CN100569731C - Phenyl benzophenone derivates and as the purposes of light trigger - Google Patents
Phenyl benzophenone derivates and as the purposes of light trigger Download PDFInfo
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- CN100569731C CN100569731C CNB2007100908219A CN200710090821A CN100569731C CN 100569731 C CN100569731 C CN 100569731C CN B2007100908219 A CNB2007100908219 A CN B2007100908219A CN 200710090821 A CN200710090821 A CN 200710090821A CN 100569731 C CN100569731 C CN 100569731C
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Abstract
The invention provides the compound shown in the formula (I) and as the purposes of light trigger, (seeing top right plot) wherein: A is O, and G is H, x=1; Perhaps, G is the residue of polyol, and the hydroxyl value in the described polyol is N, and 2≤N≤6; X is an integer, and 2≤x≤N; A represents the group of formula (seeing the bottom right formula) independently of each other, wherein: R
1And R
2One of represent hydrogen atom, another represents hydrogen atom, methyl or ethyl; A is 1 or 2; B is 4 or 5; Y is from 1 to 10 integer.
Description
Technical field
The phenyl benzophenone derivates of a class macromoleization involved in the present invention.This derivative can be used as light trigger, especially for the varnish of photocuring, printing-ink etc.The present invention also provides and comprises the radiation-curable composition of at least a compound of the present invention as light trigger.
Background technology
The light trigger that is used for lacquer formulation need possess good curing speed, particularly surface of good curing activity, low smell, low yellowness factor and good solubleness.In addition, along with the human consumer to external compound polluted responsive day by day in the food, be to observe the following legislation requirement that may formulate, the migration of compound with also should be as far as possible little by external agency dissolved tendency.The commercial goods light trigger more and more is difficult to satisfy above every requirement at present.
At present, benzophenone remains ultraviolet ray (UV) and solidifies the most widely used light trigger of overprint varnish zhe, and is simultaneously cheap again because its surface cure is good, solubleness is big, obtains easily.But the benzophenone smell is strong, and as easy as rolling off a log from printed matter the migration and be dissolved among the food.
As everyone knows, macromole benzophenone derivates and polyfunctional benzophenone derivates can be made into some low smells, be not easy to occur to move and the product of dissolved phenomenon, but these products have the low shortcoming of effective component content, and and then cause curing speed lower.
This shows, to have high functionality, good solubility arranged in formulation for coating material, height reactive behavior, solidified coating, migration and the dissolved tendency that can produce extremely low smell be significantly less than most of light triggers that have benzophenone compounds now and exist current demand.
We find that now a class meets the The compounds of this invention of above-mentioned requirements.The multifunctional character of this compounds makes it keep high relatively every gram functionality, and its macromole core group makes it have high solubleness in the ultraviolet curing prescription.The unit weight reactive behavior of light trigger is of crucial importance in ultra-violet curing.If a kind of reactive behavior of light trigger is lower than benzophenone, can strengthen the curing speed of consumption, but effect is limited to keep filling a prescription.In addition, after concentration surpassed 10～12%, the non-acrylate official can material or is demonstrated the character of softening agent, perhaps reduces the cross-linking density of cured film, so that influences its mechanical property.The compounds of this invention has not only overcome the above-mentioned defective of benzophenone and other existing light trigger, have smell extremely low, in ultraviolet curing prescription solubleness height, migration and by the little advantage of external agency tendency, and, in some cases, its unit weight reactive behavior almost is equivalent to benzophenone itself, in most of the cases, its reactive behavior is higher than normally used benzophenone surrogate.
Summary of the invention
The invention provides the compound shown in the formula (I),
Wherein,
A is O, and G is H, x=1;
Perhaps,
G is the residue of polyol, and the hydroxyl value in the described polyol is N, and 2≤N≤6;
X is an integer, and 2≤x≤N;
A represents the group of following formula independently of each other:
Or
Wherein:
Radicals R
1And R
2One of represent hydrogen atom; Another group is represented hydrogen atom, methyl or ethyl;
A is 1 or 2;
B is 4 or 5;
Y is from 1 to 10 integer.
