CN113651850A - Co-production preparation of monoacylphosphines and bisacylphosphines and their oxides - Google Patents

Co-production preparation of monoacylphosphines and bisacylphosphines and their oxides Download PDF

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CN113651850A
CN113651850A CN202010400237.4A CN202010400237A CN113651850A CN 113651850 A CN113651850 A CN 113651850A CN 202010400237 A CN202010400237 A CN 202010400237A CN 113651850 A CN113651850 A CN 113651850A
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tpo
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赵新阳
宁超
王智刚
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Shenzhen Youwei Technology Holding Co ltd
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/28—Phosphorus compounds with one or more P—C bonds
    • C07F9/50—Organo-phosphines
    • C07F9/53—Organo-phosphine oxides; Organo-phosphine thioxides
    • C07F9/5337—Phosphine oxides or thioxides containing the structure -C(=X)-P(=X) or NC-P(=X) (X = O, S, Se)
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/28—Phosphorus compounds with one or more P—C bonds
    • C07F9/30—Phosphinic acids [R2P(=O)(OH)]; Thiophosphinic acids ; [R2P(=X1)(X2H) (X1, X2 are each independently O, S or Se)]
    • C07F9/307—Acids containing the structure -C(=X)-P(=X)(R)(XH) or NC-P(=X)(R)(XH), (X = O, S, Se)
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/28—Phosphorus compounds with one or more P—C bonds
    • C07F9/50—Organo-phosphines
    • C07F9/53—Organo-phosphine oxides; Organo-phosphine thioxides
    • C07F9/5341—Organo-phosphine oxides or thioxides containing a P-P bond
    • 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
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    • C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
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    • 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
    • C08G79/00—Macromolecular compounds obtained by reactions forming a linkage containing atoms other than silicon, sulfur, nitrogen, oxygen, and carbon with or without the latter elements in the main chain of the macromolecule
    • C08G79/02—Macromolecular compounds obtained by reactions forming a linkage containing atoms other than silicon, sulfur, nitrogen, oxygen, and carbon with or without the latter elements in the main chain of the macromolecule a linkage containing phosphorus
    • C08G79/04—Phosphorus linked to oxygen or to oxygen and carbon
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids

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Abstract

The invention relates to the field of novel photocuring functional material chemicals, and discloses the co-production preparation of series of monoacylphosphines and bisacylphosphines and oxides thereof, namely monoacylphosphine oxide and bisacylphosphine oxide, for the first time, the one-pot preparation of the compounds under the same process and the same reactor is realized, and the process technology has the outstanding characteristics of low cost, economic competitiveness and environmental friendliness. The compounds are important radiation polymerization system photoinitiators containing ethylenic bond (C ═ C) unsaturation.

Description

Co-production preparation of monoacylphosphines and bisacylphosphines and their oxides
[ technical field ] A method for producing a semiconductor device
The invention relates to the field of novel photocuring functional material chemicals, and discloses the co-production preparation of series of monoacylphosphines and bisacylphosphines and oxides thereof, namely monoacylphosphine oxide and bisacylphosphine oxide, for the first time, the one-pot preparation of the compounds under the same process and the same reactor is realized, and the process technology has the outstanding characteristics of low cost, economic competitiveness and environmental friendliness. The compounds are important radiation polymerization system photoinitiators containing ethylenic bond (C ═ C) unsaturation.
[ background of the invention ]
In the field of photo-curing functional new material chemicals, some mono-or di-functional Acylphosphine (oxy) type (Acylphosphine Oxide) compounds, such as typically 2, 4, 6-trimethylbenzoyldiphenylphosphine Oxide (trade name Lucirin-TPO), ethyl 2, 4, 6-trimethylbenzoylphenylphosphonate (trade name Irgacure-TPO-L), and bis (2, 4, 6-trimethylbenzoyl) phenylphosphine Oxide (trade name Irgacure-819), respectively, are highly effective photoinitiators for ethylenically unsaturated radiation polymerization-containing systems, which are well known in the art. The light absorption characteristic of the material is wide and excellent, and the material can extend from ultraviolet short wave to a long wave band of 350-420 nm, so that the material can show excellent photopolymerization initiation capability under the irradiation of a traditional ultraviolet light source represented by a high-pressure mercury lamp and an energy-saving environment-friendly light-emitting diode (LED) light source, and can be widely applied to the fields of photocuring wood coatings, PCB circuit board ink, printing and packaging ink, adhesives, 3D additive printing, composite materials, optical fibers, TFT-LCD liquid crystal display and the like.
