetracol phenixin, oil of mirbane; The preferred 2-10 of solvent load times aromatic hydrocarbons weight.
In C step, temperature of reaction all can be carried out at-10 DEG C-100 DEG C, and preferable reaction temperature is-5 DEG C-20 DEG C.
D: intermediate (IV) synthetic: polynary aromatic ketone and halogenating agent generation halogenating reaction obtain halogenated ketone under the effect of catalyzer.
In D step, halo agent used comprises chlorine, bromine, N-bromo-succinimide (NBS), cuprous bromide, cuprous chloride, phosphorus trichloride; Preferably chlorine, bromine, cuprous bromide.
In D step, reaction both can select the solvent also can not select solvent, selects solvent can select halohydrocarbon as methylene dichloride, ethylene dichloride, chloroform, tetracol phenixin as need; Aromatic hydrocarbon is as benzene,toluene,xylene etc.; Also can select the inert solvents such as DMF (DMF), dioxane;
In D step, look raw material differential responses temperature range between-10 DEG C-120 DEG C, preferably 20 DEG C-30 DEG C.
E: reduce until the polyfunctional group alcohol ketone photoinitiator of elimination VOC discharge is synthetic: halogenated ketone intermediate obtains product by hydrolysis reaction under catalyst action.
In E step, alkaline hydrolysis alkali used is selected sodium hydroxide solution, concentration from 5%-50% all can, the preferably ionic membrane caustic soda of 10%-30%; Alkali is excessive, based on halogenated ketone, and preferred excessive 0.5-3 times molar equivalent, best preferably 0.5-1.5 times of molar equivalent.
In E step, alkaline hydrolysis catalyzer selects conventional consisting of phase-transferring agent as Tetrabutyl amonium bromide (TBAB), Tetradecyl Trimethyl Ammonium Bromide (TTAB), cetyl trimethylammonium bromide (CTAB), Cetyltrimethylammonium bromide (STAB); Preferably cetyl trimethylammonium bromide, Cetyltrimethylammonium bromide; Catalyst levels is 0.5 ‰-10% of halogenated ketone by weight, preferably 0.5 ‰-5%.
In E step, can not use solvent when alkaline hydrolysis, also can select solvent, the solvent of selecting can be alkane, halohydrocarbon, aromatic hydrocarbons, preferably methylene dichloride, chloroform, benzene.
In E step, temperature range for hydrolysis is between 20 DEG C-120 DEG C, preferably between 50 DEG C-80 DEG C.
Shown in invention formula II, reduce until eliminate that the polyfunctional group alcohol ketone photoinitiator of VOC discharge is synthetic and can obtain by currently known methods (number of patent application: 201110293714.2), the condition control of the operation of reaction and reaction and formula I compound synthetic similar.
Reduction involved in the present invention is until eliminate the polyfunctional group alcohol ketone photoinitiator of VOC discharge and have the following advantages:
(1) there is higher atmospheric boiling point, itself and VOC free discharge, under fragment molecule normal pressure after photodissociation, boiling point is not only far away higher than the boiling point of the photolysis debris molecule of existing product, and wherein the boiling point of a part of cracking after product even exceedes 250 DEG C, can be considered as VOC free discharge.
(2) multi-functional structure has effectively ensured the quantity of active function groups, and uv-absorbing efficiency is higher.
(3) increase of relative molecular mass, overcome small molecules light trigger smell large, poisonous, move strong shortcoming.
Brief description of the drawings
Fig. 1 is the infrared spectrogram of the compound prepared of embodiment 1.