Consider accessibility and economy, often also the multiple compound that meets formula (I) definition is used in the practice.Therefore, the present invention also provides a kind of composition, it is characterized in that said composition is made up of with arbitrary proportion two or more compound of formula (I).
The present invention also provides a kind of light trigger, and this light trigger contains the compound of at least a formula (I).In addition, the present invention also provides the purposes of the compound of formula (I) as light trigger.
In addition, the present invention also provides a kind of energy-curable liquid composition, and said composition contains following compositions:
Polymerisable composition wherein comprises a kind of ethylenically unsaturated monomer or oligomer at least;
Light trigger of the present invention.
The present invention also provides energy-curable liquid composition of the present invention is placed under the radiation, especially under the ultraviolet radiation, prepares the method for cured polymer.
Embodiment
For simplicity, formula of the present invention (I) compound is expressed as G-(A-COCH
2O-PBZ)
x(PBZ represents phenyl benzophenone); Will be except that (COCH
2O-PBZ)
xOutside part be expressed as G-(A-)
x, and be called the core of this compound.
In formula of the present invention (I) compound, the Sauerstoffatom that is connected on the phenyl of phenyl benzophenone can be connected on the optional position of phenyl.Consider that the being easy to get property of raw material and synthetic are convenient, preferred described Sauerstoffatom is connected on the ortho position or contraposition for benzophenone.The difference of link position is to the character of compound, and especially the character as light trigger does not have materially affect.
In formula of the present invention (I) compound, preferred A represents formula
Group; More preferably A representative
Or
A also can be
Or
Group.
In formula of the present invention (I) compound, because therefore x can exist a plurality of-A-group in this case more than or equal to 2, these groups are independently of one another, and promptly they can be the same or different, and the value of a wherein, b, y also can be identical or different.
The core G-of compound of the present invention (A-)
xGroup has great influence to the character of this compound.According to the present invention to the definition of formula (I) compound, G-(A-)
xThe polyethers and/or the polyester segment that contain one or more low polymerization degrees in the group, this makes described compound often for liquid, helps it to dissolve in formulation for coating material.Structural similitude but the compound that do not contain above-mentioned polyethers and/or polyester segment often because its for solid and/or in coating composition soluble can't the use.But core G-(A-)
xMolecular weight can not be too high, generally be not more than 1200, preferably be not more than 800, cross high molecular and make the unit weight photoinitiator levels too low.
Preferred G is the residue of ethylene glycol, propylene glycol, butyleneglycol, glycerol, TriMethylolPropane(TMP), ditrimethylolpropane, tetramethylolmethane or dipentaerythritol.
In this manual, " residue of polyol " or " alcohol residue " refers to one or more hydroxyls in polyol or the alcohol and loses remaining group after the hydrogen atom.For example, CH
2OHCH
2The residue of OH is CH
2OHCH
2O-or-OCH
2CH
2O-.In described polyol or alcohol, except hydroxyl, also can contain other functional group, as long as these functional groups do not produce substantial negative impact to the synthetic or use of The compounds of this invention.
As x in less than polyol G during contained hydroxyl value, compound of the present invention contains free hydroxyl group.When needing, perhaps The compounds of this invention is when preparing in the presence of acid, and these free hydroxyl groups can be esterified.Character to the ester that makes thus there is no particular restriction, but the preferably fatty acid ester of lower molecular weight, for example C
2-C
6Alkanoates.The example of such ester comprises acetic ester, propionic ester, butyric ester and valerate.
When the The compounds of this invention for preparing in to following embodiment carries out test analysis, digital a, b in the above-mentioned molecular formula that records and y may not be integers, this is because in the preparation of described compound, when the raw material that adopts was not the simplification compound, the product that obtains was the some kinds of mixtures with compound of formula (I) general formula.Certainly, with regard to each individual molecule of described product, a, b and y are integers, and can isolate single compound separately, and it will be appreciated by those skilled in the art that when using single raw material, can make the simplification compound, but what often adopt in actual applications, is the mixture of these compounds.
Compound of the present invention can adopt the well-known method of this compounds of preparation to be prepared, and selected definite synthetic route and reaction conditions depend on the compound that will prepare.
