CN103012478B - Preparation method for photoinitiators containing phosphorus - Google Patents
Preparation method for photoinitiators containing phosphorus Download PDFInfo
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- CN103012478B CN103012478B CN201210562489.2A CN201210562489A CN103012478B CN 103012478 B CN103012478 B CN 103012478B CN 201210562489 A CN201210562489 A CN 201210562489A CN 103012478 B CN103012478 B CN 103012478B
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Abstract
The invention relates to a preparation method for a plurality of photoinitiators containing phosphorus. The preparation method comprises the steps of taking 2,4,6-trimethylphenyl halogen methane as a raw material, allowing 2,4,6-trimethylphenyl halogen methane to react with sodium phosphine to be oxidized, obtaining a phosphine oxide intermediate, finally, executing a key reaction step, namely the reaction that alpha-carbon is oxidized into ketone, and obtaining a high-yield target oxidation product through oxidation with an oxidizer under the action of a catalyst. The raw material required by the method is low in price and easy to obtain; process equipment is simple; and the method is easy to operate and low in cost.
Description
Technical field
The present invention relates to a kind of Chemicals preparation field, the particularly preparation method of phosphorous light trigger.
Background technology
Acylphosphine oxide light trigger is the outstanding light trigger of a class, wherein most important kind TPO and 819 (also claiming BAPO).TPO has enough solubleness in reactive thinner, and absorbing wavelength can reach 430nm, and it produces the free radical (mesitylene Formyl radical and diphenylphosphine free acyl radical) that two initiating activities are very high after photolysis.And 819 maximum absorption wavelengths can reach 450nm, it produces the free radical (two mesitylene Formyl radicals and a diphenylphosphine free acyl radical) that three activity are very high after photolysis.These two kinds of light triggers belong to the good light trigger of over-all properties, are widely used in light initiation polymerization material.
The preparation of above-mentioned two photoinitiators is all for raw material usually with 2,4,6-tri-methyl chloride 1 or rice aldehyde 2.US Patent No. 4298738 discloses with 2,4,6-tri-methyl chloride 1 prepares TPO, at ambient temperature, diphenyl phosphine chloride and methyl alcohol are reacted, low-pressure distillation purifying methoxyl group diphenylphosphine, then 2,4,6-tri-methyl chloride is added drop-wise to and obtains reacting 3-8h in methoxyl group diphenylphosphine, and sherwood oil recrystallization obtains TPO.Patent WO2005/014606 discloses with 2,4,6-tri-methyl chloride and tetraphenylphosphonium chloride phosphine prepare 819, concrete grammar is that tetraphenylphosphonium chloride phosphine and sodium are obtained by reacting phenyl sodium phosphide, phenyl sodium phosphide and propyl carbinol react prepares Phenylphosphine, the Phenylphosphine obtained finally reacts preparation 819 at 70-110 DEG C with 2,4,6-tri-methyl chlorides.Chinese patent CN201010137621.6 discloses and carries out addition reaction with rice aldehyde 2 and diphenyl phosphine chloride, then prepares TPO with oxygenant as hydrogen peroxide carries out oxidation.
The preparation of 2,4,6-tri-methyl chloride 1 and rice aldehyde 2 is generally take sym-trimethylbenzene as raw material.The method of preparation 2 is generally Gattermann-Koch method, is that raw material obtains with reaction of carbon monoxide under aluminum trichloride (anhydrous) (on-catalytic dosage) exists in autoclave pressure with sym-trimethylbenzene.US Patent No. 4195040 discloses reacts generation 2 with sym-trimethylbenzene and carbon monoxide, hydrogenchloride, aluminum chloride under a pressure 20-60 normal atmosphere.The method of preparation 1 mainly contains following several at present:
1.Sokol P E.Mesitoic acid [J] .Org.Synth., 1964,44:69-71 disclose sym-trimethylbenzene and oxalyl chloride at AlCl
3then hydrolysis is reacted obtained under catalysis.In this route, raw materials used oxalyl chloride price is high, and therefore cost is higher.
2.Ilga M, Edgars S.Aryl zinc species by microwave assisted grignard formation-transmetalat-ion sequence:application in the negishi coupling [J] .Tetrahedron, 2005,61 (47): 11168-11176 disclose sym-trimethylbenzene after bromination, grignard reaction again with CO
2addition is then hydrolyzed obtained.This route preparation process is more, and raw materials used bromine price is higher, and has anhydrous operation steps troublesome poeration in route and cost is higher.
3. Lu nine chisels, the .2 such as Xu Yaxian, Yuan Guang, the synthesis [J] of 4,6-trimethylbenzoic acid. and fine chemistry industry .2001,3:1-4 disclose sym-trimethylbenzene and chloroacetyl chloride prepares 1.Total four-step reaction: 1. sym-trimethylbenzene and chloroacetyl chloride 80 DEG C of acylation reactions under ferric oxide catalysis; 2. logical chlorine carries out haloform reaction; 3. alkaline hydrolysis; 4. acidifying.This method shortcoming uses more expensive chloroacetyl chloride, and step is many, no matter operates or still have disadvantage economically.
4. US Patent No. 5616787 discloses and reacts at pressure 10 normal atmosphere and-20-40 DEG C under aluminum trichloride (anhydrous) (on-catalytic dosage) exists with sym-trimethylbenzene and carbonic acid gas, and crystallizing and drying obtains 1.This method be to equipment and reaction conditions requirement higher, the three wastes are more.
Therefore the cost of preparation 1 and 2 is higher, and to severe reaction conditions, equipment requirements is higher, and the three wastes of generation are more.
The present invention avoids use 1 and 2, and provide one to provide a kind of technical process simple, high yield, the three wastes are few, the preparation method of the phosphorous light trigger that cost is low.
Summary of the invention
The object of the invention is to overcome the defect existed in existing production technique, provide a kind of technical process simple, high yield, the three wastes are few, the preparation method of the phosphorous light trigger that cost is low.
The invention provides a kind of general preparative methods of phosphorous light trigger, the committed step being prepared phosphorous light trigger by simple raw material is: the catalytic oxidation of compound 5 benzyl position carbon, committed step is
The present invention adopts diphenyl phosphine chloride to be starting raw material, ethoxy diphenyl base phosphine is prepared with ethanol synthesis, the ethoxy diphenyl base phosphine obtained and 2,4,6-trimethylammonium halogenation benzyl 3 is obtained by reacting (2,4,6-trimethyl benzyl) diphenyl phosphine oxide (5a), finally under catalyzer and oxygenant exist, 5a benzyl position carbon (i.e. alpha-carbon) is oxidized to carbonyl and prepares TPO.
The present invention adopts tetraphenylphosphonium chloride phosphine to be starting raw material, phenyl sodium phosphide is obtained by reacting with sodium sand, do not need process, drip 2,4,6-trimethylammonium halogenation benzyl 3 obtains two (2,4,6-trimethyl benzyl) Phenylphosphine, be oxidized two (2,4 with oxygenant (as hydrogen peroxide, to chloroperoxybenzoic acid), 6-trimethyl benzyl) Phenylphosphine prepares two (2,4,6-trimethyl benzyl) phenyl phosphine oxide (5b), under catalyzer and oxygenant exist, 5b benzyl position carbon (i.e. alpha-carbon) is oxidized to carbonyl and namely obtains 819.
With preparation method provided by the invention can high yield, prepare light trigger TPO and 819 at low cost, its operational path is:
The preparation of 2,4,6-trimethylammonium halogenation benzyl 3 can be that raw material and hydrogen halide (or haloid acid), formaldehyde (or paraformaldehyde) react obtained expediently with sym-trimethylbenzene, technical process is simple, the three wastes are few, and yield is high, cost than 1 and 2 decline more.
Wherein X can be Cl, Br; As X=Cl, 3 is 2,4,6-trimethyl ammonia chloride benzyl (3a); As X=Br, 3 is 2,4,6-trimethylammonium cylite (3b).