Embodiment
1A, reference [TETRAHEDRON LETTERS 48 (46), 8230-8233 (2007)] method synthesizing methyl diethyl malonate, get 34.8g methyl-malonic ester and 24.4g1, 6-dibromo-hexane is furnished with in the there-necked flask of condenser in 500ml, under stirring at normal temperature, drip the ethanolic soln 50ml containing 13.6g sodium ethylate, dropwise, slowly be warmed up to 55 DEG C-65 DEG C, reaction 2h, continue temperature rising reflux reaction 2h, the first normal pressure desolventizing that reduces pressure again reaches 100 DEG C to still temperature after completion of the reaction, after cooling, the organic phase obtaining is mixed with the aqueous sodium hydroxide solution of 400ml10%, backflow 14h is hydrolyzed, be hydrolyzed in the complete dilute hydrochloric acid of reaction solution being poured into 400ml10%, separate out yellow oil.Gained oily matter is mixed with the diethylbenzene of double weight, stir and heat up, first azeotropic dehydration, after water has taken off, is warmed up to 176 DEG C of-179 DEG C of decarboxylations, after in reaction system without γ-ray emission, then constant temperature 30min, decarboxylation is complete.In reaction system, add water, azeotropic reclaims diethylbenzene, reclaims completely, cooling, and crude product obtains target product intermediate compound I 17.4g, outward appearance with the 90-120 sherwood oil purification of double weight: white needles solid, yield: 87.4%.
1B, get intermediate compound I 17.4g and be furnished with in the there-necked flask of condenser in 100ml, add PCl
32.2ml, is warming up to 50 DEG C and opens and stir, and continues to be warming up to 75 DEG C and continues reaction 2h, leaves standstill after completion of the reaction 30min and divides and fall down a layer phosphorous acid, and upper strata colourless transparent oil liquid is intermediate II, and total mass is 20.1g, yield nearly 100%.
1C, getting 23.3g biphenyl is dissolved in the there-necked flask that contains 50ml methylene dichloride, under normal temperature, add 22.2g aluminum trichloride (anhydrous) in batches, after be cooled to-5-0 DEG C, drip the dichloromethane solution 50ml containing intermediate II 20.1g, dropwise the rear 30 DEG C of insulation continuation reaction 3h that are naturally warming up to, after soaking time completes, material is splashed in 200ml water, stir, proceed to stratification in separating funnel, water is used respectively twice of 50ml dichloromethane extraction, merge oil phase, wash secondary with 50ml respectively, dried over sodium sulfate, after desolvation, obtain intermediate III 28.8g, yield 76.0%, intermediate III is directly carried out the next step without purifying.
1D, get 28.8g intermediate III and be dissolved in the there-necked flask that contains 100ml methylene dichloride, under normal temperature, drip bromine 9.18g, control temperature of reaction and be no more than 30 DEG C, bromine drips off rear continuation reaction 2h, to producing stopped reaction without white mist, add in 10% sodium sulfite solution 10ml and excess bromine, then alkali cleaning respectively, be washed to oil phase and be neutral, obtain intermediate compound IV 36.4g, yield 96.8% with desolvation after dried over sodium sulfate.
1E, get intermediate compound IV 36.4g in 250ml there-necked flask, add 0.36g Cetyltrimethylammonium bromide catalyzer, slowly be warming up to 80 DEG C, drip 10% sodium hydroxide solution 60ml, dropwise rear continuation reaction 4h, detect after qualified and be cooled to 60 DEG C, add 100ml dichloromethane extraction, leave standstill separatory, water is again with merging oil phase after 30ml dichloromethane extraction, wash three times, desolvation after oil phase dried over mgso, with obtaining product 1 after ethyl acetate and the washing of sherwood oil mixed solvent, 9-bis-([1, 1 '-xenyl]-4-yl)-2, 8-dihydroxyl-2, 8-dimethyl nonane-1, 9-diketone 18.9g, yield is 73.7%.
Embodiment 2-6
In embodiment 2-6, compounds process for production thereof and embodiment 1 are similar, are respectively taking the aromatic hydrocarbon shown in table three as starting raw material in the synthesis step of 1C.
Table three compound of the present invention
Embodiment 7-11
In embodiment 7-11, compounds process for production thereof and embodiment 1 are similar, just in 1A synthetic respectively taking the multi-halogenated compounds shown in table four (ZXn) as starting raw material.