For example; The compounds of this invention can be by with carrying out benzoylation to the phenyl phenoxy acetic acid and obtain (I-1) or (I-2) shown in adjacent phenyl phenoxy acetic acid shown in the formula (II) or the formula (III); core compound esterification with formula (IV) is prepared then, and the A in this core compound, x and G are as mentioned above.
(HA)
X-G (IV)
Reaction is preferably carried out under the condition that solvent exists, and the character of solvent place not essential to the present invention is as long as it has no adverse effects to reagent or reaction.The solvent that is fit to comprises: alkane, for example hexanaphthene etc.; Aromatic hydrocarbons, for example benzene, toluene or dimethylbenzene etc.
Reaction is for example carried out under the existence of sulfonic acid (for example tosic acid or methylsulfonic acid), mineral acid (for example sulfuric acid, hydrochloric acid or polyphosphoric acid) or Lewis acid (for example boron trifluoride or organic titanate) preferably at an acidic catalyst.
Temperature of reaction can change in quite on a large scale, and this depends on the condition of reaction and the character of reagent and solvent, as long as the water that temperature is high enough to remove in the reaction process to be produced gets final product to guarantee that reaction is finished.We find to react the most convenient usually under near the reaction mixture refluxed temperature.The reaction required time has very big difference, and this depends primarily on temperature of reaction.Under above-mentioned optimal conditions, only need reaction 2 to 20 hours usually.
After reaction was finished, available ordinary method was carried out aftertreatment, and for example water and/or soda lye wash mixture are dried, and solvent evaporated under reduced pressure obtains product then.
The compounds of this invention is especially suitable for use as light trigger, for example in the varnish of photocuring or printing ink as light trigger.But they also can be as light trigger in many other energy-curable liquid compositions.
Adopt the energy-curable composition of The compounds of this invention to generally include at least a radiation curable monomer and/or oligomer, The compounds of this invention, and can choose wantonly and also comprise a kind of reactive thinner.With regard to printing-ink, described composition also comprises colorant, i.e. pigment.Radiation curable monomer or oligomer be alefinically unsaturated compounds preferably, is generally acrylate oligomer or acrylate monomer.The acrylate oligomer that is fit to comprises: aliphatics or aromatics propenoic methyl carbamate, polyether acrylate, polyester acrylate and epoxy acrylate (for example outer bisphenol A epoxy acrylate).The acrylate monomer that is fit to comprises: hexylene glycol double methacrylate, Viscoat 295, ditrimethylolpropane tetraacrylate, double pentaerythritol C5 methacrylate, polyether acrylate (for example ethoxylated trimethylolpropane triacrylate, the glycerol base third oxidation triacrylate, ethoxylation tetramethylol methane tetraacrylate), and epoxy acrylate (as the Ebcryl150 of USB company), and diol acrylate (for example tri-propanediol diacrylate).
Simultaneously, energy-curable composition of the present invention preferably comprises a kind of synergistic agent at least, for example a kind of amino acrylates or a kind of dimethylaminobenzoic acid ester.With regard to printing-ink, synergistic agent is the dimethylaminobenzoic acid ester preferably, and with regard to varnish, synergistic agent is amino acrylates preferably.Some printing ink for example is used for the printing ink of flexographic printing purposes, can contain above-mentioned two kinds of dissimilar synergistic agent.
What of radiation curable monomer or oligomer, light trigger, synergistic agent and optional colorant consumption are different because of the type of varnish or printing ink, the concrete equipment and the purposes that are used to apply.But under typical situation, it is 2% to 20% of composition total weight that light trigger adds the synergistic agent consumption.
Formula (I) compound except the above composition, also comprises pigment, wax, stablizer and auxiliary rheological agents usually when being used for varnish or printing ink as light trigger.
The present invention can be further described with following indefiniteness embodiment.In the listed in an embodiment structural formula, n represents the polymerization degree, and it can roughly calculate that the value of a plurality of n in the same structural formula can be different from the molecular weight of compound.
