CN105218372A - (4-Phenylbenzoyl) benzoic ether and the purposes as light trigger thereof - Google Patents

(4-Phenylbenzoyl) benzoic ether and the purposes as light trigger thereof Download PDF

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CN105218372A
CN105218372A CN201410311886.1A CN201410311886A CN105218372A CN 105218372 A CN105218372 A CN 105218372A CN 201410311886 A CN201410311886 A CN 201410311886A CN 105218372 A CN105218372 A CN 105218372A
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formula
compound
phenylbenzoyl
phenylformic acid
light trigger
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赵文超
李静
李家齐
邵俊峰
姚丽秀
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Yingli Science And Technology Development Co Ltd Beijing
Insight High Technology Beijing Co Ltd
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Yingli Science And Technology Development Co Ltd Beijing
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Priority to CN201410311886.1A priority Critical patent/CN105218372A/en
Priority to PCT/CN2015/077081 priority patent/WO2016000477A1/en
Publication of CN105218372A publication Critical patent/CN105218372A/en
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/08—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
    • C07C69/76—Esters of carboxylic acids having a carboxyl group bound to a carbon atom of a six-membered aromatic ring
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/46—Polymerisation initiated by wave energy or particle radiation
    • C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/32—Polymers modified by chemical after-treatment
    • C08G65/329—Polymers modified by chemical after-treatment with organic compounds
    • C08G65/331—Polymers modified by chemical after-treatment with organic compounds containing oxygen
    • C08G65/332—Polymers modified by chemical after-treatment with organic compounds containing oxygen containing carboxyl groups, or halides, or esters thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/34—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives
    • C08G65/48—Polymers modified by chemical after-treatment
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/02—Printing inks
    • C09D11/10—Printing inks based on artificial resins
    • C09D11/101—Inks specially adapted for printing processes involving curing by wave energy or particle radiation, e.g. with UV-curing following the printing
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
    • C09D163/10—Epoxy resins modified by unsaturated compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

The invention provides the compound shown in formula I and synthetic method thereof and the purposes as light trigger, wherein: A is Sauerstoffatom, or A representative formula independently of each other group; G is the residue of the polyol containing n hydroxyl, and 2≤n≤6; x 1for positive integer, and 2≤x 1≤ n, x 2for n-x 1; R is hydrogen atom, C 1-C 12alkyl acyl, aryl-acyl, C 2-C 4conjugation enoyl-.

Description

(4-Phenylbenzoyl) benzoic ether and the purposes as light trigger thereof
Technical field
The present invention relates to (4-Phenylbenzoyl) benzoic ether of a kind of macromolecular.This compound can separately or mix with other light trigger as light trigger, for preparing Photocurable composition, is specially adapted to the photocuring varnish, printing-ink etc. that require low smell, low migration.The present invention also provides and comprises at least one compound of the present invention as the photopolymerization composite of light trigger preparation containing unsaturated carbon-carbon double bond compounds.
Background technology
Light trigger for photocuring lacquer formulation needs to possess good curing speed, particularly good surface curing activity, low smell, low yellowness factor and good solubleness.In addition; along with human consumer is to compound polluted sensitivity day by day external in food; especially stricter examination criteria is had for food and medicine wrapping material; define material transport amount; many small molecular weight material are got rid of outside the inventory allowed; as benzophenone; 2-hydroxy-2-methyl-1-phenyl-1-acetone; the molecular weight of the compounds such as methyl benzoylformate is little; in composition construction and after polymerization film formation, they all likely move to its contactant or volatilize in air and pollute.So the compound for light trigger moves away from carrier accompanying by it or the tendency of being dissolved by external agency also should be as far as possible little.
Benzophenone remains ultraviolet (UV) and solidifies the most widely used light trigger of overprint varnish zhe, because its surface cure is good, solubleness is large, simultaneously cheap again, but benzophenone smell is strong, and as easy as rolling off a log migration and being dissolved among packaged food from printed matter.