Table four compound of the present invention
Embodiment 12 prepares 2-hydroxyl-1-(4-(4-(2-hydroxy-2-methyl myristoyl) phenmethyl) phenyl)-2-methyl pentadecane-1-ketone
12A, get 17.4g methyl-malonic ester and 20.4g chlorinated dodecane is furnished with in the there-necked flask of condenser in 500ml, under stirring at normal temperature, drip the ethanolic soln 100ml containing 6.8g sodium ethylate, dropwise, slowly be warmed up to 55 DEG C-65 DEG C, reaction 2h, continue temperature rising reflux reaction 2h, the first normal pressure desolventizing that reduces pressure again reaches 130 DEG C to still temperature after completion of the reaction, after cooling, organic phase is mixed with the aqueous sodium hydroxide solution of 200ml10%, reflux and be hydrolyzed for 14 hours, be hydrolyzed in the complete dilute hydrochloric acid of reaction solution being poured into 200ml10%, separate out yellow oil.Gained oily matter is mixed with the diethylbenzene of double weight, stir and heat up, first azeotropic dehydration, after water has taken off, is warmed up to 176 DEG C of-179 DEG C of decarboxylations, after in reaction system without γ-ray emission, then constant temperature 30min, decarboxylation is complete.In reaction system, add water, azeotropic reclaims diethylbenzene, reclaims completely, cooling, and crude product obtains target product intermediate compound I 21.1g, outward appearance with the 90-120 sherwood oil purification of double weight: weak yellow liquid, yield: 87.1%.
12B, get intermediate compound I 211g and be furnished with in the there-necked flask of condenser in 100ml, add PCl3 2.67ml, be warming up to 50 DEG C and open stirring, continue to be warming up to 75 DEG C and continue reaction 2h, leaving standstill after completion of the reaction 30min divides and falls down a layer phosphorous acid, upper strata transparent oily liquid is intermediate II, and total mass is 22.7g, yield nearly 100%.
12C, getting 7.12g ditane is dissolved in the there-necked flask that contains 50ml methylene dichloride, under normal temperature, add 12.6g aluminum trichloride (anhydrous) in batches, after be cooled to-5-0 DEG C, drip the dichloromethane solution 50ml containing intermediate II 22.7g, dropwise the rear 30 DEG C of insulation continuation reaction 3h that are naturally warming up to, after soaking time completes, material is splashed in 200ml water, stir, stratification, water is used respectively twice of 50ml dichloromethane extraction, merge organic phase, wash secondary with 50ml respectively, dried over sodium sulfate, after desolvation, obtain intermediate III 21.6g, yield 79%, intermediate III is directly carried out the next step without purifying.
The synthetic method of 12D, 12E and 1D, 1E are similar, finally obtain target 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 example 1-12 by product boiling point after structural compounds photodissociation, result from table five: no matter be that aryl ketones by product or the boiling point of alkyl ketone by product are all greatly improved than the boiling point of by product after conventional hydroxyalkyl ketone photoinitiator cracking in table two after cracking, even after the photodissociation of some product, the boiling point of by-product has exceeded 250 DEG C, 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, synthesize the part of compounds the present invention relates to, their structure and name are listed in table six: after the cracking of compound described in table six, aromatic aldehyde by product and alkyl ketone by product are identical with table five, so the compound in table six has low VOC or even VOC free emission performance equally
Table six part of compounds of the present invention
Be similar to the similar preparation method of embodiment 12, synthesized the compound of structure as shown in Table 7, this series compound also can be used as ultraviolet initiator.After the cracking of compound described in table seven, aromatic aldehyde by product and alkyl ketone by product atmospheric boiling point are all more than 250 DEG C, so the compound in table seven has low VOC or even VOC free emission performance.
Table seven part of compounds of the present invention
Claims (7)
1. reduce until the polyfunctional group alcohol ketone photoinitiator of elimination VOC discharge is characterized in that, the chemical structure of described light trigger is suc as formula shown in I or II:
Wherein, I or II must meet following five conditions simultaneously:
(1) n is integer 2,3 or 4;
(2) Ar is substituted or non-substituted aryl, Ar
1for one of following polyaromatic:
; The feature of above-mentioned substituted or non-substituted aryl and polyaromatic is that formed its atmospheric boiling point of aromatic aldehyde is greater than 179 DEG C;
Described non-substituted aryl is including but not limited to eight yuan or eight yuan of above monocyclic aryl, fused ring aryl, assorted monocyclic aryl and assorted polyaromatics;
Described substituted aryl is including but not limited to all kinds of monosubstituted and/or polysubstituted phenyl; Substituted radical is any one of following group: phenyl, halogen, C
1-C
12alkyl, C
5-C
6cycloalkyl ,-OH ,-OM
1,-SH ,-OM
1oH, – SM
1, – SOM
1,-SO
2m
1, – SO
2nH (C
1-C
4alkyl), – NM
2m
3huo – NHCOM
1; Wherein M
1, M
2and M
3for C
1-C
12hydrocarbyl group;
(3) R, R ＇ are independently the C of straight or branched separately
1-C
12alkyl, this alkyl be not substituted or 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 after the polynary halides dehalogenation of one of following structure;
(5), while being constructed as follows the compound of alkyl ketone structure by R, R ＇, Z, its atmospheric boiling point is greater than 155 DEG C:
2. reduce according to claim 1 until the polyfunctional group alcohol ketone photoinitiator of elimination VOC discharge is characterized in that, described non-substituted aryl is naphthyl, fluorenyl or carbazyl.