Comparing embodiment
Place 2500 milliliters of toluene that contain 3.0 gram Catalyzed by p-Toluenesulfonic Acid agent to carry out azeotropic backflow 11 hours 179.2 gram (0.7 mole) 4-carboxyl methoxy benzophenones and 87.5 gram (0.35 mole) polytetrahydrofurans (molecular-weight average 250).Solution washs twice with 500 milliliters of 0.1M aqueous sodium hydroxide washes subsequently, uses 500 ml deionized water washed twice again.With azeotropic method solution is carried out the drying back then and under vacuum, remove all solvents, obtain the shallow straw yellow liquid of 244.6 grams with rotary evaporator.
Embodiment one
The preparation of adjacent phenyl phenoxy acetic acid (II):
Get a 250ml four-hole bottle, 68.4g (0.72mol) Mono Chloro Acetic Acid is dissolved in the 60ml water, place the low temperature bath to be cooled to 0 ℃, take by weighing 96.0g (0.72mol) 30% sodium hydroxide solution by dropping funnel to wherein dripping, keep dropping temperature≤5 ℃, place the sodium chloroacetate solution low temperature that obtains stand-by after dropwising.
In the 1000ml four-hole bottle 102.0g (0.60mol) orthoxenol is dissolved in the 80ml water, stirring at normal temperature takes by weighing 86.0g (0.645mol) 30% sodium hydroxide solution and slowly adds, obtain little brown clear liquid, dropwise, reflux makes sodium-o-phenyl phenolate.
The above-mentioned sodium chloroacetate solution for preparing is dripped in above-mentioned sodium-o-phenyl phenolate solution by dropping funnel, keep reaction solution to reflux, 4-5h dropwises, and continues backflow 3h.
240ml water is joined in the reaction solution, stir 10min, add 100ml toluene again, beginning feeds carbon dioxide in reaction flask, pH value=7.5 to reaction solution stop to stir, solution is transferred to layering in the separating funnel, tells water, uses 2 * 100ml toluene extraction unreacted orthoxenol completely again.
The 70ml concentrated hydrochloric acid is added drop-wise to aqueous phase by dropping funnel, keeps dropping temperature≤35 ℃, the solid granule of separating out white gradually.
Suction filtration is dried, and obtains the adjacent phenyl phenoxy acetic acid of 100.0g white, yield 73.0%.Orthoxenol in the toluene extraction liquid can drop in the reaction again.
HPLC purity assay 98.5%; Fusing point: 102.0-104.0 ℃.
Embodiment two
The preparation of 2-(4-benzoyl phenyl)-phenoxy acetic acid (I-1):
In the four-hole bottle of 250ml, add aluminum chloride 28.5g (0.21mol), 1,2-ethylene dichloride 60ml; Stir, cool off with tap water; Connect the hydrogen chloride absorption device; Add adjacent phenyl phenoxy acetic acid (II) 22.8g (0.1mol) of embodiment one preparation, temperature is controlled at 20 ℃-30 ℃.
Drip Benzoyl chloride 15.5g (0.11mol), rate of addition remains between 20 ℃-30 ℃ temperature of reaction; Begin after dripping to be warming up between 50 ℃-55 ℃, keep this temperature to stir 6 hours.
Add concentrated hydrochloric acid 50ml in the 500ml four-hole bottle, water 100ml, ice bath are cooled to about 0 ℃, and above-mentioned reaction solution is added drop-wise in the hydrochloric acid soln, keep stirring 1h between 25 ℃-40 ℃, are cooled to-10 ℃ again, filter; Drain; Filter cake is drained with the water washing of 2 * 30ml; Wet product oven dry back is a pale powder, heavy 27.5g, yield 83%.
HPLC analyzes content 98.2%, fusing point: 170-171 ℃; Ultimate analysis C
21H
16O
4: C75.70% (theoretical value 75.89%); H 4.90% (theoretical value 4.85%).
1H-NMR：3.71ppm(s，1H，COOH)4.77ppm(s，2H，ArOCH
2COO)；6.88-7.86ppm(m，13H，Ar-)。
Embodiment three
Get a 1000ml four-hole bottle, place 200 milliliters of toluene to carry out azeotropic 23.3 gram (0.07mol) Compound I-1,8.7 gram (0.035mol) polytetrahydrofurans (molecular-weight average 250) and 0.3 gram Catalyzed by p-Toluenesulfonic Acid agent and refluxed 5 hours.Reaction solution is used 50 ml deionized water washed twice again with 50 milliliters of 0.1M aqueous sodium carbonate washed twice.Reflux solution and tell moisture content with water trap is removed toluene on rotatory evaporator then, draws the light yellow dope of 29.3 grams, yield 96.3%.The HPLC analytical results: target product content adds up to 98.3%.