In view of their outstanding practical value, the industry is constantly searching for new more competitive and environmentally friendly process technologies. Although mono-or di-functional acylphosphine (oxy) compounds have certain similarity in molecular structure, their related chemical preparation method principles, product purification and byproduct disposal, and the flow of the used reaction equipment are all greatly different and incompatible, and objectively form mutually independent manufacturing-end industrial chains for practitioners in the art.
The preparation of monoacylphosphine oxygen compounds, typically described in U.S. Pat. Nos. 4710523 and 4324744, is widely practiced in industry and discloses the preparation of TPO photoinitiator compounds by the so-called Arbuzov-Michaelies reaction of diphenyl phosphite esters first prepared by condensation of diphenyl phosphine chloride with primary alcohols promoted by an organic tertiary amine type acid-binding agent and the esters then with the corresponding acid chlorides, e.g., 2, 4, 6-trimethylbenzoyl chloride. The reaction uses a refractory tertiary organic amine and produces ozone (O) to the atmosphere3) A layer of hazardous chemical chlorohydrocarbon.
A widely used process for the preparation of bisacylphosphine oxide compounds is described in the representative Chinese patent CN1211388, which discloses the reaction of an organophosphine chloride compound such as phenylphosphine dichloride with an alkali metal to obtain an oligomeric cyclic phosphine intermediate mixture which must be reduced by metallic sodium in the presence of a "proton source donor compound" tert-butanol to the corresponding phenylphosphine hydrogen intermediate, which is then further reacted with a metal salt to obtain the desired productAnd the corresponding acid chloride, such as 2, 4, 6-trimethylbenzoyl chloride, to produce the acylphosphine intermediate, which is oxidized with hydrogen peroxide to produce the bifunctional acylphosphine oxide compound. The process directly derives 'PhPCl' of Irgacure-819 from the cooperative research results of Swiss Ciba, Pasteur, Germany and Gruetzmacher team of Swiss ETH institute2The new production process of the/Na/t-BuOH method. However, the reaction principle of this method is limited to the preparation of bisacylphosphine oxide type compounds, and is not applicable to the preparation of monoacylphosphine oxide products such as TPO and TPO-L at all.
In view of the above, there is still an urgent need for technical innovation in the industry that has never been achieved, namely the "one-pot" co-production of mono-and bifunctional acylphosphine (oxy) type photoinitiator compounds, the breakthrough of which requires both the innovation of the reaction principle and the complete compatibility of the equipment hardware. The method is a key technical problem with important reality, low cost, economic competitiveness and environmental management friendliness.
[ summary of the invention ]
The present application discloses for the first time the coproduction of a series of monoacylphosphines (formula D) and bisacylphosphines (E), and their oxides, namely monoacylphosphine oxide (F) and bisacylphosphine oxide (G), from a starting material acyl halide (a) and a mixture of mono-and bishalophosphines (B and C) and a metal M, by direct action under conditions 1, followed by the action of an oxidizing agent [ O ] and conditions2, in a "one-pot" manner sharing the same process flow and the same reactor:
Figure BDA0002488055270000021
wherein R is1Is monovalent or divalent and contains 1 to 24 carbon atoms (denoted as C)1-C24The same applies hereinafter) straight-chain or branched alkyl or C3-C12Cycloalkyl, or R1Is monovalent or divalent C4-C24Substituted or unsubstituted aryl or heteroaryl; r2，R3Or R is4Independently of one another and monovalent R1The same;
x or Y are independently of each other a halogen atom;
m is metal Zn, Mg, Ni, Be, Co, Ru, Cu, Mo, Ba, Cd, Fe, Al, Cr, Mn, Ca, In;
[ O ] is an oxidant, air, oxygen, hydrogen peroxide, an organic alkyl peroxide, a peroxycarboxylic acid, ozone, (hypochlorite), nitrate, or a mixture of any two or more of the foregoing;
the conditions 1 and 2 are each, independently of one another, at least one of a solvent, a temperature, a pressure, and an additive.
The solvent is at least one selected from the group consisting of substituted or unsubstituted aromatic hydrocarbons having 1 to 24 carbons, linear or branched aliphatic hydrocarbons, (sulfoxide), amides, ethers, esters, ketones, nitriles, carboxylic acids, water, amines, carbonates, ionic liquids, and supercritical carbon dioxide.
In some preferred embodiments of the present invention, the solvent is selected from the group consisting of dimethyl sulfoxide, dimethyl sulfone, benzyl sulfoxide, benzyl sulfone, cyclobutane sulfoxide, sulfolane, trichlorosilane, dichloromethane, dichloroethane, dimethyl carbonate, diethyl carbonate, ethylene carbonate, propylene carbonate, chloroform, carbon tetrachloride, benzene, toluene, xylene, trimethylbenzene, tetramethylbenzene, acetonitrile, ethylbenzene, diethylbenzene, chlorobenzene, dichlorobenzene, anisole, nitrobenzene, heptane, hexane, petroleum ether, dioxane, tetrahydrofuran, methyl tert-butyl ether, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, propylene glycol methyl ether acetate, triethylamine, tributylamine, dimethyl isopropylamine, pyridine, N-tetramethylethylenediamine, N-alkylmorpholine, N-alkylpyrrole, N-dimethylformamide, dimethyl sulfoxide, and mixtures thereof, At least one of formylmorpholine, N-diethylformamide and N-methylpyrrolidone.
In the present invention, the reaction can also be carried out by heating and/or grinding the raw material solid phase, and/or by means of ultrasound and/or microwave irradiation, with little or no conventional "solvent" being used.
The temperature is-70 ℃ to 300 ℃. In a preferred embodiment of the invention, the temperature is from-30 ℃ to 250 ℃. In some more preferred embodiments of the invention, the temperature is from-20 ℃ to 200 ℃.
The pressure is 0.001atm-200 atm. In some preferred embodiments of the invention, the pressure is from 0.1atm to 100 atm. In some more preferred embodiments of the invention, the pressure is from 0.1atm to 20 atm.
The additive refers to a reaction promoter, a synergist, a catalyst, an oxidant, a reducing agent and/or a functional auxiliary agent; the additive is used in a catalytic amount, an equivalent amount or an excessive amount based on the molar weight of the reaction raw materials.
Preferred R1Is 2, 4, 6-trimethylbenzoyl chloride, 2, 6-dimethoxybenzoyl chloride, 1-naphthoyl chloride, (CH)3)3C-C (O) Cl; preferred X or Y is chlorine; preferred R2，R3Or R is4Independently of one another, phenyl, biphenyl, 1/2-naphthyl, 4-methoxyphenyl, 4-methylphenyl, 4-isopropylphenyl, 4-dimethylaminophenyl; preferred M are the metals Zn and Mg.
Another implementation scheme disclosed by the invention is that the starting material acyl halide (A), the mixture of the halogenated phosphines (B and C) and the metal M directly act under conditions 1 to obtain monoacylphosphine (D) and acyl phosphine halide (Q), and then under the action of an oxidant [ O ] and conditions2, monoacylphosphine oxide (F) and acyl phosphonic acid (T) are prepared by a one-pot method sharing the same process flow and the same reactor.
Acylphosphonic acid (R in T)5Is hydrogen) is a precursor compound of an acyl phosphonate. The acyl phosphonate can be prepared by esterification reaction of acyl phosphonic acid (T) and primary alcohol. A typical commercially available product of acyl phosphonate is TPO-L.
Figure BDA0002488055270000041
Wherein R is5Is hydrogen, C1-C24Linear or branched or cyclic alkyl;
preferred R5Hydrogen, methyl, ethyl, butyl, hydroxyethyl, cyclohexyl.
The third implementation scheme disclosed by the invention is that the starting material acyl halide (A), the bis-halogenated phosphine (C) and the metal M directly act under conditions 1 to obtain acyl phosphine halide (Q) and bis-acylphosphine (E), and then under the action of oxidant [ O ] and conditions2, acyl phosphonic acid (ester) (T) and bis-acylphosphine oxide (G) are prepared by a one-pot method sharing the same process and the same reactor.
Figure BDA0002488055270000051
A typical example, as shown below, TPO and 819 photoinitiator products were prepared simultaneously from 2, 4, 6-trimethylbenzoyl chloride, diphenylphosphine chloride, and phenylphosphine dichloride under the action of zinc powder to form the corresponding trivalent mono-and bisacylphosphanes, followed by oxidation with hydrogen peroxide.
Figure BDA0002488055270000052
During the performance of this example, a novel monoacylphosphine oxygen compound, shown by the following formula H, was simultaneously isolated, which is also an effective photoinitiator active species.
Figure BDA0002488055270000053
In another embodiment of the present invention, as shown below, a bisacylphosphine oxide photoinitiator compound K in the form of a polymer is obtained by reacting a divalent acid chloride and phenylphosphorus dichloride with zinc powder and hydrogen peroxide in this order.
The macromolecular photoinitiator has great significance in solving the problem of migration of the photoinitiator which is trapped for a long time in certain food packaging printing ink.
Figure BDA0002488055270000061
In a third embodiment of the present invention, as shown below, 2, 4, 6-trimethylbenzoyl chloride, diphenylphosphorus chloride, and phenylphosphorus dichloride are reacted with zinc powder to form the corresponding trivalent monoacylphosphane and acylphosphine chlorides, and then the phosphonic acid products TPO and TPO-L are simultaneously prepared under the oxidation of hydrogen peroxide.
The phosphonic acid product of TPO-L and a primary alcohol, such as ethanol, can be used to prepare TPO-L or other acyl phosphate photoinitiator compounds via a simple esterification reaction.
Figure BDA0002488055270000062
In a fourth embodiment of the invention, 2, 4, 6-trimethylbenzoyl chloride and phenylphosphorus dichloride are reacted with zinc powder to form the corresponding trivalent bisacylphosphine alkane and acylphosphine chloride, and then the phosphonic acid product 819 and TPO-L is prepared simultaneously under the oxidation of hydrogen peroxide.
Figure BDA0002488055270000071
In the fifth embodiment of the present invention, 2, 4, 6-trimethylbenzoyl chloride, diphenyl phosphorus chloride and phenyl phosphorus dichloride are reacted with zinc powder to produce corresponding trivalent monoacylphosphane, acylphosphine chloride and bisacylphosphine, and then the phosphonic acid products TPO and TPO-L and 819 three photoinitiator compounds are prepared simultaneously under the oxidation of hydrogen peroxide.
Figure BDA0002488055270000072
In conclusion, the invention firstly discloses the co-production technology of representative photoinitiator compounds, such as TPO and 819, TPO and TPO-L, 819 and TPO-L, and TPO-L and 819, which are outstanding, makes full use of the resource sharing and 100 percent utilization of raw materials, makes full use of the resource sharing of a reactor and a flow process, combines the two, and practices the atom economy and the process convenience prominently, which is an unprecedented technical breakthrough in the industry.
In the examples we will further illustrate.
[ detailed description ] embodiments
The gist of the present invention is further illustrated by the following specific examples:
the first embodiment is as follows: co-production of TPO and 819
Under the protection of nitrogen and at room temperature, 1.4 g of zinc powder, 15 ml of ethyl acetate and 4.0 g of 2, 4, 6-trimethylbenzoyl chloride are added into a 100 ml reaction bottle in sequence under stirring, then a mixture of 1.08 g of phenyl phosphorus dichloride and 1.32 g of diphenyl phosphorus chloride in 5 ml of ethyl acetate is added into the mixture dropwise, and the temperature is kept for 2 hours after the dropwise addition is finished. After the reaction is finished, 15 ml of water and 1.6 ml of 30% hydrogen peroxide are respectively added into the system, the reaction is continued for half an hour, after the detection reaction is finished, a little saturated sodium bicarbonate solution is added for neutralization, and then the neutralization is carried out by extraction, water washing and concentration, and silica gel column chromatography separation is carried out to obtain 1.7 g 819 (yield 68%) and 1.9 g TPO (yield 91%).
The above reaction was repeated but the solvent was changed to dimethyl carbonate to give 1.5 g 819 and 1.8 g TPO;
the reaction was repeated except that the zinc powder was changed to magnesium chips to give 1.1 g 819 and 1.6 g TPO.
Example two: co-production of TPO and 819
Under the protection of nitrogen and at room temperature, 17.2 kg of zinc powder, 200 liters of ethyl acetate and 49 kg of 2, 4, 6-trimethylbenzoyl chloride are sequentially added into a cubic enamel reaction kettle, then a mixture of 13.3 kg of phenyl phosphorus dichloride and 16.2 kg of diphenyl phosphorus chloride in 80 liters of ethyl acetate is dripped, and the temperature is kept for 6 hours after the dripping is finished. After the reaction is finished, respectively adding 180 liters of water and 20 liters of 30 percent hydrogen peroxide into the system, continuing the reaction for half an hour, after the detection reaction is finished, adding a proper amount of saturated sodium bicarbonate solution for neutralization, extracting, washing with water, concentrating, pulping by using ice-cold heptane, and separating to obtain 18.7 kilograms of 819 and 23.1 kilograms of TPO.
In which 1.1 kg of monoacylphosphine-oxy compound H are simultaneously separated off. HRMS high resolution mass spectrometry data: molecular formula C28H27O3P2(M + H): theoretical 473.1435, experimental 473.1441; molecular formula C28H26O3P2Na (M + Na): theoretical 495.1255, experimental 495.1259.
Example three: preparation of macromolecular polymerization type bisacylphosphine oxide
Under nitrogen protection and at room temperature, 1.3 g of zinc powder and 15 ml of ethyl acetate are added in sequence to a 100 ml reaction flask, a mixture of 3.8 g of previously prepared 3, 3' -methylene-bis (2, 4, 6-trimethylbenzoyl chloride) and 1.8 g of freshly distilled phenylphosphonium dichloride in 5 ml of ethyl acetate is added dropwise, and the temperature is kept for 2 hours after the dropwise addition is finished. After the reaction is finished, respectively adding 15 ml of water and 1.4 ml of 30% hydrogen peroxide into the system, continuously reacting for half an hour, after the detection reaction is finished, adding a small amount of saturated sodium bicarbonate solution for neutralization, extracting, washing with water, concentrating, pulping in ice-cold heptane, and separating to obtain 2.3 g of yellow amorphous powder solid product K.
Example four: evaluation of photocuring Property
Samples of the ethylenically (acrylate) containing UV radiation curable material formulation system were prepared according to the following formulation (in weight percent): bisphenol a epoxy acrylate (Ebecryl 605): 32 percent; aminoacrylate (Ebecryl 7100): 10 percent; acryloyl morpholine: 54 percent; photoinitiator H or K: 4 percent. The above examples were applied to cardboard to form a coating of about 20-25 microns using a UV high pressure mercury lamp (about 20 cm from the substrate) as the source of radiation and a variable speed conveyor test. The criterion for completing photopolymerization curing is that repeated nail scratching and scratching can not generate marks. The formulations containing photoinitiators H and K all showed good photo-initiated polymerization cure in one pass at a linear speed of 22 m/min.
Example five: co-production of TPO and TPO-L phosphonic acid
0.8 g of zinc powder, 15 ml of ethyl acetate and 2.2 g of 2, 4, 6-trimethylbenzoyl chloride are added to an 80 ml reaction flask in turn under nitrogen protection and stirring at room temperature, a mixture of 1.08 g of phenyldichlorophosphorus chloride and 1.32 g of diphenylphosphorus chloride in 5 ml of ethyl acetate is added dropwise to the mixture, and the mixture is kept warm for 2 hours after the dropwise addition is finished. After the reaction is finished, respectively adding 15 ml of water and 1.4 ml of 30% hydrogen peroxide into the system, continuously reacting for half an hour, after the detection reaction is finished, adding a proper amount of saturated sodium bicarbonate solution to neutralize until the pH is slightly alkaline to 7-8, and then extracting, washing with water, concentrating and separating by silica gel column chromatography to obtain 1.2 g of TPO-L phosphonic acid and 1.7 g of TPO.
Example six: co-production of TPO and 819 and TPO-L phosphonic acid
Under the protection of nitrogen and at room temperature, 1.7 g of zinc powder, 15 ml of ethyl acetate and 4.8 g of 2, 4, 6-trimethylbenzoyl chloride are added into a 100 ml reaction bottle in sequence under stirring, then a mixture of 1.8 g of phenyldichlorophosphate and 1.4 g of diphenylphosphoryl chloride in 5 ml of ethyl acetate is added dropwise into the mixture, and the mixture is kept for 2 hours after the dropwise addition is finished. After the reaction is finished, 15 ml of water and 1.6 ml of 30% hydrogen peroxide are respectively added into the system, the reaction is continued for half an hour, after the detection reaction is finished, a small amount of saturated sodium bicarbonate solution is added for neutralization, and then the neutralization, extraction, water washing and concentration are carried out, and silica gel column chromatography separation is carried out to obtain 1.6 g 819, 2.0 g TPO and 0.8 g TPO-L phosphonic acid.
The 0.8 g TPO-L phosphonic acid is placed in 20 ml absolute ethyl alcohol to react overnight at about 55 ℃ in a warm manner, and 0.74 g TPO-L photoinitiator product is obtained.
Example seven: 819 and TPO-L phosphonic acid Co-production
Under the protection of nitrogen and at room temperature, 1.4 g of zinc powder, 15 ml of ethyl acetate and 4.1 g of 2, 4, 6-trimethylbenzoyl chloride are added into a 100 ml reaction bottle in sequence under stirring, then 2.5 g of a solution of phenyldichlorophosphate in 5 ml of ethyl acetate is added into the mixture dropwise, and the mixture is kept for 2 hours after the dropwise addition is finished. After the reaction is finished, 20 ml of water and 1.5 ml of 30% hydrogen peroxide are respectively added into the system, the reaction is continued for half an hour, after the detection reaction is finished, a saturated sodium bicarbonate solution is added for neutralization to alkalescence, and then extraction, water washing and concentration are carried out, and silica gel column chromatography separation is carried out to obtain 1.5 g 819 and 1.4 g of TPO-L phosphonic acid.
It should be emphasized that the above-described embodiments are merely illustrative and not restrictive, and that any adjustments or variations, such as reaction conditions or parameters, which may be commonly employed by a person skilled in the art based on the disclosure of this application do not depart from the gist of the present invention, and the scope of protection of this patent shall be governed by the terms of the relevant claims.

Claims (11)

1. A co-production preparation technique of monoacylphosphine (structural formula D) and bisacylphosphine (E), and oxides thereof, namely monoacylphosphine oxide (F) and bisacylphosphine oxide (G); directly acting starting materials of acyl halide (A), a mixture of mono-and di-halogenated phosphine (B and C) and metal M under conditions 1; then under the action of an oxidant (O) and conditions2, the catalyst is prepared in a one-pot method mode by sharing the same process and the same reactor:
Figure FDA0002488055260000011
wherein R is1Is monovalent or divalent and contains 1 to 24 carbon atoms (denoted as C)1-C24The same applies hereinafter) straight-chain or branched alkyl or C3-C12Cycloalkyl, or R1Is monovalent or divalent C4-C24Substituted or unsubstituted aryl or heteroaryl; r2，R3Or R is4Independently of one another and monovalent R1The same; x or Y are independently of each other a halogen atom; m is metal Zn, Mg, Ni, Be, Co, Ru, Cu, Mo, Ba, Cd, Fe, Al, Cr, Mn, Ca, In; or a mixed-metal system formed from any two or more of the foregoing; [ O ] is an oxidant, air, oxygen, hydrogen peroxide, an organic alkyl peroxide, a peroxycarboxylic acid, ozone, (hypochlorite), nitrate, or a mixture of any two or more of the foregoing; the conditions 1 and 2 are each, independently of one another, at least one of a solvent, a temperature, a pressure, and an additive.
2. A coproduction preparation technology of monoacylphosphine oxide (F) and acylphosphonic acid (ester) (T); the method is characterized in that a starting material acyl halide (A), a halogenated phosphine mixture (B and C) and a metal M directly act under conditions 1 to obtain monoacylphosphine (D) and acylphosphine halide (Q), and then under the action of an oxidant [ O ] and conditions2, the monoacylphosphine (D) and the acylphosphine halide (Q) are prepared by a one-pot method sharing the same process flow and the same reactor:
Figure FDA0002488055260000021
wherein R5 is hydrogen, C1-C24Linear or branched or cyclic alkyl;
the other definitions are the same as in claim 1, below.
3. A coproduction preparation technology of acyl phosphonic acid (ester) (T) and bisacyl phosphine oxide (G); directly acting starting materials of acyl halide (A), bis-halogenated phosphine (C) and metal M under conditions 1 to obtain acyl phosphine halide (Q) and bis-acyl phosphine (E); then under the action of an oxidant [ O ] and conditions2, the catalyst is prepared by a one-pot method sharing the same process flow and the same reactor:
Figure FDA0002488055260000022
4. the process technology of claims 1-3, wherein the solvent is selected from at least one of substituted or unsubstituted aromatic hydrocarbons containing 1-24 carbons, linear or branched or cyclic aliphatic hydrocarbons, (sulfoxides), amides, ethers, esters, ketones, nitriles, carboxylic acids, water, amines, carbonates, ionic liquids, and supercritical carbon dioxide. The temperature is-70 ℃ to 300 ℃. The pressure is 0.001atm-200 atm. The additive refers to a reaction promoter, a synergist, a catalyst, an oxidant, a reducing agent and/or a functional auxiliary agent; the use amount of the additive is 0.0001-10000 equivalents based on the molar weight of the reaction raw materials.
5. Process technology according to claims 1-3Preferred is R1Is 2, 4, 6-trimethylbenzoyl chloride, 2, 6-dimethoxybenzoyl chloride, 1-naphthoyl chloride, (CH)3)3C-C (O) Cl; preferred X or Y is chlorine; preferred R2，R3Or R is4Independently of one another, phenyl, biphenyl, 1/2-naphthyl, 4-methoxyphenyl, 4-methylphenyl, 4-isopropylphenyl, 4-dimethylaminophenyl; preferred R5Is hydrogen, methyl, ethyl, or hydroxyethyl; preferably, M is a metal Zn or Mg or a combination of both.
6. The process technology of claims 1-3, wherein TPO and 819 photoinitiator products are prepared simultaneously from 2, 4, 6-trimethylbenzoyl chloride, diphenylphosphorus chloride, and phenylphosphorus dichloride with metal M under conditions 1 followed by "one pot" under the action of oxidant [ O ] and conditions 2:
Figure FDA0002488055260000031
7. the process of claims 1-3, wherein TPO and TPO-L phosphonic acid (ester) photoinitiator products are prepared simultaneously from 2, 4, 6-trimethylbenzoyl chloride, diphenylphosphorus chloride, and phenylphosphorus dichloride with metal M under conditions 1 to form the corresponding trivalent monoacylphosphanes and acylphosphine chlorides, followed by "one-pot" under the action of oxidant [ O ] and conditions 2:
Figure FDA0002488055260000041
8. the process technology of claims 1-3, wherein 2, 4, 6-trimethylbenzoyl chloride and phenyl phosphorus dichloride and metal M are reacted under conditions 1 to form corresponding trivalent bisacylphosphine and monoacylphosphine chlorides, and then the reactants are reacted under the conditions2 and O oxidant to obtain 819 and TPO-L phosphonic acid (ester) photoinitiator products:
Figure FDA0002488055260000042
9. the process of claims 1-3, wherein 2, 4, 6-trimethylbenzoyl chloride, diphenylphosphorus chloride, and phenylphosphorus dichloride are reacted with metal M under conditions 1 to form the corresponding trivalent monoacylphosphanes, acylphosphine chlorides, bisacylphosphines, followed by "one pot" under the action of oxidant [ O ] and conditions2 to simultaneously prepare phosphonic acid (ester) products of TPO, TPO-L, and 819 three photoinitiator compounds:
Figure FDA0002488055260000051
10. a monoacyl diphosphine oxygen compound shown in a structural formula H, and application thereof as a photoinitiator substance for radiation polymerization curing of an alkene-containing unsaturated system:
Figure FDA0002488055260000052
11. a polymer-form bisacylphosphine oxide photoinitiator compound shown in a structural formula K and application thereof as an alkene-containing unsaturated system radiation polymerization curing photoinitiator substance; the catalyst is prepared from bivalent acyl chloride, phenyl phosphorus dichloride and metal M under the action of conditions 1, an oxidant [ O ] and conditions2 in sequence:
Figure FDA0002488055260000053
CN202010400237.4A 2020-05-12 2020-05-12 Co-production preparation of monoacylphosphines and bisacylphosphines and their oxides Pending CN113651850A (en)

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