3. reduce according to claim 1 until the polyfunctional group alcohol ketone photoinitiator of elimination VOC discharge is characterized in that the phenyl that described substituted aryl is replaced by following group: phenyl, halogen, C
1-C
12alkyl ,-OM
1, – SM
1huo – NM
2m
3; Wherein M
1, M
2and M
3for C
1-C
12hydrocarbyl group.
4. reduce according to claim 1 until the polyfunctional group alcohol ketone photoinitiator of elimination VOC discharge is characterized in that, when described R, R ＇ are substituted alkyl, replaced by following group: C
1-C
4alkoxyl group, C
5-C
6cycloalkyl, heterocyclic radical, phenoxy group, halogen or benzene.
5. described in claim 1, reduce until the polyfunctional group alcohol ketone photoinitiator of elimination VOC discharge is characterized in that, described light trigger specifically comprises following compound:
1,10-dibiphenylyl-2,9-dihydroxyl-2,9-dimethyl nonane-1,10-diketone,
2,9-dihydroxyl-1,10-bis-(1,3,5-trimethylammonium) phenyl-2,9-dimethyl decane-1,10-diketone,
2,9-dihydroxyl-1,10-docosyl phenyl-2,9-dimethyl decane-1,10-diketone,
2,9-dihydroxyl-1,10-bis-(4-methoxyl group) phenyl-2,9-dimethyl decane-1,10-diketone,
2,9-dihydroxyl-1,10-bis-(2,4-dichloro) phenyl-2,9-dimethyl decane-1,10-diketone,
2,9-dihydroxyl-1,10-bis-(4-hydroxy ethoxy) phenyl-2,9-dimethyl decane-1,10-diketone,
3,3'-(Isosorbide-5-Nitrae-phenylene) two (2-hydroxyl-1-xenyl-2-methylpropane-1-ketone),
3,3'-(hexanaphthene-Isosorbide-5-Nitrae-bis-base) 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''-(1,3,5-phenylene) three (2-hydroxyl-1-xenyl-2-methylpropane-1-ketone),
2,6-dihydroxyl-4,4-bis-(2-hydroxyl-1-xenyl-2-methylpropane-1-ketone)-2,6-dimethyl-1,7-dibiphenylyl heptane-1,7-diketone,
2-hydroxyl-1-(4-(4-(2-hydroxy-2-methyl myristoyl) phenmethyl) phenyl)-2-methyl pentadecane-1-ketone,
3,3'-(Isosorbide-5-Nitrae-phenylene) two (2-hydroxyl-1-(1，3，5-trimethyl-benzene base)-2-methylpropane-1-ketone),
3,3'-(Isosorbide-5-Nitrae-phenylene) two (2-hydroxyl-1-(4-dodecylphenyl)-2-methylpropane-1-ketone),
3,3'-(Isosorbide-5-Nitrae-phenylene) two (2-hydroxyl-1-(4-methoxyphenyl)-2-methylpropane-1-ketone),
3,3'-(Isosorbide-5-Nitrae-phenylene) two (2-hydroxyl-1-(2,4 dichloro benzene base)-2-methylpropane-1-ketone),
3,3'-(Isosorbide-5-Nitrae-phenylene) two (2-hydroxyl-1-(4-hydroxy ethoxy phenyl)-2-methylpropane-1-ketone),
3,3'-(hexanaphthene-Isosorbide-5-Nitrae-bis-base) two (2-hydroxyl-1-(1,3,5-trimethylammonium) phenyl-2-methylpropane-1-ketone),
3,3'-(hexanaphthene-Isosorbide-5-Nitrae-bis-base) two (2-hydroxyl-1-(4-dodecyl) phenyl-2-methylpropane-1-ketone),
3,3'-(hexanaphthene-Isosorbide-5-Nitrae-bis-base) two (2-hydroxyl-1-(4-methoxyl group) phenyl-2-methylpropane-1-ketone),
3,3'-(hexanaphthene-Isosorbide-5-Nitrae-bis-base) two (2-hydroxyl-1-(2,4-dichloro) phenyl-2-methylpropane-1-ketone),