Can see from operational path above, the committed step preparing phosphorous light trigger is the catalytic oxidation of compound 5.In this catalytic oxidation stage, oxygenant can be hydrogen peroxide (H
2o
2the aqueous solution), peroxy tert-butyl alcohol (t-BuOOH/t-BuOH), Peracetic Acid (AcOOH/AcOH), nitric acid (HNO
3) etc. a kind of or their mixing.Catalyzer can be Multimetal oxide, metal-salt or metal complexes MLn, M=Pb, V, Cr, Cu, Ce, Ag; L=O, AcO
-, Cl
-, acac
-, BF
4 -, Salan, NH
3, NO
2, CO; N=1-6, such as CrO
3, Cr (CO)
6, Cr (OAc)
3, K
2cr
2o
7, Pb (OAc)
2, VO (acac)
2, V
2o
5, Salan Cu, Ce (NH
4)
2(NO
3)
6(CAN), AgBF
4deng.
The solvent suitable according to the different choice of substrate, oxygenant and catalyzer.These solvents can be that aprotic polar solvent is as DMF, N, N-N,N-DIMETHYLACETAMIDE, acetonitrile, methyl-sulphoxide, dioxan etc., also can be proton polar solvent alcohols as methyl alcohol, ethanol, propyl alcohol, Virahol, fourth alcohol and water, can also be that haloalkane hydro carbons is as methylene dichloride, ethylene dichloride chloroform.
The preparation method of phosphorous light trigger provided by the invention is the preparation method of the phosphorous light trigger that a kind of technical process is simple, high yield, the three wastes are few, cost is low, has good IP prospecting.
Embodiment
The present invention will be described further by following embodiment.
The reagent that the present invention uses is commercially available prod.
The preparation of embodiment 1:2,4,6-trimethyl ammonia chloride benzyl
Get 400g sym-trimethylbenzene, 1.1L hydrochloric acid (36%), after 0.5g phase-transfer catalyst Cetyltrimethylammonium bromide (CTAB) mixes, stirring at room temperature 2h, 110g paraformaldehyde is added under stirring, heat up 75 DEG C, reaction 4h, GC monitors reaction, after reaction terminates, be down to room temperature, add a small amount of Virahol breakdown of emulsion, with dichloromethane extraction, the organic phase obtained first is washed with the sodium hydroxide solution of 2mol/L, then wash, with anhydrous sodium sulfate drying, fractionation, collect the cut that boiling point is 130-140 DEG C, namely 2, 4, 6-trimethyl ammonia chloride benzyl, yield is 85%, fusing point 38 DEG C.
The preparation of embodiment 2:2,4,6-trimethylammonium cylite
Get 400g sym-trimethylbenzene, after 1.5L hydrogen bromide (40%), 0.7g phase-transfer catalyst Cetyltrimethylammonium bromide (CTAB) mix, stirring at room temperature 2h, 110g paraformaldehyde is added under stirring, intensification 40-45 DEG C, reaction 3.5h, GC monitors reaction, after reaction terminates, is down to room temperature, add a small amount of Virahol breakdown of emulsion, use 600ml dichloromethane extraction, stir, in separating funnel stratification, separate organic layer, water layer 300ml ethylene dichloride extracting twice, merges organic layer, uses 5%N
ahCO
3aqueous solution 400ml washes once, point water-yielding stratum, then 400ml washing twice, dried over mgso, precipitation, and underpressure distillation, collects: 118 DEG C/2mmHg cut 622g, yield: 90%, GC:98.5%, fusing point: 52 DEG C.
Embodiment 3: the preparation of phenyl sodium phosphide
Under nitrogen protection; room temperature is by sodium block (10.3g; 0.448mol) be suspended in 400g dry toluene, be stirred and heated to backflow, start vigorous stirring 0.5-1h when temperature is raised to 98 DEG C; sodium sand can be formed; under reflux conditions, dichlorophenyl phosphine (20.1g, 0.112mol) is dissolved in 170g toluene, is added drop-wise in sodium sand; within 1 hour, drip and finish, back flow reaction obtains bright yellow precipitate in 24 hours.Because phenyl sodium phosphide is unstable, directly next step reaction need not be separated.
The preparation of embodiment 4: two (2,4,6-trimethyl benzyl) Phenylphosphine
In nitrogen protection; under reflux conditions; 1,3,5-trimethylammonium-2-brooethyl benzene (47.7g is dripped in the mixture that embodiment 3 obtains; 0.224mol) (be dissolved in advance in 130g toluene); within 2 hours, drip and finish, be then warming up to backflow, back flow reaction 10 hours; obtain dusty blue mixture; TLC or GC monitors reaction, after reaction terminates, is cooled to room temperature; stop nitrogen protection; add 7ml Virahol to stir, destroy unreacted sodium, until bubble-free produces, (churning time is longer; determine that sodium destroys completely), dusty blue gradually becomes brown color.Need not process, sodium destroys completely, and gained solution directly carries out next step reaction.
The preparation of embodiment 5: two (2,4,6-trimethyl benzyl) phenylphosphine oxide
Example 4 gained solution, at 35-40 DEG C, slowly drips the hydrogen peroxide (37.4g of 30%, 0.33mol), within 0.5 hour, drip and finish, then react 5 hours, white solid can be separated out, TLC detection reaction, after reaction terminates, be down to room temperature, slowly add 5% sodium bicarbonate aqueous solution 120ml, stir 10 minutes, in separating funnel, separate organic layer, 40ml washes three times, anhydrous magnesium sulfate drying, precipitation, obtains target compound crude product.Crude product is added 70ml sherwood oil (60-90 DEG C) to wash and starch, suction filtration, dries, and obtains two (2,4,6-trimethyl benzyl) phenylphosphine oxide 38.9g, grayish white powdery solid, fusing point: 174-176 DEG C, yield: 89%.
The preparation (Salan Cu makees catalyzer) of embodiment 6: two (2,4,6-trimethylbenzoyl) phenylphosphine oxide (819)
By two (2,4,6-trimethyl benzyl) phenylphosphine oxide 5b (0.02mol, 7.80g), catalyst S alan Cu (0.1%mol) and 30%H
2o
2(44.6ml, 4mol) be dissolved in 20ml acetonitrile, in 70-80 DEG C of insulation a few hours until compound 5b disappears (monitoring with TLC) under stirring, after reacting completely, low pressure steams solvent and water, resistates is dissolved in toluene, respectively wash once with saturated NaCl solution, water respectively, organic phase anhydrous Na
2sO
4drying, obtains product (2,4,6-trimethylbenzoyl) phenylphosphine oxide (819) 6.94g through recrystallization after sloughing solvent, productive rate 83%.
The preparation (Salan Cu makees catalyzer) of embodiment 7:2,4,6-trimethyl benzoyl diphenyl base phosphorus oxide (TPO)
By 2,4,6-trimethyl benzyl diphenyl phosphate oxidation 5a (0.02mol, 6.68g), catalyst S alan Cu (0.1%mol) and 30%H
2o
2(22.3ml, 0.2mol) be dissolved in 20ml acetonitrile, in 70-80 DEG C of insulation a few hours until compound 5a disappears (monitoring with TLC) under stirring, after reacting completely, low pressure steams solvent and water, resistates is dissolved in toluene, respectively wash once with saturated NaCl solution, water respectively, organic phase anhydrous Na
2sO
4drying, obtains product 2,4,6-trimethyl benzoyl diphenyl base phosphorus oxide (TPO) 6.00g through sherwood oil recrystallization after sloughing solvent, fusing point: 90 DEG C, yield 88%.
Preparation (the CrO of embodiment 8:2,4,6-trimethyl benzoyl diphenyl base phosphorus oxide (TPO)
3make catalyzer)
2,4,6-trimethyl benzyl diphenyl phosphate oxidation 5a (0.02mol, 6.68g) is dissolved in 30ml CH
2cl
2in, add catalyzer CrO
3(4%mol) drip the peroxy tert-butyl alcohol aqueous solution (0.08mol) of 70% under stirring in 0-5 DEG C, at about 10 DEG C stirring reaction 30h after adding, the saturated NaHSO of 40ml used respectively by reaction mixture
3solution and the saturated NaCl solution of 30ml are washed, and point oil-yielding stratum, uses anhydrous Na
2sO
4drying, obtains thick product and obtains 2,4,6-trimethyl benzoyl diphenyl base phosphorus oxide (TPO) 5.78g through recrystallization, productive rate 83% after desolventizing.
Preparation (the VO (acac) of embodiment 9:2,4,6-trimethyl benzoyl diphenyl base phosphorus oxide (TPO)
2make catalyzer)
2,4,6-trimethyl benzyl diphenyl phosphate oxidation 5a (0.02mol, 6.68g) is dissolved in 30ml (CH
2cl)
2in, add catalyst V O (acac)
2(5%mol) drip 70% peroxy tert-butyl alcohol solution (0.08mol) in stirred at ambient temperature, after adding, react 5h at temperature therewith.Saturated NaHSO used respectively by reaction mixture
3solution 40ml and saturated NaCl solution 30ml washes, and point oil-yielding stratum, uses anhydrous Na
2sO
4drying, obtains thick product and obtains 2,4,6-trimethyl benzoyl diphenyl base phosphorus oxide (TPO) 5.50g through recrystallization, productive rate 79% after desolventizing.
Claims (2)
1. the preparation method of a phosphorous light trigger; it is characterized in that step that it comprises is by 2; 4,6-trimethyl benzyl diphenyl phosphine oxide or two (2,4; 6-trimethyl benzyl) there is preparation 2 at catalyzer, oxygenant, solvent in the benzyl position carbon of phenyl phosphine oxide; 4,6-trimethyl benzoyl diphenyl base phosphine oxide or two (2,4; 6-trimethylbenzoyl) phenyl phosphine oxide, reaction scheme:
Wherein: used catalyst is selected from CrO
3, VO (acac)
2, a kind of in Salan Cu or their mixing; Oxygenant used is selected from a kind of in hydrogen peroxide, peroxy tert-butyl alcohol or their mixing; Solvent for use is selected from a kind of in DMF, N,N-dimethylacetamide, acetonitrile, methyl-sulphoxide, diox, methylene dichloride, ethylene dichloride, chloroform or their mixing.
2. the preparation method of phosphorous light trigger according to claim 1, is characterized in that solvent for use is selected from a kind of in acetonitrile, methyl-sulphoxide, diox, methylene dichloride, ethylene dichloride or their mixing.
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Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104151358B (en) * | 2014-08-22 | 2016-05-11 | 张家港吉慕特化工科技有限公司 | The preparation method of two (2,4, the 6-trimethylbenzoyl) phenyl phosphine oxides of a kind of light trigger |
| CN105541913B (en) * | 2015-12-03 | 2017-08-25 | 天津久日新材料股份有限公司 | A kind of preparation method of 2,4,6 trimethyl benzoyl diphenyl base phosphine oxide |
| CN106905364A (en) * | 2017-01-10 | 2017-06-30 | 山东科技大学 | A kind of environmental protection preparation method of 2,4,6 trimethyl benzoyl diphenyl base phosphine oxide |
| CN106883265B (en) * | 2017-01-10 | 2018-08-31 | 山东科技大学 | A method of efficiently, being recycled synthesis 2,4,6- trimethylbenzoy-dipheny phosphine oxides |
| CN110343134B (en) * | 2019-08-04 | 2022-03-15 | 张震 | Preparation method of photoinitiator bis (2,4, 6-trimethylbenzoyl) phenylphosphine oxide |
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Address after: 300403 Beichen District, Chen Chen Road, No. 22, No. Patentee after: TIANJIN JIURI NEW MATERIALS CO., LTD. Address before: 300403 Beichen District, Chen Chen Road, No. 22, No. Patentee before: Tianjin Jiuri Chemical Co., Ltd. |