At present, some macromolecular benzophenone derivates and polyfunctional benzophenone derivates have been disclosed on market or on technical information, this compounds such as disclosed in document ZL200710090821.9 and document ZL201010294407.1 has low smell, is not easy the features such as migration, but the light-initiated inefficient problem of these product ubiquities.Contriver also discloses a kind of macromole benzophenone derivates light trigger product in patent ZL201010294407, and this product also exists active lower slightly problem.If the reactive behavior of macromolecular benzophenone derivates light trigger is lower than a benzophenone, although by strengthening consumption to keep the curing speed of filling a prescription, limited efficiency; Excessive consumption can bring disadvantageous effect to cured film: reduce mechanical property etc.In addition, some macromolecular benzophenone derivates complicate fabrication process, are difficult to scale production, do not have practical value.
As can be seen here, to having height reactive behavior, in formulation for coating material, have that the smell of good solubility, solidified coating is extremely low, migration and be there is current demand by the light trigger that tendency is significantly less than most of existing benzophenone and analogue thereof.
Summary of the invention
Contriver has found a kind of compound i.e. (4-Phenylbenzoyl) benzoic ether meeting above-mentioned requirements under study for action uncannily.Effective group property of this compounds ensures that it has high initiating activity, multiple functionalizedly makes it keep the relatively high effective group content of unit weight, and its core group makes it in photopolymerization composite, have good solubleness and low migration.
The invention provides the compound shown in formula I,
Wherein,
G is the residue of polyol, and the hydroxyl value in described polyol is Integer n, and 2≤n≤6; x 1for positive integer, and 2≤x 1≤ n, x 2for n-x 1;
A is Sauerstoffatom or A representative formula independently of each other group, 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 the integer from 1 to 30;
R is hydrogen atom, C 1-C 12alkyl acyl, aryl-acyl, C 2-C 4conjugation enoyl-.
The present invention also provides a kind of light trigger, and this light trigger contains the compound of at least one formula I.In addition, the present invention also provides the purposes of compound as light trigger of formula I.
Consider accessibility and economy, often also the multiple compound meeting formula I definition is used in practice.Therefore, the present invention also provides a kind of photoinitiator composite, it is characterized in that said composition is made up of with arbitrary proportion two or more the compound of formula I.
In addition, the present invention also provides a kind of photopolymerization composite, and said composition contains following compositions:
Polymerisable composition, wherein at least comprises a kind of ethylenically unsaturated monomer or oligomer;
Light trigger of the present invention.
The present invention also provides a kind of method of being solidified by photopolymerization composite of the present invention, coats on base material by photopolymerization composite, is placed under photoirradiation, especially under ultraviolet radiation, realizes coating curing.
Except formula I, one or more mixtures of the known light trigger of other types can also be contained in the composition, and improve the additive of composition properties; Known light trigger has OmnipolBP, OmnipolTX etc. of IGM Resins Corporation; As two (p-(dimethylamino)-benzoic acid) ester of material such as polyoxyethylene glycol of polymerization promotor, the P115 of Cytec company.Add additive in the composition as matting agent, defoamer, flow agent etc., the properties of composition can be regulated.
The consumption of light trigger of the present invention accounts for the 0.1-15% of composition weight, and consumption is under normal circumstances that 1-10% can play good photopolymerization.
Prepared photopolymerization composite can be designed to be suitable for using on various substrate surface, such as paper, timber, plastics, metal, and with the normally used method coating of those skilled in the art and irradiation light, to complete solidification process.2-provided by the invention (4-Phenylbenzoyl) benzoic acid ester compounds overcome the initiating activity of benzophenone and other existing light trigger low, manufacture the deficiencies such as difficulty, have that smell is extremely low, high, the migration of solubleness and by the little advantage of external agency tendency in ultraviolet curing formula; Photocuring experimental evaluation result proves that its unit weight reaction space charge force is almost equivalent to benzophenone itself, and its reactive behavior is significantly higher than normally used benzophenone alternative, the product of such as comparing embodiment.
Embodiment
For simplicity, 4-Phenylbenzoyl phenyl in formula I of the present invention is called the effective group of photocuring, is connected in (A) x by carbonyl (-CO-) 1-G-(AR) x 2a on, and claim (A) x 1-G-(AR) x 2for the core of this compound.
In formula I of the present invention ,-the CO-A-be connected on 4-Phenylbenzoyl benzene can be connected on the optional position of phenyl, such as and 4-Phenylbenzoyl form ortho position, a position or alignment.