3,3'-(hexanaphthene-Isosorbide-5-Nitrae-bis-base) 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-(1,3,5-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-(2,4-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''-(1,3,5-phenylene) three (2-hydroxyl-1-(1,3,5-trimethylammonium) phenyl-2-methylpropane-1-ketone),
3,3', 3''-(1,3,5-phenylene) three (2-hydroxyl-1-(4-dodecyl) phenyl-2-methylpropane-1-ketone),
3,3', 3''-(1,3,5-phenylene) three (2-hydroxyl-1-(4-methoxyl group) phenyl-2-methylpropane-1-ketone),
3,3', 3''-(1,3,5-phenylene) three (2-hydroxyl-1-(2,4-dichloro) phenyl-2-methylpropane-1-ketone),
3,3', 3''-(1,3,5-phenylene) three (2-hydroxyl-1-(4-hydroxy ethoxy) phenyl-2-methylpropane-1-ketone),
2,6-dihydroxyl-4,4-bis-(2-hydroxyl-1-mesitylene base-2-methylpropane-1-ketone)-2,6-dimethyl-1,7-dibiphenylyl heptane-1,7-diketone,
2,6-dihydroxyl-4,4-bis-(2-hydroxyl-1-(4-dodecyl) phenyl-2-methylpropane-1-ketone)-2,6-dimethyl-1,7-dibiphenylyl heptane-1,7-diketone,
2,6-dihydroxyl-4,4-bis-(2-hydroxyl-1-(4-methoxyl group) phenyl-2-methylpropane-1-ketone)-2,6-dimethyl-1,7-dibiphenylyl heptane-1,7-diketone,
2,6-dihydroxyl-4,4-bis-(2-hydroxyl-1-(2,4-dichloro) phenyl-2-methylpropane-1-ketone)-2,6-dimethyl-1,7-dibiphenylyl heptane-1,7-diketone,
2,6-dihydroxyl-4,4-bis-(2-hydroxyl-1-(4-hydroxy ethoxy) phenyl-2-methylpropane-1-ketone)-2,6-dimethyl-1,7-dibiphenylyl heptane-1,7-diketone,
2-hydroxyl-1-(4-(4-(2-hydroxy-2-methyl myristoyl) phenoxy group) the phenyl)-2-methyl tetradecane-1-ketone,
1,1'-(sulfo-two (4,1-phenylene)) two (the 2-hydroxy-2-methyl tetradecane-1-ketone),
1,1'-((methyl azane two bases) two (4,1-phenylene)) two (the 2-hydroxy-2-methyl tetradecane-1-ketone),
1,1'-(9-ethyl-9H-carbazole-3,6-bis-bases) two (the 2-hydroxy-2-methyl tetradecane-1-ketone),
1,1'-(carbonyl diurethane (3,1-phenylene)) two (the 2-hydroxy-2-methyl tetradecane-1-ketone),
1,1', 1''-(first three bases three (benzene-4,1-bis-bases)) three (the 2-hydroxy-2-methyl tetradecane-1-ketone).
6. shown in the described I formula of one of preparation claim 1-5, reduce until the method for the polyfunctional group alcohol ketone photoinitiator of elimination volatile organic compounds discharge is characterized in that, prepare target compound by following five step reactions steps:
A, the polynary substituted carboxylic acid that first preparation contains α-hydrogen atom:
B, the polynary replacement carboxylic acid halides of being prepared by above-mentioned polynary substituted carboxylic acid:
In formula, X is halogen;
C, prepare polynary aryl ketones by above-mentioned polynary replacement carboxylic acid halides by friedel-crafts reaction:
D, the polynary halogenated aryl ketone of being prepared by above-mentioned polynary aryl ketones:
In formula, X is halogen;
E, prepare multi-hydroxy ketone by the aryl ketones of polynary halo:
Can make target compound by above-mentioned five step reactions steps.