1H-NMR：1.59-1.74ppm(m，7.2H，CH
2CH
2)；3.36ppm(m，4.7H，CH
2OCH
2)；4.19-4.23ppm(t，2H，COOCH
2)；4.71ppm(S，2H，ArOCH
2COO)；6.88-7.86ppm(m，13H，Ar-)。
Embodiment four
Get a 1000ml four-hole bottle, place 200 milliliters of toluene to carry out azeotropic 34.9 gram (0.105mol) Compound I-1,10.0 gram (0.05mol) polyoxyethylene glycol (molecular-weight average 200) and 0.4 gram tosic acid and refluxed 5.5 hours.Reaction solution is used 100 ml deionized water washed twice again with 100 milliliters of 0.1M aqueous sodium carbonate washed twice.Spend the night with 5 gram anhydrous sodium sulfate dryings then, filter the back and remove toluene, draw the light yellow high viscosity oily liquid of 39.5 grams, yield 97.3% with Rotary Evaporators.The HPLC analytical results: target compound content adds up to 98.5%.
1H-NMR：3.66-3.76ppm(m，8H，CH
2OCH
2)；4.30-4.33ppm(t，2H，COOCH
2)；4.71ppm(S，2H，ArOCH
2COO)；6.88-7.86ppm(m，13H，Ar-)。
Embodiment five
Get a 1000ml four-hole bottle, place 200 milliliters of toluene to carry out azeotropic 26.7 gram (0.08mol) Compound I-1,11.5 gram (0.02mol) ethoxylation tetramethylolmethanes (molecular-weight average 576) and 0.5 gram tosic acid and refluxed 8 hours.Reaction solution is used 100 ml deionized water washed twice again with 100 milliliters of 0.1M aqueous sodium carbonate washed twice.Spend the night with anhydrous sodium sulfate drying then, filter the back and on Rotary Evaporators, remove toluene, get light yellow thick liquid 35.5 grams, yield 96.5%.The HPLC analytical results: target compound content adds up to 98.1%.
1H-NMR：3.0ppm(m，2H，C-CH
2O)；3.40-3.83ppm(m，8H，CH
2O)；4.30-4.43ppm(t，2H，COOCH
2)；4.71ppm(S，2H，ArOCH
2COO)；6.88-7.86ppm(m，13H，Ar-)。
Embodiment six
Get a 1000ml four-hole bottle, place 200 milliliters of toluene to carry out azeotropic 33.2 gram (0.1mol) Compound I-1,15.7 gram (0.025mol) pentaerythritol propoxylate (molecular-weight average 629) and 0.8 gram Catalyzed by p-Toluenesulfonic Acid agent and refluxed 6 hours.Reaction solution is used 100 ml deionized water washed twice again with 100 milliliters of 0.1M aqueous sodium carbonate washed twice.Spend the night with 5 gram anhydrous magnesium sulfate dryings then, filter the back and on Rotary Evaporators, remove toluene, get light yellow viscous liquid 45.2 grams, yield 96%.The HPLC analytical results: target compound content adds up to 98.0%.
Embodiment seven
Preparation to phenyl phenoxy acetic acid (III):
Get a 250ml four-hole bottle, 68.4g (0.72mol) Mono Chloro Acetic Acid is dissolved in the 60ml water, place the low temperature bath to be cooled to 0 ℃, take by weighing 96.0g (0.72mol) 30% sodium hydroxide solution by dropping funnel to wherein dripping, keep dropping temperature≤5 ℃, place the sodium chloroacetate solution low temperature that obtains stand-by after dropwising.
In the 1000ml four-hole bottle 102.0g (0.60mol) p-phenyl phenol is dissolved in the 80ml water, stirring at normal temperature takes by weighing 86.0g (0.645mol) 30% sodium hydroxide solution and slowly adds, obtain little brown clear liquid, dropwise, reflux makes p-phenyl phenol sodium.
The above-mentioned sodium chloroacetate solution for preparing is dripped in above-mentioned p-phenyl phenol sodium solution by dropping funnel, keep reaction solution to reflux, 4-5h dropwises, and continues backflow 3h.
240ml water is joined in the reaction solution, stir 10min, add 100ml toluene again, beginning feeds carbon dioxide in reaction flask, pH value=7.5 to reaction solution stop to stir, solution is transferred to layering in the separating funnel, tells water and uses 2 * 100ml toluene extraction unreacted p-phenyl phenol completely again.
The 70ml concentrated hydrochloric acid is added drop-wise to aqueous phase by dropping funnel, keeps dropping temperature≤35 ℃, the solid granule of separating out white gradually.
Suction filtration, the oven dry, obtain 98.0g white to the phenyl phenoxy acetic acid, yield 71.5%.P-phenyl phenol in the toluene extraction liquid can drop in the reaction again.
HPLC purity assay 98.8%.Fusing point: 186.4-188.3 ℃.
Embodiment eight
The preparation of 4-(4-benzoyl phenyl)-phenoxy acetic acid (I-2):
Four-hole bottle to 250ml adds aluminum chloride 28.5g (0.21mol), 1,2-ethylene dichloride 60ml; Stir, cool off with tap water; Connect the hydrogen chloride absorption device; Add embodiment seven preparations to phenyl phenoxy acetic acid (III) 22.8g (0.1mol), temperature is controlled at 20 ℃-30 ℃.
Drip Benzoyl chloride 15.5g (0.11mol), rate of addition remains between 20 ℃-30 ℃ temperature of reaction; Begin after dripping to be warming up between 50 ℃-55 ℃, keep this temperature to stir 6 hours.
Add concentrated hydrochloric acid 50ml in the 500ml four-hole bottle, water 100ml, ice bath are cooled to about 0 ℃, and above-mentioned reaction solution is added drop-wise in the hydrochloric acid soln, keep stirring 1h between 25 ℃-40 ℃, are cooled to-10 ℃ again, filter; Drain; Filter cake is drained with the water washing of 2 * 30ml; Wet product oven dry back is a pale powder, heavy 26.0g, yield 78.5%.
HPLC analyzes content 98.5%; Fusing point: 205.0-206.2 ℃.
Ultimate analysis C
21H
16O
4: C 75.70% (theoretical value 75.89%); H 4.89% (theoretical value 4.91%).
1H-NMR：4.75ppm(s，2H，ArOCH
2COO)；7.03-7.82ppm(m，13H，Ar-)。
Embodiment nine
Get a 1000ml four-hole bottle, place 200 milliliters of toluene to carry out azeotropic 23.3 gram (0.07mol) Compound I-2,8.7 gram (0.035mol) polytetrahydrofurans (molecular-weight average 250) and 0.3 gram Catalyzed by p-Toluenesulfonic Acid agent and refluxed 5 hours.Reaction solution is used 50 ml deionized water washed twice again with 50 milliliters of 0.1M aqueous sodium carbonate washed twice.Reflux solution and tell moisture content with water trap is removed toluene on rotatory evaporator then, obtains the light yellow dope of 29.0 grams, yield 95.3%.The HPLC analytical results: target compound content adds up to 98.4%.
1H-NMR：1.59-1.74ppm(m，7.2H，CH
2CH
2)；3.36ppm(m，4.7H，CH
2OCH
2)；4.19-4.23ppm(t，2H，COOCH
2)；4.69ppm(S，2H，ArOCH
2COO)；7.03-7.82ppm(m，13H，Ar-)。
Embodiment ten
Get a 1000ml four-hole bottle, place 200 milliliters of toluene to carry out azeotropic 26.7 gram (0.08mol) Compound I-2,11.5 gram (0.02mol) ethoxylation tetramethylolmethanes (molecular-weight average 576) and 0.5 gram tosic acid and refluxed 8 hours.Reaction solution is used 100 ml deionized water washed twice again with 100 milliliters of 0.1M aqueous sodium carbonate washed twice.Spend the night with anhydrous sodium sulfate drying then, filter the back and on Rotary Evaporators, remove toluene, get light yellow thick liquid 35.3 grams, yield 96.0%.The HPLC analytical results: target compound content adds up to 98.0%.
1H-NMR：3.0ppm(m，2H，C-CH
2O)；3.40-3.83ppm(m，8H，CH
2O)；4.30-4.43ppm(t，2H，COOCH
2)；4.69ppm(S，2H，ArOCH
2COO)；7.03-7.82ppm(m，13H，Ar-)。
More than the source of experiment agents useful for same sees the following form one.
Table one
| Material name | Supplier |
| Adjacent phenyl phenoxy acetic acid | Insight High Technology Co., Ltd. (Jiangsu) |
| To the phenyl phenoxy acetic acid | Insight High Technology Co., Ltd. (Jiangsu) |
| Benzoyl chloride | Beijing chemical reagents corporation |
| Aluminum chloride | Tianjin Beijing-Tianjin insecticide factory |
| 1, the 2-ethylene dichloride | Chemical plant in Zibo City's richness |
| 36% hydrochloric acid | Beijing northization fine chemicals company limited |
| 1, the 4-dioxane | Medication chemistry factory is risen in the river by Taixing City, Jiangsu Province |
| PTHF250 | BASF |
| Tosic acid | 5-linked chemical plant, Shanghai |
| Toluene | Jin Yuan chemical plant, Zhou village, Zibo City |
| 30% sodium hydroxide solution | Bohai Sea sky, Tianjin chemical industry company limited |
| Macrogol 200 | The friendly chemical plant of Beijingization |
| The ethoxylation tetramethylolmethane | Tianjin proud son of heaven chemical industry company limited |
| Pentaerythritol propoxylate | Tianjin proud son of heaven chemical industry company limited |
Embodiment 11
Curing performance relatively
Will be by the foregoing description three to six, nine and ten, and the prepared product of comparing embodiment makes corresponding ultraviolet curing varnish preparation as light trigger, also benzophenone and phenyl benzophenone made corresponding ultraviolet curing varnish preparation as light trigger in addition.The prescription of described preparation sees Table two.
Table two
| System component | Per-cent (%) |
| Light trigger | 7 |
| The amino acrylates synergistic agent (P115, UCB) | 8 |
| Epoxy acrylate oligomer (6210G, Changxing company) | 25 |
| Polyfunctional monomer, GPTA (EM2385 glycerol base propoxylation triacrylate, Changxing company) | 60 |
The varnish preparation of preparation gained being executed printing on the tinplate with the excellent spreader of 10 micro wires, is that the medium pressure mercury Jupiter is cured with 100 meters/component velocity in 60 watts/centimetre with a power.Record obtains surface of good and thoroughly solidifies number of pass times under the needed lamp.Its result is as shown in the table.
Table three
| Light trigger | The required number of pass times of completely solidified |
| Benzophenone | 4 |
| The product of comparing embodiment (V) | 5 |
| Phenyl benzophenone (PBZ) | 3 |
| The product of embodiment three (I-3) | 4 |
| The product of embodiment four (I-4) | 4 |
| The product of embodiment five (I-5) | 4 |
| The product of embodiment six (I-6) | 4 |
| The product of embodiment nine (I-7) | 4 |
| The product of embodiment ten (I-8) | 4 |
These results show that compound of the present invention is equivalent at least or near the curing speed of benzophenone with regard to curing speed.Stink after all examples solidify all is lower than benzophenone.Yellowness factor after all examples solidify is all close.
Claims (12)
1. the compound shown in the formula (I):
Be connected in the formula (I) on the phenyl ring-0-is positioned at the ortho position or the contraposition of benzophenone base;
Wherein:
A represents formula
Wherein:
R
1And R
2One of represent hydrogen atom, another represents hydrogen atom, methyl or ethyl;
A is 1 or 2;
Y is from 1 to 10 integer;
G is the residue of polyol, and wherein the hydroxyl value in the polyol is N, and 2≤N≤6;
X is an integer, and 2≤x≤N.
2. the described compound of claim 1, wherein A representative
3. the described compound of claim 1, wherein residue G-(A-)
xMolecular weight be not more than 1200.
4. the described compound of claim 1, wherein residue G-(A-)
xMolecular weight be not more than 800.
5. the described compound of claim 1, wherein G is the residue of ethylene glycol, propylene glycol, butyleneglycol, glycerol, TriMethylolPropane(TMP), ditrimethylolpropane, tetramethylolmethane or dipentaerythritol.
6. the preparation method of the compound shown in the formula (I),
Be connected in the formula (I) on the phenyl ring-O-is positioned at the ortho position or the contraposition of benzophenone base;
Its preparation method comprises: make 2-(4-benzoyl phenyl)-phenoxy acetic acid or 4-(4-benzoyl phenyl)-phenoxy acetic acid and structural formula be (HA)
xThe compound of-G carries out esterification, and wherein the definition of A, G, x is with claim 1.
7. the compound of one of claim 1-5 is as the purposes of light trigger.
8. a composition is characterized in that being made up of with arbitrary proportion the two or more compound among one of claim 1-5.
9. a light trigger is characterized in that containing at least a compound among one of claim 1-5.
10. energy-curable liquid composition is characterized in that containing following compositions:
Polymerisable composition wherein comprises a kind of ethylenically unsaturated monomers or oligomer at least;
The described light trigger of claim 9.
11. the described energy-curable liquid composition of claim 10, wherein composition is varnish or printing-ink.
12. a method for preparing the solidified polymeric composition comprises the energy-curable liquid composition in claim 10 or 11 is exposed under the ultraviolet radiation.
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| CNB2007100908219A CN100569731C (en) | 2006-08-08 | 2007-04-06 | Phenyl benzophenone derivates and as the purposes of light trigger |
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| WOPCT/CN2006/002001 | 2006-08-08 | ||
| PCT/CN2006/002001 WO2008019527A1 (en) | 2006-08-08 | 2006-08-08 | Phenyl benzophenone derivates and uses as photoinitiators |
| CNB2007100908219A CN100569731C (en) | 2006-08-08 | 2007-04-06 | Phenyl benzophenone derivates and as the purposes of light trigger |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102101896B (en) * | 2009-12-18 | 2013-03-27 | 北京英力科技发展有限公司 | Application of 2-methyl-4'-phenyl benzophenone serving as photo initiator |
| CN102260358B (en) * | 2010-05-31 | 2012-10-03 | 江苏英力科技发展有限公司 | Use of 2-methoxy-4'-benzoylbiphenyl as photoinitiator |
| CN102060673A (en) * | 2010-12-24 | 2011-05-18 | 淄博德丰化工有限公司 | Process for preparing o-phenylphenol sodium salt |
| WO2013016839A1 (en) | 2011-07-29 | 2013-02-07 | 北京英力科技发展有限公司 | Mercapto-benzophenone compounds, compositions and preparation methods thereof |
| CN102766045B (en) * | 2012-07-31 | 2014-03-05 | 惠州市华泓新材料有限公司 | Benzophenone derivative and application thereof as photoinitiator |
| CN103193900B (en) * | 2013-03-11 | 2014-12-17 | 常州大学 | Polymerizable benzophenone photoinitiator and preparation method thereof |
| CN103193899B (en) * | 2013-03-11 | 2015-07-01 | 常州大学 | Hydrogen-abstraction compound photoinitiator and preparation method thereof |
| CN106032396B (en) * | 2015-03-12 | 2019-12-03 | 北京英力科技发展有限公司 | Fluororesin and the preparation method and application thereof with photoinitiator group |
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| US5407971A (en) * | 1992-02-10 | 1995-04-18 | Minnesota Mining And Manufacturing Company | Radiation crosslinked elastomers |
| US20030073870A1 (en) * | 2001-08-29 | 2003-04-17 | Council Of Scientific & Industrial Research | Process for the preparation of phenyl ketones |
| CN1599713A (en) * | 2001-10-18 | 2005-03-23 | 科茨兄弟公开有限公司 | Multi-functional photoinitiators |
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| CN1599713A (en) * | 2001-10-18 | 2005-03-23 | 科茨兄弟公开有限公司 | Multi-functional photoinitiators |
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