In formula I of the present invention, concrete A is Sauerstoffatom or representative formula group; More specifically A represention oxygen atom, group, 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 the integer from 1 to 30;
G is the residue of polyol, and the hydroxyl value in described polyol is Integer n, and 2≤n≤6; x 1for positive integer, and 2≤x 1≤ n, x 2for n-x 1;
R is hydrogen atom, C 1-C 12alkyl acyl, aryl-acyl, C 2-C 4conjugation enoyl-.
In formula I of the present invention, due to x 1can be more than or equal to the integer of 2, therefore there is multiple-A-group in this case, these groups are independent of one another, and namely they can be the same or different, and the value of a, b, y wherein also can be identical or different; Work as x 1during=n, x 2=0.
Core (A) x of compound of the present invention 1-G-(A) x 2the character of group on this compound has great impact.According to the definition of the present invention to formula I, (A) x 1-G-(A) x 2polyethers containing one or more low polymerization degree in group and/or polyester segment, this makes described compound often for liquid, contributes to it and dissolves in formulation for coating material.Group (A) x 1-G-(A) x 2molecular weight be not more than 2000, cross high molecular make unit weight photoinitiator levels 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 " residue of alcohol " refers to remaining group after polyol or alcohol lose one or more hydroxyl.Such as, HOCH 2cH 2the residue of OH is HOCH 2cH 2-or-CH 2cH 2-.In described polyol or alcohol, except hydroxyl, also other functional group can be contained, as long as these functional groups are not to synthesis or the substantial negative impact of use generation of the compounds of this invention.
Work as x 1when being less than hydroxyl value n contained in polyol G, compound of the present invention contains free hydroxyl group or these free hydroxyl groups are esterified.Particular restriction be there is no to the character of ester obtained thus, comprise the C of lower molecular weight 1-C 12fatty acid ester, C 2-C 4olefin(e) acid ester, the example of such ester comprises acetic ester, propionic ester, butyric ester, valerate or acrylate.
When the compounds of this invention prepared in following embodiment carries out test analysis, digital a, b and y in the above-mentioned molecular formula recorded may not be integers, this is due in the preparation of described compound, when the raw material adopted is not single compound, the product obtained is the several mixture with the compound of formula I general formula.Certainly, with regard to each individual molecules of described product, a, b and y are integers, and single compound can be isolated separately, and it will be appreciated by those skilled in the art that when using single polyol for raw material, single pure compound can be obtained, but what in actual applications, often adopt is the mixture of these polyol different polymerization degrees.
The compounds of this invention is by being prepared the core compound esterification of 2-(4-Phenylbenzoyl) phenylformic acid such as shown in formula II or 3-(4-Phenylbenzoyl) phenylformic acid shown in formula III and formula IV; the definition of A and G in this core compound is with A and G in type I compound, x=x 1+ x 2.
(HA) x-G(IV)
Esterification is preferably carried out in the presence of a solvent, and the character place not essential to the present invention of solvent, as long as it has no adverse effects to reagent or reaction.The solvent be applicable to comprises: alkane, such as hexanaphthene; Aromatic hydrocarbons, such as benzene, toluene or dimethylbenzene.
Esterification is selected at an acidic catalyst, such as, carries out under the existence of sulfonic acid (such as tosic acid or methylsulfonic acid), mineral acid (such as sulfuric acid, hydrochloric acid or polyphosphoric acid) or Lewis acid (such as boron trifluoride or organic titanate).
Esterification reaction temperature 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 temperature is high enough to remove the water produced in reaction process, to ensure that reaction completes.We find usually to carry out reacting the most convenient at close to reaction mixture refluxed temperature.Complete reaction required time and have very large difference, this depends primarily on temperature of reaction.Under above-mentioned optimal conditions, usually only need reaction 2 to 20 hours.
Work as x 1when to be less than in polyol G contained hydroxyl value n, above-mentioned esterification products contains free hydroxyl group, and these free hydroxyl groups are by another Esterification with hydroxy-acid group.These acid comprise acetic acid, butyric acid, acrylic or methacrylic acid.And complete esterification by the process that above-mentioned esterification is identical.
After having reacted, using conventional procedures carries out aftertreatment, and such as use water and/or soda lye wash mixture, be dried, then solvent evaporated under reduced pressure obtains product.
The compounds of this invention is especially suitable for use as light trigger, such as in the varnish or ink of photocuring as light trigger.But they also can as light trigger in other photopolymerization composites many, and consumption accounts for the 0.1%-15% of composition total weight
The Photocurable composition of the compounds of this invention is adopted to generally include at least one photo-curing monomer and/or oligomer, the compounds of this invention, and reactive thinner of can choosing any one kind of them.With regard to printing-ink, described composition also comprises colorant, i.e. pigment.Photo-curing monomer or oligomer are preferably alefinically unsaturated compounds, are generally acrylate oligomer or acrylate monomer.The acrylate oligomer be applicable to comprises: aliphatics or aromatic urethane acrylates, polyether acrylate, polyester acrylate and epoxy acrylate (such as outer bisphenol A epoxy acrylate).The acrylate monomer be applicable to comprises: hexylene glycol double methacrylate, Viscoat 295, ditrimethylolpropane tetraacrylate, double pentaerythritol C5 methacrylate, polyether acrylate (such as ethoxylated trimethylolpropane triacrylate, glycerol base third are oxidized triacrylate, ethoxylation tetramethylol methane tetraacrylate), with epoxy acrylate (Ebecryl500 as Cytec company), and diol acrylate (such as tri-propanediol diacrylate).
Meanwhile, photopolymerization composite of the present invention preferably at least comprises a kind of synergistic agent, such as a kind of amino acrylates or a kind of p-(dimethylamino)-benzoic acid ester.With regard to printing-ink, synergistic agent is preferably p-(dimethylamino)-benzoic acid ester, and with regard to varnish, synergistic agent is preferably amino acrylates.Some ink, such as, for the ink of flexographic printing applications, can containing above-mentioned two kinds of dissimilar synergistic agent.
The number of photo-curing monomer or oligomer, light trigger, synergistic agent and optional colorant consumption is because of the type of varnish or ink, different for the concrete equipment that applies and purposes.
Formula I in for varnish or ink as light trigger time, except the above composition, usually also comprise pigment, wax, stablizer and auxiliary rheological agents.
The present invention can be further described with following nonlimiting examples.In structural formula listed in an embodiment, n represents the polymerization degree, and it can roughly calculate out from the molecular weight of compound, and the value of the multiple n in same structure formula can be different.
Comparing embodiment 1
179.2g (0.7 mole) 4-Carboxymethoxybenzophenone and 87.5g (0.35 mole) polytetrahydrofuran (molecular-weight average 250) are placed in 2500 milliliters of toluene containing the agent of 3.0g Catalyzed by p-Toluenesulfonic Acid to carry out azeotropic and reflux 11 hours.Solution washes twice with 500 milliliters of 0.1M aqueous sodium hydroxide solutions subsequently, then washes twice by 500 ml deionized water.Then remove all solvents under vacuo with rotary evaporator after drying being carried out to solution with azeotropic method, obtain the shallow straw yellow liquid of 244.6g.
Comparing embodiment 2
In 500 milliliters of four-hole bottles, add 100 grams of (0.5 mole) Macrogol 200s, 82.5 grams of (1.0 moles) o-benzoyl yl benzoic acid methyl esters and sodium methylate 8g, be warmed up to 130 DEG C of stirring reactions 8 hours, reclaim methyl alcohol simultaneously.Wash with water after cooling, remove moisture under reduced pressure, obtain the two o-benzoylbenzoic acid Macrogol 200 ester (in structural formula VI, the mixture of n=4-10 compound) of 180 grams of light yellow product, total content is 98.15%, and yield is 97.4%,
Embodiment 1
2-(4-Phenylbenzoyl) benzoic preparation:
Aluminum chloride 40g (0.3mol), 1,2-ethylene dichloride 80ml is added in the four-hole bottle of 250ml; Stir, cool with cooling tank; Connect hydrogen chloride absorption device; Add phthalic anhydride 20g (0.135mol), temperature controls at-10 DEG C-0 DEG C.
Biphenyl 27.1g (0.176mol) is dissolved in the ethylene dichloride of 60ml and drops to above-mentioned reaction solution, temperature of reaction is remained between-5 DEG C-0 DEG C, keep this temperature to stir 2 hours.
In 500ml four-hole bottle, add concentrated hydrochloric acid 50ml, water 100ml, ice bath is cooled to about 0 DEG C, is added drop-wise in hydrochloric acid soln by above-mentioned reaction solution, stirs 1h, then be cooled to-10 DEG C between keeping 25 DEG C-40 DEG C, filters; Drain; The filter cake sodium hydroxide water 300ml of 2% washs 2h, drains; Wet product, with being white powder after filtering drying after 5% aqueous hydrochloric acid 300ml washing 2h, weighs 27.9g, yield 68.4%.
HPLC analyzes content 98.8%, fusing point: 226.9-228.5 DEG C; Ultimate analysis C 20h 14o 3: C79.40% (theoretical value 79.46%); H4.80% (theoretical value 4.67%).
Embodiment 2
3-(4-Phenylbenzoyl) benzoic preparation:
Aluminum chloride 28.5g (0.21mol), 1,2-ethylene dichloride 60ml is added in the four-hole bottle of 250ml; Stir, cool with tap water; Connect hydrogen chloride absorption device; Add m-phthaloyl chloride 20.5g (0.1mol), temperature controls at 0 DEG C-5 DEG C.Add biphenyl 15.5g (0.1mol) in batches, temperature of reaction is remained between 0 DEG C-5 DEG C, keep this temperature to stir 6 hours.
In 500ml four-hole bottle, add concentrated hydrochloric acid 50ml, water 100ml, ice bath is cooled to about 0 DEG C, is added drop-wise in hydrochloric acid soln by above-mentioned reaction solution, stirs 1h, then be cooled to-10 DEG C between keeping 25 DEG C-40 DEG C, filters; Drain; The filter cake water washing of 2 × 30ml, drains; Wet product is pale powder after drying, heavy 27.8g, yield 92%.
It is 98.1% that HPLC analyzes 3-(4-Phenylbenzoyl) benzoic acid content, fusing point: 199.5-207 DEG C; Ultimate analysis C 20h 14o 3: C79.35% (theoretical value 79.46%); H4.76% (theoretical value 4.67%).
The preparation of embodiment 3 polytetrahydrofuran two [2-(4-Phenylbenzoyl) phenylformic acid] ester
In 500ml four-hole bottle, 30.3g (0.1mol) compound ii, 12.5g (0.05mol) polytetrahydrofuran (molecular-weight average 250) and the agent of 0.86g Catalyzed by p-Toluenesulfonic Acid are placed in 200ml toluene and carry out azeotropic and reflux 48 hours.Reaction solution 50ml0.1M aqueous sodium carbonate washes twice, then washes twice by 50 ml deionized water.Then reflux solution divide water outlet with water trap, decompression precipitation removing toluene, uses petrol ether/ethyl acetate to carry out column chromatography by unreacted compound ii removing completely.When eluent is that petrol ether/ethyl acetate=2:1 obtains target product, draw 28.7g clear yellow viscous thing after underpressure distillation solvent, yield 67.1%.HPLC analytical results: target product content adds up to 99.0%, HPLC-MS analytical results in table 1.
Table 1 liquid chromatography-mass spectrometry result
In table
The preparation of embodiment 4 polytetrahydrofuran two [2-(4-Phenylbenzoyl) phenylformic acid] ester
According to embodiment 3 technological process, its Raw polytetrahydrofuran (molecular-weight average 250) polytetrahydrofuran (molecular-weight average 1000) replaces, obtain thick pale yellow shape liquid, yield 82%, HPLC analytical results: target compound content adds up to 98.0%.
The preparation of embodiment 5 poly(oxyethylene glycol) 400 two [2-(4-Phenylbenzoyl) phenylformic acid] ester
In 1000ml four-hole bottle, 30.3g (0.1mol) compound ii, 20.0g (0.05mol) polyoxyethylene glycol (molecular-weight average 400) and 0.86g tosic acid are placed in 200ml toluene and carry out azeotropic and reflux 48 hours.Reaction solution 100 milliliter of 5% aqueous sodium carbonate washes twice, then washes twice by 100 ml deionized water.Then spend the night with 5g anhydrous sodium sulfate drying, after filtering, decompression removing toluene, draws 46.9 grams of yellow, viscous liquid, yield 93.2%.HPLC analytical results: target compound content adds up to 98.0%. 1H-NMR:4.66ppm(m,21.8H,OCH 2CH 2O)；7.41-8.31ppm(m,26H,ArH)。
The preparation of embodiment 6 Polyethylene Glycol-600 two [2-(4-Phenylbenzoyl) phenylformic acid] ester
According to embodiment 5 technique, its Raw polyoxyethylene glycol (molecular-weight average 400) polyoxyethylene glycol (molecular-weight average 600) replaces, obtain thick pale yellow shape liquid, yield 90%, HPLC analytical results: target compound content adds up to 98.2%.
1H-NMR:4.66ppm(m,32H,OCH 2CH 2O)；7.41-8.31ppm(m,26H,ArH)。
The preparation of embodiment 7 polyethylene glycol-800 two [2-(4-Phenylbenzoyl) phenylformic acid] ester
According to embodiment 5 technique, its Raw polyoxyethylene glycol (molecular-weight average 400) polyoxyethylene glycol (molecular-weight average 800) replaces, obtain thick pale yellow shape liquid, yield 89%, HPLC analytical results: target compound content adds up to 97.6%.
1H-NMR:4.66ppm(m,44H,OCH 2CH 2O)；7.41-8.31ppm(m,26H,ArH)。
The preparation of embodiment 8 glycol ether two [2-(4-Phenylbenzoyl) phenylformic acid] ester
In 250ml four-hole bottle, 28.5g (0.09mol) compound ii, 5g (0.047mol) glycol ether and 0.8g tosic acid are placed in 100 milliliters of toluene and carry out azeotropic and reflux 54 hours.Reaction solution 100 milliliters of 0.1M aqueous sodium carbonates wash twice, then wash twice by 100 ml deionized water.Then spend the night with anhydrous sodium sulfate drying, underpressure distillation removing toluene after filtering, uses petrol ether/ethyl acetate to carry out column chromatography by unreacted compound ii removing completely.Obtain target product when eluent is petrol ether/ethyl acetate=3:1, after precipitation, obtain off-white color solid 16.0g.HPLC analytical results: target compound content adds up to 98.9%. 1H-NMR:3.41-3.45ppm(m,4H,-CH 2OCH 2-)；4.11－4.17ppm(m,4H,-CH 2O-)；7.35-8.07ppm(m,26H,ArH)。
The preparation of embodiment 9 tetraethylene-glycol two [2-(4-Phenylbenzoyl) phenylformic acid] ester
In 250ml four-hole bottle, 28.5g (0.09mol) compound ii, 9.13g (0.047mol) tetraethylene-glycol and 0.8g tosic acid are placed in 100 milliliters of toluene and carry out azeotropic and reflux 54 hours.Reaction solution 100 milliliters of 0.1M aqueous sodium carbonates wash twice, then wash twice by 100 ml deionized water.Then spend the night with anhydrous sodium sulfate drying, removed under reduced pressure toluene after filtering, uses petrol ether/ethyl acetate to carry out column chromatography by unreacted compound ii removing completely.Obtain target product when eluent is petrol ether/ethyl acetate=3:1, after precipitation, obtain off-white color solid 18.4g.HPLC analytical results: target compound content adds up to 98.0%. 1H-NMR:3.42-3.49ppm(m,8H,-OCH 2CH 2O-)；3.49-3.53ppm(m,4H,-CH 2O)；4.18－4.21ppm(m,4H,CH 2O-)；7.32-8.07ppm(m,26H,ArH)。
The preparation of embodiment 102-(4-Phenylbenzoyl) benzoic acid ethoxymethyl trihydroxymethylpropanyl ester
In 250ml four-hole bottle, 27.2g (0.09mol) compound ii, 13.5g (0.03mol) ethoxylated trimethylolpropane (molecular-weight average 450) and the agent of 0.5g Catalyzed by p-Toluenesulfonic Acid are placed in 100 milliliters of toluene and carry out azeotropic and reflux 54 hours.Reaction solution 100 milliliters of 0.1M aqueous sodium carbonates wash twice, then wash twice by 100 ml deionized water.Then spend the night with 5g anhydrous magnesium sulfate drying, after filtration, remove toluene on a rotary evaporator, obtain thick pale yellow shape liquid 38.2g, yield 93.8%.HPLC analytical results: target compound content adds up to 98.0%.
The preparation of embodiment 11 ethylene glycol bisthioglycolate [3-(4-Phenylbenzoyl) phenylformic acid] ester
In 250ml four-hole bottle, 30.2g (0.1mol) compound III, 3.0g (0.05mol) ethylene glycol and 0.8g tosic acid are placed in 100 milliliters of toluene and carry out azeotropic and reflux 48 hours.Reaction solution 100 milliliters of 0.1M aqueous sodium carbonates wash twice, then wash twice by 100 ml deionized water.Then spend the night with anhydrous sodium sulfate drying, after filtration, remove toluene on a rotary evaporator, use petrol ether/ethyl acetate to carry out column chromatography by unreacted compound III removing completely.Obtain target product when eluent is petrol ether/ethyl acetate=5:1, obtain white solid 22.6 grams after underpressure distillation solvent, fusing point 130.2-131.5 DEG C, yield 71.7%.HPLC analytical results: target compound content adds up to 98.5%. 1H-NMR:4.71ppm(s,4H,-OCH 2CH 2O-)；7.40-7.70ppm(m,16H,ArH)；7.85-7.88ppm(d，4H，ArH)；8.00-8.02(d，2H，ArH)；8.25-8.27(d，2H，ArH)；8.48(s，2H，ArH)。
The preparation of embodiment 12 tetraethylene-glycol two [3-(4-Phenylbenzoyl) phenylformic acid] ester
By the method for embodiment 9, replace compound ii by compound III, obtain pale yellow waxy thing I-7, yield 65.2%.Melting range 62.0-68.5 DEG C, HPLC analytical results: target compound content adds up to 96.6%.
1H-NMR:3.63-3.65(d,8H,2-0CH 2CH 2O-),3.80-3.83(t,4H,-CH 20CH 2-),4.47-4.50ppm(t,4H,-COOCH 2)；7.40-7.70ppm(m,16H,ArH)；7.86-7.89ppm(d，4H，ArH)；8.00-8.02(d，2H，ArH)；8.26-8.28(d，2H，ArH)；8.47(s，2H，2ArH)。
The source of more than testing main agents used sees the following form 2.
Table 2
Material name Supplier
Biphenyl Chemical Reagent Co., Ltd., Sinopharm Group
Phthalic anhydride Insight High Technology Co., Ltd. (Jiangsu)
M-phthaloyl chloride Beijing chemical reagents corporation
Aluminum chloride Tianjin Beijing-Tianjin insecticide factory
Tosic acid 5-linked chemical plant, Shanghai
PTHF250 INVISTA company
PTHF1000 Aladdin Reagent Company
Poly(oxyethylene glycol) 400 Hua You chemical plant, Beijing
Polyethylene Glycol-600 Hua You chemical plant, Beijing
Polyethylene glycol-800 Hua You chemical plant, Beijing
Ethoxylation tetramethylolmethane Tianjin proud son of heaven Chemical Co., Ltd.
Pentaerythritol propoxylate Tianjin proud son of heaven Chemical Co., Ltd.
Embodiment 13
Curing performance compares
Respectively by the product in above-described embodiment 3 to 12, and the product obtained by comparing embodiment 1,2 makes corresponding UV curable varnish formulation as light trigger, also benzophenone and phenyl benzophenone are made corresponding UV curable varnish formulation as light trigger in addition.The formula of described varnish formulations, in table 3, obtains varnish formulations A-K totally ten two.
Table 3
System component Weight percent (%)
Light trigger 7
Amino acrylates auxiliary agent (Ebecryl P115, Cytec company) 8
Epoxy acrylate oligomer (6210G, Changxing company) 25
Polyfunctional monomer, GPTA (EM2385 Glycerol propoxylate triacrylate, Changxing company) 60
Being executed with 10 micro wire rod spreaders by the varnish formulations of preparation gained prints on tinplate, is that in 100 watts/centimetre, medium pressure mercury lamp is cured with 100 ms/min of speed with a power.Record obtains number of pass times under good surface and the lamp thoroughly required for solidification, evaluates smell rank: be 5 to the maximum, minimum is 1 at once.Its result is as shown in table 4 below.
Table 4
Preparation is numbered Light trigger contained by preparation The required number of pass times of solidification completely The smell rank of cured film
A The product (I-1) of embodiment 3 3 1
B The product (I-3) of embodiment 5 3 1
C The product (I-5) of embodiment 7 5 1
D The product (I-6) of embodiment 8 2 1
E The product (I-7) of embodiment 9 4 1
F The product (I-8) of embodiment 10 2 1
G The product (I-10) of embodiment 12 3 1
H The product (V) of comparing embodiment 1 6 1
I The product (VI) of comparing embodiment 2 8 1
J Benzophenone (BP) 3 5
K Phenyl benzophenone (PBZ) 2 4
These results show that compound of the present invention is at least equivalent to regard to curing speed or close to the curing speed of benzophenone, its curing speed is apparently higher than other benzophenone macromolecular photoinitiators in comparing embodiment 1 or comparing embodiment 2.All compositions that is light trigger with the product of embodiment, the stink completely after solidification is all lower than benzophenone.Yellowness factor after all example solidifications is all close.

Claims (16)

1. the compound shown in formula I
Wherein:
G is the residue of polyol, but G is not the aminated compounds residue of nitrogen atom, and the hydroxyl value in described polyol is Integer n, and 2≤n≤6; x 1for positive integer, and 2≤x 1≤ n, x 2for n-x 1;
A is Sauerstoffatom or A representative formula independently of each other group, 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 the integer from 1 to 30;
R is hydrogen atom, C 1-C 12alkyl acyl, aryl-acyl, C 2-C 12conjugation enoyl-.
2. the compound described in claim 1 ,-the CO-A be connected in its Chinese style I on phenyl ring is positioned at ortho position, a position of 4-Phenylbenzoyl.
3. the compound described in claim 1 or 2, wherein A representative formula group.
4. compound according to claim 3, wherein A representative
5. the compound described in claim 1 or 2, wherein A representative formula group.
6. the compound described in claim 1 or 2, wherein A representative formula group.
7. the compound described in claim 1 or 2, wherein residue (A-) x 1g-(A) x 2molecular weight be not more than 1200.
8. compound according to claim 7, wherein residue (A-) x 1g-(A) x 2molecular weight be not more than 800.
9. the compound described in claim 1 or 2, wherein G is the residue of ethylene glycol, propylene glycol, butyleneglycol, glycerol, TriMethylolPropane(TMP), ditrimethylolpropane, tetramethylolmethane or dipentaerythritol.
10. the preparation method of the formula I of claim 1, comprising:
2-(4-Phenylbenzoyl) phenylformic acid, 3-(4-Phenylbenzoyl) phenylformic acid or 4-(4-Phenylbenzoyl) phenylformic acid and structural formula is made to be (HA) xthe compound of-G carries out esterification, wherein x=x 1+ x 2.
The preparation method of the formula I of 11. claims 10, comprising:
2-(4-Phenylbenzoyl) phenylformic acid, 3-(4-Phenylbenzoyl) phenylformic acid or 4-(4-Phenylbenzoyl) phenylformic acid and structural formula is made to be (HA) xthe compound of-G carries out esterification, wherein x=x 1+ x 2;
Work as x 2be more than or equal to 1; And R is when being acyl group, back esterification products carries out second time esterification with ROH again and obtains formula I.
Described in one of 12. claim 1-9, formula I is as the purposes of light trigger.
13. 1 kinds of light triggers, is characterized in that containing formula I described in one of at least one claim 1-9.
14. 1 kinds of photopolymerization composites, is characterized in that containing following compositions:
Polymerisable composition, wherein at least comprises a kind of ethylenically unsaturated monomers or oligomer;
Light trigger according to claim 13.
15. photopolymerization composite according to claim 14, be varnish or printing-ink.
16. 1 kinds of methods that photopolymerization composite is solidified, comprise and first being coated on base material by the photopolymerization composite described in claim 13 or 14, are then exposed under ultraviolet radiation and complete coating curing.
CN201410311886.1A 2014-07-02 2014-07-02 (4-Phenylbenzoyl) benzoic ether and the purposes as light trigger thereof Pending CN105218372A (en)

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CN108623717A (en) * 2017-03-20 2018-10-09 常州强力电子新材料股份有限公司 A kind of polyfunctionality benzoyl class macromolecular photoinitiator and preparation method thereof

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CN108623717A (en) * 2017-03-20 2018-10-09 常州强力电子新材料股份有限公司 A kind of polyfunctionality benzoyl class macromolecular photoinitiator and preparation method thereof
CN108623717B (en) * 2017-03-20 2021-09-28 常州强力电子新材料股份有限公司 Multifunctional benzoyl macromolecular photoinitiator and preparation method thereof

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