According to claim 6 the reduction shown in formula I until eliminate the preparation method of the polyfunctional group alcohol ketone photoinitiator of VOC discharge, it is characterized in that, described steps A, the method for the polycarboxylic acid that preparation contains α-hydrogen atom is diethyl malonate, concrete steps are:
Wherein: X is halogen, ZXn is polynary halides, and the meaning of R is identical with formula I.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110338097.3A CN102504054B (en) | 2011-11-01 | 2011-11-01 | Hydroxy-ketone photoinitiator containing multiple functional groups for reducing and eliminating VOC (volatile organic compounds) emission |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110338097.3A CN102504054B (en) | 2011-11-01 | 2011-11-01 | Hydroxy-ketone photoinitiator containing multiple functional groups for reducing and eliminating VOC (volatile organic compounds) emission |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102504054A CN102504054A (en) | 2012-06-20 |
| CN102504054B true CN102504054B (en) | 2014-07-02 |
Family
ID=46216193
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201110338097.3A Active CN102504054B (en) | 2011-11-01 | 2011-11-01 | Hydroxy-ketone photoinitiator containing multiple functional groups for reducing and eliminating VOC (volatile organic compounds) emission |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102504054B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| 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 |
-
2011
- 2011-11-01 CN CN201110338097.3A patent/CN102504054B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| 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 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102504054A (en) | 2012-06-20 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Streitwieser, Jr et al. | Kinetics and isotope effects in solvolyses of ethyl trifluoromethanesulfonate | |
| CN106883114B (en) | A kind of fluorenes class polyfunctionality photoinitiator and its preparation and application | |
| CN101412670B (en) | Method for synthesizing loxoprofen sodium | |
| CN102504054B (en) | Hydroxy-ketone photoinitiator containing multiple functional groups for reducing and eliminating VOC (volatile organic compounds) emission | |
| WO2012122747A1 (en) | A method for preparing 2,5-dimethylphenylacetic acid | |
| CN109879785A (en) | A kind of preparation method of eight bromines S ether | |
| CN103601628B (en) | Contraposition or position functionalization aromatic ketone compounds, its preparation method and Photoepolymerizationinitiater initiater thereof | |
| JPS63119434A (en) | 3-bromo-4-fluoro-benzaldehyde acetal and manufacture | |
| CN111138260A (en) | Preparation method of α -hydroxyketone bifunctional photoinitiator | |
| CN102417553B (en) | Hydroxyalkyl aryl ketone photoinitiator capable of reducing volatile organic compound (VOC) discharge until elimination of VOC discharge | |
| CN107556155B (en) | A kind of method of the bis- bromine compounds of synthesis α, β- | |
| CN103058984B (en) | Synthesis method of watermelon ketone | |
| CN105566368A (en) | Synthesis method of N-substituted piperidine-4-borate | |
| CN101684067B (en) | Clean production method of antioxidant 1790 intermediate | |
| CN108358871B (en) | Synthetic method of 2-benzyl-2-dimethylamino-1- (4-morpholinylphenyl) butanone | |
| Eliel et al. | Alkylations with substituted furfurylamines | |
| CN101781205B (en) | Method for synthesizing substitutional crylic acid phenyl ester | |
| Miura et al. | Synthesis, x-ray analysis, and acidolysis of exo-and endo-1-methylindene ozonides | |
| CN101781161B (en) | Method for preparing trifluoromethyl styrene compound | |
| CN104892345B (en) | A kind of method synthesizing n-propylbenzene | |
| CN107628925A (en) | A kind of preparation method of 2 phenyl halogenation methylbenzene and its derivative | |
| CN110357772A (en) | A kind of preparation method of pair of benzene butoxybenzoic acid | |
| CN100572346C (en) | Prepare the method for fulvene compound and the method for this compound ansa-metallocene compounds of use | |
| JPS61215378A (en) | Production of 2-phenylbenzotriazole | |
| JP5461037B2 (en) | Method for producing bromine-containing fluorene compound |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |