WO2020113585A1 - 酰基膦氧类化合物及其制备方法 - Google Patents

酰基膦氧类化合物及其制备方法 Download PDF

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WO2020113585A1
WO2020113585A1 PCT/CN2018/119922 CN2018119922W WO2020113585A1 WO 2020113585 A1 WO2020113585 A1 WO 2020113585A1 CN 2018119922 W CN2018119922 W CN 2018119922W WO 2020113585 A1 WO2020113585 A1 WO 2020113585A1
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compound
organic solvent
hours
acid solution
grignard reagent
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PCT/CN2018/119922
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English (en)
French (fr)
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钟晓锋
吴进
岳祥军
黄铁男
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安庆莱霆光电科技有限公司
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Priority to PCT/CN2018/119922 priority Critical patent/WO2020113585A1/zh
Priority to JP2021554784A priority patent/JP7432616B2/ja
Priority to KR1020217021263A priority patent/KR20210105377A/ko
Priority to US17/311,649 priority patent/US20220106340A1/en
Priority to EP18942325.4A priority patent/EP3892625A4/en
Priority to CN201880099925.2A priority patent/CN113454095B/zh
Publication of WO2020113585A1 publication Critical patent/WO2020113585A1/zh

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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 System
    • 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 System
    • 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
    • C07F9/5325—Aromatic phosphine oxides or thioxides (P-C aromatic linkage)
    • 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 System
    • C07F9/02—Phosphorus compounds
    • C07F9/28—Phosphorus compounds with one or more P—C bonds
    • C07F9/50—Organo-phosphines
    • C07F9/5022—Aromatic phosphines (P-C aromatic linkage)
    • 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
    • Y02P20/55—Design of synthesis routes, e.g. reducing the use of auxiliary or protecting groups

Definitions

  • the present disclosure relates to the field of initiators, in particular to an acylphosphine oxide compound and a preparation method thereof.
  • a photoinitiator also known as a photosensitizer or photocuring agent, is a reagent that can absorb radiation energy and undergo chemical changes to produce an active intermediate with the ability to initiate polymerization.
  • acylphosphine oxide compounds are a type of photoinitiators with high photoinitiation activity, which are widely used.
  • TPO (2,4,6-trimethylbenzoyl)diphenylphosphine oxide
  • the industrial preparation methods of TPO mainly include two types: first, diphenylphosphine chloride is subjected to an esterification reaction with methanol in an alkaline environment to obtain a diphenylphosphinic acid methyl ester intermediate, diphenylphosphinic acid The methyl phosphonate intermediate is condensed with 2,4,6-trimethylbenzoyl chloride to obtain TPO. Second, diphenylphosphine chloride is hydrolyzed to obtain diphenylphosphine oxide, which is condensed with 2,4,6-trimethylbenzaldehyde and oxidized to obtain TPO.
  • the preparation method of diphenylphosphine chloride is: after the catalytic reaction of benzene and phosphorus trichloride with aluminum trichloride, the unreacted benzene and phosphorus trichloride, phenylphosphine chloride are collected by atmospheric distillation first, and then The residue in the kettle was decomplexed with sodium chloride and distilled to collect diphenylphosphine chloride.
  • the embodiments of the present disclosure provide an acylphosphine oxide compound and a preparation method thereof, which can solve the above technical problems.
  • the specific technical solutions are as follows:
  • the embodiments of the present disclosure provide a method for preparing an acylphosphine oxide compound, wherein the method includes:
  • R 1 is hydrogen, C 1 -C 6 alkyl, methoxy, methylthio, dimethylamino, chloroformyl, phenyl, benzoyl, (4-dimethylamino)phenyl, ⁇ -Naphthyl, ⁇ -naphthyl or (9-ethyl-9H-carbazole)-3-yl;
  • R 2 is the same as R 1 ;
  • n is the number of substitution of R 1 on the corresponding benzene ring, n is 1, 2 or 3;
  • n is the number of substitutions of R 2 on the corresponding benzene ring, and m is 1, 2, or 3.
  • the method further includes:
  • Lewis acid was added to the reaction system composed of the compound B and the compound C.
  • the molar ratio of the compound B, the compound C, the organic base, and the Lewis acid is 1:1-2:1-5:0.01-2.
  • the Lewis acid is selected from trimethylchlorosilane, trimethylbromosilane, trimethyliodosilane, triethylchlorosilane, tripropylchlorosilane, tributylchlorosilane, Tert-Butyldimethylchlorosilane, tert-butyldiphenylchlorosilane, trimethylchlorosilane-sodium bromide, trimethylchlorosilane-sodium iodide, trimethylsilyl methanesulfonate, methanesulfonic acid At least one of t-butyldimethylsilyl ester, trifluoromethanesulfonic acid trimethylsilyl ester, and trifluoromethanesulfonic acid t-butyldimethylsilyl ester.
  • the organic base is selected from triethylamine, tripropylamine, N,N-diisopropylethylamine, N,N-dimethylaniline, pyridine, 2,6-dimethyl At least one of pyridine, 2-picoline, 3-picoline, and 4-picoline.
  • the organic solvent is selected from toluene, xylene, tetrahydrofuran, 2-methyltetrahydrofuran, dioxane, ethylene glycol dimethyl ether, methyl tert-butyl ether, dichloromethane, At least one of 1,2-dichloroethane, acetonitrile, N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, dimethyl sulfoxide, and sulfolane.
  • the reaction temperature of the compound B and the compound C is -20°C-150°C, and the reaction time is 1-8 hours.
  • reaction of Compound B and Compound C under the conditions of an organic base and an organic solvent includes:
  • the compound B is added to the first reactor to react the compound B and the compound C.
  • the adding the compound B to the first reactor includes:
  • the second mixed liquid was added dropwise to the first reactor.
  • the acquiring the first mixed liquid including the compound C and the organic solvent includes:
  • R 2 is hydrogen, C 1 -C 6 alkyl, methoxy, methylthio, dimethylamino, chloroformyl, phenyl, benzoyl, (4-dimethylamino)phenyl, ⁇ -Naphthyl, ⁇ -naphthyl or (9-ethyl-9H-carbazole)-3-yl;
  • n is the number of substitution of R 2 on the corresponding benzene ring, m is 1, 2 or 3;
  • X is chlorine, bromine or iodine.
  • the molar ratio of the diethyl phosphite to the Grignard reagent is 1:3-5.
  • the acid solution is selected from at least one of hydrochloric acid solution, hydrobromic acid solution, hydroiodic acid solution, sulfuric acid solution, acetic acid solution, oxalic acid solution, and citric acid solution.
  • the reaction temperature of the Grignard reagent and the diethyl phosphite is -20°C-150°C, and the reaction time is 1-4 hours.
  • the Grignard reagent and diethyl phosphite are reacted in an organic solvent, and then quenched by an acid solution and then treated, including:
  • the third mixed solution of the Grignard reagent and the organic solvent is prepared by the following method:
  • the magnesium powder and the aromatic halide are reacted to obtain a third mixed solution including the Grignard reagent and the organic solvent;
  • R 2 is hydrogen, C 1 -C 6 alkyl, methoxy, methylthio, dimethylamino, chloroformyl, phenyl, benzoyl, (4-dimethylamino)phenyl, ⁇ -Naphthyl, ⁇ -naphthyl or (9-ethyl-9H-carbazole)-3-yl;
  • n is the number of substitution of R 2 on the corresponding benzene ring, m is 1, 2 or 3;
  • X is chlorine, bromine or iodine.
  • the molar ratio of the aromatic halide to the magnesium powder is 1:1-2.
  • the initiator is selected from at least one of iodine and dibromoethane.
  • reaction time of the magnesium powder and the aromatic halide is 2-4 hours.
  • the embodiments of the present disclosure provide an acylphosphine oxide compound, wherein the chemical structural formula of the compound is as follows:
  • R 1 is hydrogen, C 1 -C 6 alkyl, methoxy, methylthio, dimethylamino, chloroformyl, phenyl, benzoyl, (4-dimethylamino)phenyl, ⁇ -Naphthyl, ⁇ -naphthyl or (9-ethyl-9H-carbazole)-3-yl;
  • R 2 is the same as R 1 ;
  • n is the number of substitution of R 1 on the corresponding benzene ring, n is 1, 2 or 3;
  • n is the number of substitutions of R 2 on the corresponding benzene ring, and m is 1, 2, or 3.
  • the compound B and the compound C are reacted to obtain the acylphosphine oxide compound under the condition of an organic base and an organic solvent.
  • the preparation method does not use diphenylphosphine chloride as a raw material for production, and does not involve an oxidation operation. It has the characteristics of safety, environmental protection, easy operation, and high yield, which is beneficial to the production of acylphosphine oxide compounds.
  • the acylphosphine oxide compound prepared by this method has stable quality, high purity, high yield and low cost, which is beneficial to industrial production.
  • the embodiments of the present disclosure provide a method for preparing an acylphosphine oxide compound.
  • the method includes:
  • R 1 is hydrogen, C 1 -C 6 alkyl, methoxy, methylthio, dimethylamino, chloroformyl, phenyl, benzoyl, (4-dimethylamino)phenyl, ⁇ -Naphthyl, ⁇ -naphthyl or (9-ethyl-9H-carbazole)-3-yl;
  • R 2 is the same as R 1 ;
  • n is the number of substitution of R 1 on the corresponding benzene ring, n is 1, 2 or 3;
  • n is the number of substitutions of R 2 on the corresponding benzene ring, and m is 1, 2, or 3.
  • substitution position of R 1 on the corresponding benzene ring may be the ortho position, meta position or para position of the acyl group.
  • substitution position of R 2 on the corresponding benzene ring may be the ortho position, meta position or para position of the phosphine group.
  • the acylphosphine oxide compound can be used as a photoinitiator, which has the advantages of high initiation polymerization activity, fast photocuring speed, excellent thermal stability, low post-polymerization effect, no residue, etc., and can be applied to ultraviolet light Curing coatings, printing inks, ultraviolet curing adhesives, optical fiber coatings, photoresists, photopolymerizable printing plates, three-dimensional lithographic resins, tooth fillings, etc.
  • the usage amount of the organic solvent is not specifically limited, and it is sufficient to dissolve the components and to satisfy the reaction.
  • the compound B and the compound C are reacted to obtain the acylphosphine oxide compound under the condition of an organic base and an organic solvent.
  • the preparation method does not use diphenylphosphine chloride as a raw material for production, and does not involve an oxidation operation. It has the characteristics of safety, environmental protection, easy operation, and high yield, which is beneficial to the production of acylphosphine oxide compounds.
  • the acylphosphine oxide compound prepared by this method has stable quality, high purity, high yield and low cost, which is beneficial to industrial production.
  • the preparation method of the acylphosphine oxide compound provided by the embodiment of the present disclosure further includes: adding a Lewis acid to the reaction system composed of the compound B and the compound C.
  • reaction system composed of Compound B and Compound C includes: Compound B, Compound C, an organic base, and an organic solvent.
  • compound B and compound C By adding a Lewis acid to the reaction system composed of compound B and compound C, compound B and compound C can be promoted to produce compound A without side reactions.
  • the molar ratio of compound B, compound C, organic base, and Lewis acid has an important influence on whether the acylphosphine oxide compound can be efficiently prepared. Based on this, the molar ratio of compound B, compound C, organic base, and Lewis acid can be 1:1-2:1-5:0.01-2, and the molar ratio of compound B, compound C, organic base, and Lewis acid can also be 1:1:1-3:1.
  • the molar ratio of compound B, compound C, organic base, and Lewis acid may be 1:1:1:0.01, 1:1.1:1.1:0.3, 1:1.4:2:0.5, 1:1.7:2.4: 0.7, 1:1.8:3:0.9, 1:1:1:1, 1:1:2:1, 1:1:3:1, 1:1.9:4:1.5, 1:2:5:2, etc. .
  • the compound B and the compound C can sufficiently react, and the reaction rate is fast, which facilitates the production of acylphosphine oxide compounds with high efficiency and high yield.
  • the Lewis acid is selected from trimethylchlorosilane, trimethylbromosilane, trimethyliodosilane, triethylchlorosilane, tripropylchlorosilane, Butylchlorosilane, tert-butyldimethylchlorosilane, tert-butyldiphenylchlorosilane, trimethylchlorosilane-sodium bromide, trimethylchlorosilane-sodium iodide, trimethylsilyl methanesulfonate At least one of an ester, t-butyldimethylsilyl methanesulfonate, trimethylsilyl trifluoromethanesulfonate, and t-butyldimethylsilyl trifluoromethanesulfonate.
  • the Lewis acid may be selected from any one, two, three, four, five, six, seven, ... of the above.
  • the ratio of each component is not specifically limited.
  • Lewis acids can effectively promote the reaction between compound B and compound C, and they have good mutual solubility with other components, and are inexpensive and easy to obtain.
  • the Lewis acid After adding the Lewis acid, it may be stirred for 0.8 to 1.5 hours, for example, 0.8 hours, 0.9 hours, 1 hour, 1.1 hours, 1.2 hours, 1.3 hours, 1.4 hours, 1.5 hours, and the like.
  • the organic base can absorb the hydrogen chloride generated by the reaction of the compound B and the compound C, and the organic base will not cause side reactions.
  • An embodiment of the present disclosure gives an example of the type of organic base: the organic base is selected from triethylamine, tripropylamine, N,N-diisopropylethylamine, N,N-dimethylaniline, pyridine, 2, At least one of 6-lutidine, 2-picoline, 3-picoline, and 4-picoline.
  • the organic base is selected from any one, two, three, four, five, six, seven, eight, and nine of the above.
  • the ratio of each component is not specifically limited.
  • the mass ratio of the two can be 1:1, 1:2, 1:3, 2:1, 2 :3 etc.
  • the mass ratio of the three can be 1:1:1, 1:2: 1, 1:3:1, 2:1:1, 2:3:1, 2:2:1, 2:3:1, 2:1:3, 2:3:3, etc.
  • the above-mentioned organic bases can not only effectively promote the reaction between compound B and compound C to form compound A. And it's cheap and easy to get.
  • the organic solvent can make the compound B and the compound C fully and uniformly dispersed, which is conducive to the reaction between the two.
  • An embodiment of the present disclosure gives an example of the type of organic solvent: the organic solvent is selected from toluene, xylene, tetrahydrofuran, 2-methyltetrahydrofuran, dioxane, ethylene glycol dimethyl ether, methyl tert-butyl ether , Dichloromethane, 1,2-dichloroethane, acetonitrile, N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, dimethyl sulfoxide, sulfolane At least one.
  • the organic solvent may be selected from any one, two, three, four, ..., or all of the above.
  • the ratio of each component is not specifically limited.
  • the mass ratio of toluene and tetrahydrofuran can be 1:1, 1:1.2, 1:1.4, 1:1.5, 1:1.7, 1:1.9, 1:2 Wait.
  • the above-mentioned organic solvents make the compound B and the compound C have good mutual solubility, and are inexpensive and easy to obtain.
  • the reaction temperature of compound B and compound C may be -20°C-150°C, for example, -20°C, -10°C, -5°C, 0°C, 10°C, 20°C, 30°C, 40°C, 50°C, 60 °C, 70 °C, 80 °C, 90 °C, 100 °C, 110 °C, 120 °C, 130 °C, 140 °C, 150 °C, etc.
  • the reaction time may be 1-8 hours, for example, 1 hour, 1.8 hours, 1.9 hours, 2 hours, 2.1 hours, 2.2 hours, 2.3 hours, 2.4 hours, 2.5 hours, 3 hours, 3.5 hours, 4 hours, 4.5 hours , 5 hours, 5.5 hours, 6 hours, 6.5 hours, 7 hours, 7.5 hours, 8 hours, etc.
  • the embodiments of the present disclosure give the following two examples on how to make the compound B, compound C, organic base, and organic solvent mixed react:
  • reaction of Compound B and Compound C under the conditions of an organic base and an organic solvent includes:
  • Step A Obtain a first mixed solution including Compound C and an organic solvent, and mix it with an organic base in a first reactor.
  • obtaining the first mixed solution including Compound C and the organic solvent can be obtained by mixing Compound C and the organic solvent, or can be obtained by the following steps:
  • the Grignard reagent and diethyl phosphite are reacted in an organic solvent, and then quenched by an acid solution for post-treatment to obtain a first mixed solution including Compound C and an organic solvent;
  • R 2 is hydrogen, C 1 -C 6 alkyl, methoxy, methylthio, dimethylamino, chloroformyl, phenyl, benzoyl, (4-dimethylamino)phenyl, ⁇ -Naphthyl, ⁇ -naphthyl or (9-ethyl-9H-carbazole)-3-yl;
  • n is the number of substitution of R 2 on the corresponding benzene ring, m is 1, 2 or 3;
  • X is chlorine, bromine or iodine.
  • the molar ratio of diethyl phosphite to Grignard reagent has an important influence on whether they can react sufficiently. Based on this, in the embodiments of the present disclosure, the molar ratio of diethyl phosphite to Grignard reagent It can be 1:3-5, and the molar ratio of diethyl phosphite to Grignard reagent can also be 1:3-3.5.
  • the molar ratio of diethyl phosphite to Grignard reagent can be 1:3, 1:3.1, 1:3.3, 1:3.5, 1:3.7, 1:3.9, 1:4, 1:4.1, 1: 4.3, 1:4.5, 1:4.7, 1:4.9, 1:5, etc.
  • the reaction temperature between Grignard reagent and diethyl phosphite can be -20°C-150°C, for example, it can be -20°C, -10°C, -5°C, 0°C, 10°C, 20°C, 30°C, 40°C , 50 °C, 60 °C, 70 °C, 80 °C, 90 °C, 100 °C, 110 °C, 120 °C, 130 °C, 140 °C, 150 °C and so on.
  • the reaction time of Grignard reagent and diethyl phosphite can be 1-4 hours, for example, it can be 1 hour, 1.5 hours, 2 hours, 2.5 hours, 2.8 hours, 2.9 hours, 3 hours, 3.1 hours, 3.2 hours, 3.3 Hours, 3.4 hours, 3.5 hours, 4 hours, etc.
  • the molar ratio of the above-mentioned diethyl phosphite and Grignard reagent, the reaction temperature and the reaction time are combined to facilitate the sufficient reaction of the diethyl phosphite and the Grignard reagent.
  • a first mixed solution including compound C and an organic solvent can be obtained in high yield.
  • the acid solution is selected from at least one of hydrochloric acid solution, hydrobromic acid solution, hydroiodic acid solution, sulfuric acid solution, acetic acid solution, oxalic acid solution, and citric acid solution.
  • the acid solution is selected from any one, two, three, four, five, six, and seven of the above.
  • the ratio of each component is not specifically limited.
  • the molar ratio of the acetic acid solution and the citric acid solution may be 1:1, 1:2, 1:3, 2:1, 2:3, and so on.
  • the mass concentration of the acid solution may be 30%-60%.
  • Step B Compound B is added to the first reactor to make Compound B and Compound C react.
  • Adding compound B to the first reactor includes but is not limited to the following methods:
  • the second mixed liquid was added dropwise to the first reactor.
  • the Grignard reagent and diethyl phosphite are reacted in an organic solvent, and then quenched by an acid solution to post-process, including: adding phosphorous acid to the second reactor with a third mixed solution of Grignard reagent and organic solvent Diethyl ester, react Grignard reagent with diethyl phosphite, and then quench the reaction with acid solution.
  • the third mixed solution of the Grignard reagent and the organic solvent can be directly obtained by mixing the Grignard reagent and the organic solvent, or can be prepared by the following method:
  • the magnesium powder and the aromatic halide are reacted to obtain a third mixed solution including the Grignard reagent and the organic solvent.
  • R 2 is hydrogen, C 1 -C 6 alkyl, methoxy, methylthio, dimethylamino, chloroformyl, phenyl, benzoyl, (4-dimethylamino)phenyl, ⁇ -Naphthyl, ⁇ -naphthyl or (9-ethyl-9H-carbazole)-3-yl;
  • n is the number of substitution of R 2 on the corresponding benzene ring, m is 1, 2 or 3;
  • X is chlorine, bromine or iodine.
  • the step of separating the Grignard reagent can be omitted to efficiently prepare the acylphosphine oxide compound.
  • the molar ratio of aromatic halogen to magnesium powder has an important influence on whether the two can fully react. Based on this, the molar ratio of aromatic halogen to magnesium powder can be 1:1-2, and the molar ratio of aromatic halogen to magnesium powder can also be 1:1-1.2. For example, the molar ratio of aromatic halogen to magnesium powder may be 1:1, 1:1.2, 1:1.4, 1:1.5, 1:1.7, 1:1.9, 1:2, and so on.
  • the initiator may be selected from at least one of iodine and dibromoethane. That is, the initiator is selected from iodine, dibromoethane, a mixture of iodine and dibromoethane.
  • the above-mentioned initiators have good initiating effects, and can ensure that the aromatic halide fully reacts with the magnesium powder. Moreover, the above-mentioned initiators are inexpensive and easy to obtain.
  • the reaction time of magnesium powder and aromatic halide may be 2-4 hours, for example, 2 hours, 2.2 hours, 2.5 hours, 2.7 hours, 2.8 hours, 2.9 hours, 3 hours, 3.1 hours, 3.2 hours, 3.3 hours, 3.4 hours , 3.5 hours, 3.7 hours, 4 hours, etc. In this way, it can be ensured that the aromatic halide and the magnesium powder react fully under the triggering effect of the initiator.
  • the mixed solution of the initiator, the aromatic halogen and the organic solvent can be added dropwise to the second reactor, and then the mixed solution of the aromatic halogen and the organic solvent can be added dropwise to the second reactor.
  • the initiator can cause the magnesium powder to react with the aromatic halide, and then the aromatic halide added to continue the reaction, which is beneficial to reduce the amount of initiator.
  • Diethyl phosphite can be added to the second reactor in a dropwise manner to react Grignard reagent with diethyl phosphite to obtain a reaction solution, which is stirred for 1-4 hours, and then cooled to room temperature. Subsequently, the reaction solution was added dropwise to the acid solution to perform quenching reaction, and finally compound C was obtained.
  • the room temperature involved in the embodiments of the present disclosure may be 20°C-30°C, for example, 20°C, 21°C, 22°C, 23°C, 24°C, 25°C, 26°C, 27°C, 28°C, 29°C, 30°C etc.
  • the specific room temperature can be determined according to the actual operating environment.
  • the first reactor and the second reactor may be the same reactor.
  • the Grignard reagent and compound C are not separately separated, and the corresponding mixed solution is directly used for preparation, which avoids the discharge of intermediates and is easy for industrial production.
  • the acylphosphine oxide compound can be obtained by washing treatment and separation treatment.
  • the washing process can wash away impurities in the mixed liquid, and the washing process can be washed by an organic solvent or water.
  • the separation treatment may be vacuum distillation, extraction and other treatments.
  • the compound B and the compound C are reacted to obtain the acylphosphine oxide compound under the conditions of an organic base, an organic solvent and a Lewis acid.
  • the preparation method does not use diphenylphosphine chloride as a raw material for production, and does not involve an oxidation operation. It has the characteristics of safety, environmental protection, easy operation, and high yield, which is beneficial to the production of acylphosphine oxide compounds.
  • the acylphosphine oxide compound prepared by this method has stable quality, high purity, high yield and low cost, which is beneficial to industrial production.
  • the embodiments of the present disclosure provide an acylphosphine oxide compound, wherein the chemical structural formula of the compound is as follows:
  • R 1 is hydrogen, C 1 -C 6 alkyl, methoxy, methylthio, dimethylamino, chloroformyl, phenyl, benzoyl, (4-dimethylamino)phenyl, ⁇ -Naphthyl, ⁇ -naphthyl or (9-ethyl-9H-carbazole)-3-yl;
  • R 2 is the same as R 1 ;
  • n is the number of substitution of R 1 on the corresponding benzene ring, n is 1, 2 or 3;
  • n is the number of substitutions of R 2 on the corresponding benzene ring, and m is 1, 2, or 3.
  • the acylphosphine oxide compounds provided in the embodiments of the present disclosure are obtained by reacting compound B and compound C under the conditions of an organic base and an organic solvent.
  • the product quality of the acylphosphine oxide compound is stable, the purity is high, and the photoinitiation activity is relatively High, can be widely used in industrial production.
  • this example provides a (2,4,6-trimethylbenzoyl)diphenylphosphine oxide (TPO), whose chemical structural formula is as follows:
  • the TPO is prepared by the following method:
  • the temperature of the mixed solution including Grignard reagent and tetrahydrofuran in the flask was 40°C-50°C, and 138 g of diethyl phosphite was added dropwise to the flask under stirring for 30 minutes. After continuing to stir the reaction for 3 hours under the state of micro-reflux, the temperature was lowered to room temperature. Then, under stirring conditions, 500 ml of a citric acid solution with a mass concentration of 50% was slowly added to the flask, stirring was continued for 30 minutes, and the layer was left to stand for 30 minutes. The organic phase was separated and concentrated under reduced pressure at 40°C-50°C to obtain an organic residue (including diphenylphosphine oxide), and tetrahydrofuran was recovered.
  • the aqueous phase was mixed with 1 liter of toluene, stirred at room temperature for 30 minutes, and allowed to stand for 30 minutes. Then, the toluene phase was separated and combined with the organic residue separated above to obtain diphenylphosphine oxide (compound C) and toluene And a mixture of impurities such as hydrogen chloride.
  • the mixture was washed with 300 ml of 10% sodium bicarbonate aqueous solution and 300 ml of water in sequence, and about 400 ml of toluene was distilled off under reduced pressure at 50°C-60°C, the remainder was diphenyl oxidation A mixture of phosphine and toluene.
  • the mixture of diphenylphosphine oxide and toluene is mixed with 220 g of triethylamine in the flask, and 105 g of trimethylchlorosilane is added dropwise to the flask under the condition of 40°C-50°C
  • the mixed solution with 100 ml of toluene was added dropwise for 1 hour, and stirring was continued for 1 hour after the addition was completed.
  • a mixture of 185 g of 2,4,6-trimethylbenzoyl chloride (Compound B) and 200 ml of toluene was added dropwise to the flask for 2 hours. Then, the reaction was stirred at 50°C for 2 hours, and the temperature was lowered to room temperature.
  • the reaction liquid in the flask was washed twice with 500 ml of water. After washing, the organic phase was separated and the volatiles were distilled off under reduced pressure at 40-50°C. Then, 600 ml of isopropyl ether was added to the organic phase, and the mixture was stirred and beaten at 55°C-65°C for 2 hours, and then stirred and beaten at 5°C-10°C for 1 hour, and suction filtered to obtain a filter cake. After washing the filter cake with cold isopropyl ether, it was dried under reduced pressure at 40°C-50°C to obtain 324 g of the TPO provided in this example, with a purity of 99.6%. The TPO was calculated based on diethyl phosphite The rate is 93%.
  • this example provides a (2,4,6-trimethylbenzoyl)bis(p-tolyl)phosphine oxide, the chemical structure of which is as follows:
  • the (2,4,6-trimethylbenzoyl)bis(p-tolyl)phosphine oxide is prepared by the following method:
  • the temperature of the mixed solution including Grignard reagent and tetrahydrofuran in the flask was 40°C-50°C, and 138 g of diethyl phosphite was added dropwise to the flask under stirring for 30 minutes. After continuing to stir the reaction for 3 hours under the state of micro-reflux, the temperature was lowered to room temperature. Then, under stirring conditions, 500 ml of a citric acid solution with a mass concentration of 50% was slowly added to the flask, stirring was continued for 30 minutes, and the layer was left to stand for 30 minutes.
  • the organic phase was separated and concentrated under reduced pressure at 40°C-50°C to obtain an organic residue (including bis(p-tolyl)phosphine oxide), and tetrahydrofuran was recovered.
  • the aqueous phase was mixed with 1 liter of toluene, stirred at room temperature for 30 minutes, and allowed to stand for 30 minutes. Then, the toluene phase was separated and combined with the organic residue separated above to obtain bis(p-tolyl)phosphine oxide (compound C), a mixture of toluene, hydrogen chloride and other impurities.
  • the mixture was washed with 300 ml of 10% sodium bicarbonate aqueous solution and 300 ml of water in sequence, and about 400 ml of toluene was distilled off under reduced pressure at 50°C-60°C, and the remainder was di(p- Tolyl) a mixture of phosphine oxide and toluene.
  • the mixture of bis(p-tolyl)phosphine oxide and toluene is mixed with 220 g of triethylamine in the flask, and 197 g of three is added dropwise to the flask under the condition of 40°-50°C
  • the mixed solution of methyl iodide silane and 100 ml of toluene was added dropwise for 1 hour, and stirring was continued for 1 hour after the addition.
  • a mixed liquid of 195 g of 2,4,6-trimethylbenzoyl chloride (Compound B) and 200 ml of toluene was added dropwise to the flask for 2 hours. Then, the reaction was stirred at 50°C for 2 hours, and the temperature was lowered to room temperature.
  • the reaction liquid in the flask was washed twice with 500 ml of water. After washing, the organic phase was separated and the volatiles were distilled off under reduced pressure at 40-50°C. Then, 600 ml of isopropyl ether was added to the organic phase, and the mixture was stirred and beaten at 55°C-65°C for 2 hours, and then stirred and beaten at 5°C-10°C for 1 hour, and filtered with suction to obtain a filter cake.
  • this example provides a (p-dimethylaminobenzoyl) diphenylphosphine oxide, the chemical structure of which is as follows:
  • the (p-dimethylaminobenzoyl) diphenylphosphine oxide is prepared by the following method:
  • the temperature of the mixed solution including Grignard reagent and tetrahydrofuran in the flask was 40°C-50°C, and 138 g of diethyl phosphite was added dropwise to the flask under stirring for 30 minutes. After continuing to stir the reaction for 3 hours under the state of micro-reflux, the temperature was lowered to room temperature. Then, under stirring, 500 ml of citric acid solution with a mass concentration of 50% was slowly added to the flask, stirring was continued for 30 minutes, and the layer was left to stand for 30 minutes. The organic phase was separated and concentrated under reduced pressure at 40°C-50°C to obtain an organic residue (including diphenylphosphine oxide), and tetrahydrofuran was recovered.
  • the aqueous phase was mixed with 1 liter of toluene, stirred at room temperature for 30 minutes, and allowed to stand for 30 minutes. Then, the toluene phase was separated and combined with the organic residue separated above to obtain diphenylphosphine oxide (compound C) and toluene And a mixture of impurities such as hydrogen chloride.
  • the mixture was washed with 300 ml of 10% sodium bicarbonate aqueous solution and 300 ml of water in sequence, and about 400 ml of toluene was distilled off under reduced pressure at 50°C-60°C, the remainder was diphenyl oxidation A mixture of phosphine and toluene.
  • the mixture of diphenylphosphine oxide and toluene is mixed with 220 g of triethylamine in the flask, and 148 g of trimethylbromosilane is added dropwise to the flask under the condition of 40°C-50°C
  • the mixed solution with 100 ml of toluene was added dropwise for 1 hour, and stirring was continued for 1 hour after the addition was completed.
  • a mixed liquid of 176 g of p-dimethylaminobenzoyl chloride (Compound B) and 200 ml of toluene was added dropwise to the flask for 2 hours. Then, the reaction was stirred at 50°C for 2 hours, and the temperature was lowered to room temperature.
  • the reaction liquid in the flask was washed twice with 500 ml of water. After washing, the organic phase was separated and the volatiles were distilled off under reduced pressure at 40-50°C. Then, 600 ml of isopropyl ether was added to the organic phase, and the mixture was stirred and beaten at 55°C-65°C for 2 hours, and then stirred and beaten at 5°C-10°C for 1 hour, and filtered by suction to obtain a filter cake.
  • this example provides a (p-methoxybenzoyl) diphenylphosphine oxide, the chemical structure of which is as follows:
  • the (p-methoxybenzoyl)diphenylphosphine oxide is prepared by the following method:
  • the temperature of the mixed solution including Grignard reagent and tetrahydrofuran in the flask was 40°C-50°C, and 138 g of diethyl phosphite was added dropwise to the flask under stirring for 30 minutes. After continuing to stir the reaction for 3 hours under the state of micro-reflux, the temperature was lowered to room temperature. Then, under stirring conditions, 500 ml of a citric acid solution with a mass concentration of 50% was slowly added to the flask, stirring was continued for 30 minutes, and the layer was left to stand for 30 minutes. The organic phase was separated and concentrated under reduced pressure at 40°C-50°C to obtain an organic residue (including diphenylphosphine oxide), and tetrahydrofuran was recovered.
  • the aqueous phase was mixed with 1 liter of toluene, stirred at room temperature for 30 minutes, and allowed to stand for 30 minutes. Then, the toluene phase was separated and combined with the organic residue separated above to obtain diphenylphosphine oxide (compound C) and toluene And a mixture of impurities such as hydrogen chloride.
  • the mixture was washed with 300 ml of 10% sodium bicarbonate aqueous solution and 300 ml of water in sequence, and about 400 ml of toluene was distilled off under reduced pressure at 50°C-60°C, the remainder was diphenyl oxidation A mixture of phosphine and toluene.
  • the mixture of diphenylphosphine oxide and toluene is mixed with 220 g of triethylamine in the flask, and 105 g of trimethylchlorosilane is added dropwise to the flask under the condition of 40°C-50°C
  • the mixed solution with 100 ml of toluene was added dropwise for 1 hour, and stirring was continued for 1 hour after the addition was completed.
  • a mixture of 164 g of p-methoxybenzoyl chloride (Compound B) and 200 ml of toluene was added dropwise to the flask for 2 hours. Then, the reaction was stirred at 50°C for 2 hours, and the temperature was lowered to room temperature.
  • the reaction liquid in the flask was washed twice with 500 ml of water. After washing, the organic phase was separated and the volatiles were distilled off under reduced pressure at 40-50°C. Then, 600 ml of isopropyl ether was added to the organic phase, and the mixture was stirred and beaten at 55°C-65°C for 2 hours, and then stirred and beaten at 5°C-10°C for 1 hour, and filtered with suction to obtain a filter cake.
  • this example provides a (p-methylthiobenzoyl) diphenylphosphine oxide, the chemical structure of which is as follows:
  • the (p-methylthiobenzoyl)diphenylphosphine oxide is prepared by the following method:
  • the temperature of the mixed solution including Grignard reagent and tetrahydrofuran in the flask was 40°C-50°C, and 138 g of diethyl phosphite was added dropwise to the flask under stirring for 30 minutes. After continuing to stir the reaction for 3 hours under the state of micro-reflux, the temperature was lowered to room temperature. Then, under stirring conditions, 500 ml of a citric acid solution with a mass concentration of 50% was slowly added to the flask, stirring was continued for 30 minutes, and the layer was left to stand for 30 minutes. The organic phase was separated and concentrated under reduced pressure at 40°C-50°C to obtain an organic residue (including diphenylphosphine oxide), and tetrahydrofuran was recovered.
  • the aqueous phase was mixed with 1 liter of toluene, stirred at room temperature for 30 minutes, and allowed to stand for 30 minutes. Then, the toluene phase was separated and combined with the organic residue separated above to obtain diphenylphosphine oxide (compound C) and toluene And a mixture of impurities such as hydrogen chloride.
  • the mixture was washed with 300 ml of 10% sodium bicarbonate aqueous solution and 300 ml of water in sequence, and about 400 ml of toluene was distilled off under reduced pressure at 50°C-60°C, the remainder was diphenyl oxidation A mixture of phosphine and toluene.
  • the mixture of diphenylphosphine oxide and toluene is mixed with 220 g of triethylamine in the flask, and 105 g of trimethylchlorosilane is added dropwise to the flask under the condition of 40°C-50°C
  • the mixed solution with 100 ml of toluene was added dropwise for 1 hour, and stirring was continued for 1 hour after the addition was completed.
  • a mixture of 181 g of p-methylthiobenzoyl chloride (Compound B) and 200 ml of toluene was added dropwise to the flask for 2 hours. Then, the reaction was stirred at 50°C for 2 hours, and the temperature was lowered to room temperature.
  • the reaction liquid in the flask was washed twice with 500 ml of water. After washing, the organic phase was separated and the volatiles were distilled off under reduced pressure at 40-50°C. Then, 600 ml of isopropyl ether was added to the organic phase, and the mixture was stirred and beaten at 55°C-65°C for 2 hours, and then stirred and beaten at 5°C-10°C for 1 hour, and filtered by suction to obtain a filter cake.
  • this example provides a (p-tolylbenzoyl) diphenylphosphine oxide, the chemical structure of which is as follows:
  • the (p-tolylbenzoyl)diphenylphosphine oxide is prepared by the following method:
  • the temperature of the mixed solution including Grignard reagent and tetrahydrofuran in the flask was 40°C-50°C, and 138 g of diethyl phosphite was added dropwise to the flask under stirring for 30 minutes. After continuing to stir the reaction for 3 hours under the state of micro-reflux, the temperature was lowered to room temperature. Then, under stirring conditions, 500 ml of a citric acid solution with a mass concentration of 50% was slowly added to the flask, stirring was continued for 30 minutes, and the layer was left to stand for 30 minutes. The organic phase was separated and concentrated under reduced pressure at 40°C-50°C to obtain an organic residue (including diphenylphosphine oxide), and tetrahydrofuran was recovered.
  • the aqueous phase was mixed with 1 liter of toluene, stirred at room temperature for 30 minutes, and allowed to stand for 30 minutes. Then, the toluene phase was separated and combined with the organic residue separated above to obtain diphenylphosphine oxide (compound C) and toluene And a mixture of impurities such as hydrogen chloride.
  • the mixture was washed with 300 ml of 10% sodium bicarbonate aqueous solution and 300 ml of water in sequence, and about 400 ml of toluene was distilled off under reduced pressure at 50°C-60°C, the remainder was diphenyl oxidation A mixture of phosphine and toluene.
  • the mixture of diphenylphosphine oxide and toluene is mixed with 220 g of triethylamine in the flask, and 105 g of trimethylchlorosilane is added dropwise to the flask under the condition of 40°C-50°C
  • the mixed solution with 100 ml of toluene was added dropwise for 1 hour, and stirring was continued for 1 hour after the addition was completed.
  • a mixed liquid of 208 g of p-phenylbenzoyl chloride (Compound B) and 200 ml of toluene was added dropwise to the flask for 2 hours. Then, the reaction was stirred at 50°C for 2 hours, and the temperature was lowered to room temperature.
  • the reaction liquid in the flask was washed twice with 500 ml of water. After washing, the organic phase was separated and the volatiles were distilled off under reduced pressure at 40-50°C. Then, 600 ml of isopropyl ether was added to the organic phase, and the mixture was stirred and beaten at 55°C-65°C for 2 hours, and then stirred and beaten at 5°C-10°C for 1 hour, and filtered with suction to obtain a filter cake.
  • this example provides a (1,4-phthaloyl)bis(diphenylphosphine oxide), whose chemical structural formula is as follows:
  • the (1,4-phthaloyl)bis(diphenylphosphine oxide) is prepared by the following method:
  • the temperature of the mixed solution including Grignard reagent and tetrahydrofuran in the flask was 40°C-50°C, and 138 g of diethyl phosphite was added dropwise to the flask under stirring for 30 minutes. After continuing to stir the reaction for 3 hours under the state of micro-reflux, the temperature was lowered to room temperature. Then, 500 ml of a citric acid solution with a mass concentration of 50% was slowly added to the flask under stirring, stirring was continued for 30 minutes, and the layer was left to stand for 30 minutes. The organic phase was separated and concentrated under reduced pressure at 40°C-50°C to obtain an organic residue (including diphenylphosphine oxide), and tetrahydrofuran was recovered.
  • the aqueous phase was mixed with 1 liter of toluene, stirred at room temperature for 30 minutes, and allowed to stand for 30 minutes. Then, the toluene phase was separated and combined with the organic residue separated above to obtain diphenylphosphine oxide (compound C) and toluene And a mixture of impurities such as hydrogen chloride.
  • the mixture was washed with 300 ml of 10% sodium bicarbonate aqueous solution and 300 ml of water in sequence, and about 400 ml of toluene was distilled off under reduced pressure at 50°C-60°C, the remainder was diphenyl oxidation A mixture of phosphine and toluene.
  • the mixture of diphenylphosphine oxide and toluene is mixed with 220 g of triethylamine in the flask, and 203 g of trifluoromethanesulfonic acid is added dropwise to the flask under the condition of 40°C-50°C
  • the mixed solution of trimethylsilyl ester and 100 ml of toluene was added dropwise for 1 hour, and stirring was continued for 1 hour after the addition was completed.
  • a mixed solution of 97 g of 1,4-phthaloyl chloride (Compound B) and 200 ml of toluene was added dropwise to the flask for 2 hours. Then, the reaction was stirred at 50°C for 2 hours, and the temperature was lowered to room temperature.
  • the reaction liquid in the flask was washed twice with 500 ml of water. After washing, the organic phase was separated and the volatiles were distilled off under reduced pressure at 40-50°C. Then, 600 ml of isopropyl ether was added to the organic phase, and the mixture was stirred and beaten at 55°C-65°C for 2 hours, and then stirred and beaten at 5°C-10°C for 1 hour, and filtered with suction to obtain a filter cake. After the filter cake was washed with cold isopropyl ether, it was dried under reduced pressure at 40°C-50°C to obtain 243 g of (1,4-phthaloyl)bis(diphenylphosphine oxide) provided in this example. The purity is 99.8%, and the yield of (1,4-phthaloyl)bis(diphenylphosphine oxide) based on diethyl phosphite is 91%.
  • the method for preparing acylphosphine oxide compounds provided by the embodiments of the present disclosure can obtain products with stable product quality, high purity, and high yield, which is beneficial to industrial production.

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Abstract

本申请公开了一种酰基膦氧类化合物及其制备方法，属于引发剂领域。该方法包括：在有机碱及有机溶剂的条件下，使化合物B和化合物C反应，得到酰基膦氧类化合物；其中，化合物B的化学结构式如下：(B) 化合物C的化学结构式如下：(C) 酰基膦氧类化合物的化学结构式如下：(A)其中，R 1为氢、C 1-C 6烷基、甲氧基、甲硫基、二甲氨基、氯甲酰基、苯基、苯甲酰基、(4-二甲胺基)苯基、α-萘基、β-萘基或(9-乙基-9H-咔唑)-3-基； R 2与R 1相同； n为R 1在对应苯环上的取代个数，n为1、2或3； m为R 2在对应苯环上的取代个数，m为1、2或3。该制备方法安全、环保、产率高。

Description

酰基膦氧类化合物及其制备方法 技术领域
本公开涉及引发剂领域，特别涉及一种酰基膦氧类化合物及其制备方法。
背景技术
光引发剂又称光敏剂或光固化剂，是一种能吸收辐射能并发生化学变化，产生具有引发聚合能力的活性中间体的试剂。其中，酰基膦氧类化合物是一类光引发活性较高的光引发剂，其应用广泛。
相关技术提供了一种商业化使用的(2,4,6-三甲基苯甲酰基)二苯基氧化膦((2,4,6-trimethylbenzoyl)diphenylphosphine oxide，TPO)，其化学结构式如下：
Figure PCTCN2018119922-appb-000001
其中，TPO的工业制备方法主要包括两种：第一、使二苯基氯化膦在碱性环境中与甲醇进行酯化反应制得二苯基亚膦酸甲酯中间体，二苯基亚膦酸甲酯中间体与2,4,6-三甲基苯甲酰氯进行缩合反应，得到TPO。第二、使二苯基氯化膦经水解后得到二苯基氧化膦，二苯基氧化膦与2,4,6-三甲基苯甲醛缩合并被氧化得到TPO。而二苯基氯化膦的制备方法为：将苯和三氯化磷经三氯化铝催化反应后，先常压蒸馏收集未反应的苯和三氯化磷、苯基氯化膦，然后将釜残经氯化钠解络合后蒸馏收集二苯基氯化膦。
在制备二苯基氯化膦的过程中，容易产生游离磷，存在安全隐患，且二苯基氯化膦的产率低，易产生氯化氢、三氯化铝等工艺废料，污染环境。由于二苯基氯化膦的生产过程中存在诸多问题，限制了TPO的生产，而且在第二种制备TPO的方法中，氧化过程也存在安全隐患。
发明内容
本公开实施例提供了一种酰基膦氧类化合物及其制备方法，可解决上述技术问题。具体技术方案如下：
一方面，本公开实施例提供了一种酰基膦氧类化合物的制备方法，其中，所述方法包括：
在有机碱及有机溶剂的条件下，使化合物B和化合物C反应，得到所述酰基膦氧类化合物；
其中，所述化合物B的化学结构式如下：
Figure PCTCN2018119922-appb-000002
所述化合物C的化学结构式如下：
Figure PCTCN2018119922-appb-000003
所述酰基膦氧类化合物的化学结构式如下：
Figure PCTCN2018119922-appb-000004
其中，R 1为氢、C 1-C 6烷基、甲氧基、甲硫基、二甲氨基、氯甲酰基、苯基、苯甲酰基、(4-二甲胺基)苯基、α-萘基、β-萘基或(9-乙基-9H-咔唑)-3-基；
R 2与R 1相同；
n为R 1在对应苯环上的取代个数，n为1、2或3；
m为R 2在对应苯环上的取代个数，m为1、2或3。
在一种可能的设计中，所述方法还包括：
在所述化合物B和所述化合物C构成的反应体系中加入路易斯酸。
在一种可能的设计中，所述化合物B、所述化合物C、所述有机碱、所述路易斯酸的摩尔比为1:1-2:1-5:0.01-2。
在一种可能的设计中，所述路易斯酸选自三甲基氯硅烷、三甲基溴硅烷、三甲基碘硅烷、三乙基氯硅烷、三丙基氯硅烷、三丁基氯硅烷、叔丁基二甲基氯硅烷、叔丁基二苯基氯硅烷、三甲基氯硅烷-溴化钠、三甲基氯硅烷-碘化钠、甲磺酸三甲基硅酯、甲磺酸叔丁基二甲基硅酯、三氟甲磺酸三甲基硅酯、三氟甲磺酸叔丁基二甲基硅酯中的至少一种。
在一种可能的设计中，所述有机碱选自三乙胺、三丙胺、N,N-二异丙基乙胺、N,N-二甲基苯胺、吡啶、2,6-二甲基吡啶、2-甲基吡啶、3-甲基吡啶、4-甲基吡啶中的至少一种。
在一种可能的设计中，所述有机溶剂选自甲苯、二甲苯、四氢呋喃、2-甲基四氢呋喃、二氧六环、乙二醇二甲醚、甲基叔丁基醚、二氯甲烷、1,2-二氯乙烷、乙腈、N,N-二甲基甲酰胺、N,N-二甲基乙酰胺、N-甲基吡咯烷酮、二甲亚砜、环丁砜中的至少一种。
在一种可能的设计中，所述化合物B和所述化合物C的反应温度为-20℃-150℃，反应时间为1-8小时。
在一种可能的设计中，所述在有机碱及有机溶剂条件下，使化合物B和化合物C反应，包括：
获取包括所述化合物C和所述有机溶剂的第一混合液，并与所述有机碱在第一反应器中混合；
向所述第一反应器中加入所述化合物B，使所述化合物B和所述化合物C反应。
在一种可能的设计中，所述向所述第一反应器中加入所述化合物B，包括：
获取包括有所述化合物B和所述有机溶剂的第二混合液；
向所述第一反应器中滴加所述第二混合液。
在一种可能的设计中，所述获取包括所述化合物C和所述有机溶剂的第一混合液，包括：
使格氏试剂和亚磷酸二乙酯于所述有机溶剂中反应，再经酸溶液淬灭反应后处理，得到包括所述化合物C和所述第一有机溶剂的第一混合液；
所述格氏试剂的化学结构式如下：
Figure PCTCN2018119922-appb-000005
其中，R 2为氢、C 1-C 6烷基、甲氧基、甲硫基、二甲氨基、氯甲酰基、苯基、苯甲酰基、(4-二甲胺基)苯基、α-萘基、β-萘基或(9-乙基-9H-咔唑)-3-基；
m为R 2在对应苯环上的取代个数，m为1、2或3；
X为氯、溴或碘。
在一种可能的设计中，所述亚磷酸二乙酯与所述格氏试剂的摩尔比为1:3-5。
在一种可能的设计中，所述酸溶液选自盐酸溶液、氢溴酸溶液、氢碘酸溶液、硫酸溶液、醋酸溶液、草酸溶液、柠檬酸溶液中的至少一种。
在一种可能的设计中，所述格氏试剂和所述亚磷酸二乙酯的反应温度为-20℃-150℃，反应时间为1-4小时。
在一种可能的设计中，使格氏试剂和亚磷酸二乙酯于有机溶剂中反应，再经酸溶液淬灭反应后处理，包括：
向具有所述格氏试剂和所述有机溶剂的第三混合液的第二反应器中加入所述亚磷酸二乙酯，使所述格氏试剂与所述亚磷酸二乙酯反应，再经所述酸溶液淬灭反应后处理。
在一种可能的设计中，所述格氏试剂和所述有机溶剂的第三混合液通过以下方法制备得到：
在引发剂和所述有机溶剂的条件下，使镁粉和芳卤反应，得到包括所述格氏试剂和所述有机溶剂的第三混合液；
其中，所述芳卤的化学结构式如下：
Figure PCTCN2018119922-appb-000006
其中，R 2为氢、C 1-C 6烷基、甲氧基、甲硫基、二甲氨基、氯甲酰基、苯基、苯甲酰基、(4-二甲胺基)苯基、α-萘基、β-萘基或(9-乙基-9H-咔唑)-3- 基；
m为R 2在对应苯环上的取代个数，m为1、2或3；
X为氯、溴或碘。
在一种可能的设计中，所述芳卤与所述镁粉的摩尔比为1:1-2。
在一种可能的设计中，所述引发剂选自碘和二溴乙烷中的至少一种。
在一种可能的设计中，所述镁粉和所述芳卤的反应时间为2-4小时。
另一方面，本公开实施例提供了一种酰基膦氧类化合物，其中，所述化合物的化学结构式如下：
Figure PCTCN2018119922-appb-000007
其中，R 1为氢、C 1-C 6烷基、甲氧基、甲硫基、二甲氨基、氯甲酰基、苯基、苯甲酰基、(4-二甲胺基)苯基、α-萘基、β-萘基或(9-乙基-9H-咔唑)-3-基；
R 2与R 1相同；
n为R 1在对应苯环上的取代个数，n为1、2或3；
m为R 2在对应苯环上的取代个数，m为1、2或3。
本公开实施例提供的技术方案带来的有益效果至少包括：
本公开实施例提供的酰基膦氧类化合物的制备方法，在有机碱和有机溶剂的条件下，使化合物B和化合物C反应得到酰基膦氧类化合物。该制备方法没有以二苯基氯化膦为生产原料，并且未涉及氧化操作，其具有安全、环保、易操作、产率高等特点，利于酰基膦氧类化合物的生产。通过该方法制备得到的酰基膦氧类化合物的质量稳定、纯度高、收率高、成本低，利于工业化生产。
具体实施方式
为使本公开的目的、技术方案和优点更加清楚，下面将结合附图对本公开实施方式作进一步地详细描述。
一方面，本公开实施例提供了一种酰基膦氧类化合物的制备方法，该方法 包括：
在有机碱及有机溶剂的条件下，使化合物B和化合物C反应，得到酰基膦氧类化合物；
其中，化合物B的化学结构式如下：
Figure PCTCN2018119922-appb-000008
化合物C的化学结构式如下：
Figure PCTCN2018119922-appb-000009
酰基膦氧类化合物的化学结构式如下：
Figure PCTCN2018119922-appb-000010
其中，R 1为氢、C 1-C 6烷基、甲氧基、甲硫基、二甲氨基、氯甲酰基、苯基、苯甲酰基、(4-二甲胺基)苯基、α-萘基、β-萘基或(9-乙基-9H-咔唑)-3-基；
R 2与R 1相同；
n为R 1在对应苯环上的取代个数，n为1、2或3；
m为R 2在对应苯环上的取代个数，m为1、2或3。
需要说明的是，R 1在对应苯环上的取代位置可以为酰基的邻位、间位或对位。R 2在对应苯环上的取代位置可以为膦氧基的邻位、间位或对位。
本发明实施例中，该酰基膦氧类化合物可以作为光引发剂，其具有引发聚 合活性高、光固化速度快、热稳定性优良、后聚合效应低、无残留等优点，能够应用于紫外光固化涂料、印刷油墨、紫外光固化粘合剂、光导纤维涂料、抗光蚀剂、光聚合印版、立体平版树脂、牙齿填充料等。
在本公开实施例中，对于有机溶剂的使用量不作具体限定，能够满足使各组分溶解，并且能满足发生反应即可。
化合物B和化合物C之间的化学反应可以参见以下化学方程式：
Figure PCTCN2018119922-appb-000011
本公开实施例提供的酰基膦氧类化合物的制备方法，在有机碱及有机溶剂条件下，使化合物B和化合物C反应得到酰基膦氧类化合物。该制备方法没有以二苯基氯化膦为生产原料，并且未涉及氧化操作，其具有安全、环保、易操作、产率高等特点，利于酰基膦氧类化合物的生产。通过该方法制备得到的酰基膦氧类化合物的质量稳定、纯度高、收率高、成本低，利于工业化生产。
本公开实施例提供的酰基膦氧类化合物的制备方法还包括：在化合物B和化合物C构成的反应体系中加入路易斯酸。
可以理解的是，化合物B和化合物C构成的反应体系包括：化合物B、化合物C、有机碱、有机溶剂。
通过在化合物B和化合物C构成的反应体系中加入路易斯酸，能够促进化合物B和化合物C生成化合物A，并且不会产生副反应。
化合物B、化合物C、有机碱、路易斯酸的摩尔比对于能否高效制备得到酰基膦氧类化合物具有重要的影响。基于此，化合物B、化合物C、有机碱、路易斯酸的摩尔比可以为1:1-2:1-5:0.01-2，化合物B、化合物C、有机碱、路易斯酸的摩尔比还可以为1:1:1-3:1。
举例来说，化合物B、化合物C、有机碱、路易斯酸的摩尔比可以为1:1:1:0.01、1:1.1:1.1:0.3、1:1.4:2:0.5、1:1.7:2.4:0.7、1:1.8:3:0.9、1:1:1:1、1:1:2:1、1:1:3:1、1:1.9:4:1.5、1:2:5:2等。
如此，能够使化合物B和化合物C充分发生反应，且反应速率快，利于 高效、高产率地制得酰基膦氧类化合物。
本公开实施例就路易斯酸的种类给出一种示例：路易斯酸选自三甲基氯硅烷、三甲基溴硅烷、三甲基碘硅烷、三乙基氯硅烷、三丙基氯硅烷、三丁基氯硅烷、叔丁基二甲基氯硅烷、叔丁基二苯基氯硅烷、三甲基氯硅烷-溴化钠、三甲基氯硅烷-碘化钠、甲磺酸三甲基硅酯、甲磺酸叔丁基二甲基硅酯、三氟甲磺酸三甲基硅酯、三氟甲磺酸叔丁基二甲基硅酯中的至少一种。
其中，路易斯酸可以选自上述任一种、两种、三种、四种、五种、六种、七种、……。当路易斯酸为混合物时，对于各组分的比例不作具体限定。
上述几种路易斯酸能够有效促进化合物B和化合物C的反应，其与其他组分的互溶性好，而且价格低廉，容易获取。
在添加路易斯酸后，可以搅拌0.8-1.5小时，例如可以为0.8小时、0.9小时、1小时、1.1小时、1.2小时、1.3小时、1.4小时、1.5小时等。
如此，能够有效保证路易斯酸的催化效果，以促进化合物B和化合物C反应。
有机碱能够吸收化合物B和化合物C反应产生的氯化氢，而且有机碱不会产生副反应。本公开实施例就有机碱的种类给出一种示例：有机碱选自三乙胺、三丙胺、N,N-二异丙基乙胺、N,N-二甲基苯胺、吡啶、2,6-二甲基吡啶、2-甲基吡啶、3-甲基吡啶、4-甲基吡啶中的至少一种。
即有机碱选自上述任一种、两种、三种、四种、五种、六种、七种、八种、九种。当有机碱为混合物时，对于各组分的比例不作具体限定。举例来说，当有机碱为三乙胺和N,N-二异丙基乙胺的混合物时，两者的质量比可以为1:1、1:2、1:3、2:1、2:3等。当有机碱为三乙胺、N,N-二异丙基乙胺、N,N-二甲基苯胺三者的混合物时，三者的质量比可以为1:1:1、1:2:1、1:3:1、2:1:1、2:3:1、2:2:1、2:3:1、2:1:3、2:3:3等。
上述几种有机碱不仅能够有效促进化合物B和化合物C反应生成化合物A。而且价格低廉，容易获取。
有机溶剂能够使化合物B和化合物C充分均匀分散，利于两者均匀地发生反应。本公开实施例就有机溶剂的种类给出一种示例：有机溶剂选自甲苯、二甲苯、四氢呋喃、2-甲基四氢呋喃、二氧六环、乙二醇二甲醚、甲基叔丁基醚、二氯甲烷、1,2-二氯乙烷、乙腈、N,N-二甲基甲酰胺、N,N-二甲基乙酰胺、N-甲基吡咯烷酮、二甲亚砜、环丁砜中的至少一种。
即有机溶剂可以选自上述任一种、两种、三种、四种、……、或者全部。当有机溶剂为混合物时，对于各组分的比例不作具体限定。举例来说，当有机溶剂为甲苯和四氢呋喃的混合物时，甲苯和四氢呋喃的质量比可以为1:1、1:1.2、1:1.4、1:1.5、1:1.7、1:1.9、1:2等。
上述几种有机溶剂使化合物B和化合物C的互溶性好，并且价格低廉，容易获取。
化合物B和化合物C的反应温度可以为-20℃-150℃，例如可以为-20℃、-10℃、-5℃、0℃、10℃、20℃、30℃、40℃、50℃、60℃、70℃、80℃、90℃、100℃、110℃、120℃、130℃、140℃、150℃等。反应时间可以为1-8小时，例如可以为1小时、1.8小时、1.9小时、2小时、2.1小时、2.2小时、2.3小时、2.4小时、2.5小时、3小时、3.5小时、4小时、4.5小时、5小时、5.5小时、6小时、6.5小时、7小时、7.5小时、8小时等。
如此，能够保证化合物B和化合物C在有机碱和有机溶剂的条件下充分发生反应。
本公开实施例关于如何使化合物B、化合物C、有机碱、有机溶剂混合反应给出以下两种示例：
(1)作为第一种示例，将化合物B、化合物C、有机碱、有机溶剂均添加至第一反应器中，搅拌混合反应。
(2)作为第二种示例，在有机碱及有机溶剂条件下，使化合物B和化合物C反应，包括：
步骤A、获取包括化合物C和有机溶剂的第一混合液，并与有机碱在第一反应器中混合。
其中，获取包括化合物C和有机溶剂的第一混合液可以通过将化合物C和有机溶剂混合得到，也可以通过以下步骤得到：
使格氏试剂和亚磷酸二乙酯于有机溶剂中反应，再经酸溶液淬灭反应后处理，得到包括化合物C和有机溶剂的第一混合液；
格氏试剂的化学结构式如下：
Figure PCTCN2018119922-appb-000012
其中，R 2为氢、C 1-C 6烷基、甲氧基、甲硫基、二甲氨基、氯甲酰基、苯 基、苯甲酰基、(4-二甲胺基)苯基、α-萘基、β-萘基或(9-乙基-9H-咔唑)-3-基；
m为R 2在对应苯环上的取代个数，m为1、2或3；
X为氯、溴或碘。
如此，能够省去分离化合物C的步骤，以高效地制备酰基膦氧类化合物。
其中，亚磷酸二乙酯与格氏试剂的摩尔比对两者之间能否充分反应具有重要的影响，基于此，在本公开实施例中，亚磷酸二乙酯与格氏试剂的摩尔比可以为1:3-5，亚磷酸二乙酯与格氏试剂的摩尔比还可以为1:3-3.5。例如，亚磷酸二乙酯与格氏试剂的摩尔比可以为1:3、1:3.1、1:3.3、1:3.5、1:3.7、1:3.9、1:4、1:4.1、1:4.3、1:4.5、1:4.7、1:4.9、1:5等。
格氏试剂与亚磷酸二乙酯的反应温度可以为-20℃-150℃，例如可以为-20℃、-10℃、-5℃、0℃、10℃、20℃、30℃、40℃、50℃、60℃、70℃、80℃、90℃、100℃、110℃、120℃、130℃、140℃、150℃等。格氏试剂与亚磷酸二乙酯的反应时间可以为1-4小时，例如可以为1小时、1.5小时、2小时、2.5小时、2.8小时、2.9小时、3小时、3.1小时、3.2小时、3.3小时、3.4小时、3.5小时、4小时等。
如此，通过上述亚磷酸二乙酯与格氏试剂的摩尔比、反应温度和反应时间的配合作用，利于亚磷酸二乙酯和格氏试剂充分反应。
使亚磷酸二乙酯与格氏试剂在有机溶剂中反应后，经酸溶液淬灭反应后处理，可以高收率得到包括化合物C和有机溶剂的第一混合液。
作为一种示例，酸溶液选自盐酸溶液、氢溴酸溶液、氢碘酸溶液、硫酸溶液、醋酸溶液、草酸溶液、柠檬酸溶液中的至少一种。
即酸溶液选自上述任一种、两种、三种、四种、五种、六种、七种。当酸溶液为混合物时，对于各组分的比例不作具体限定。举例来说，当酸溶液为醋酸溶液和柠檬酸溶液的混合物时，醋酸溶液和柠檬酸溶液的摩尔比可以为1:1、1:2、1:3、2:1、2:3等。
上述几种酸溶液的价格低廉，容易获取，且淬灭效应和水化效果好。
其中，酸溶液的质量浓度可以为30％-60％。
亚磷酸二乙酯与格氏试剂之间的化学反应可以参见以下化学方程式：
Figure PCTCN2018119922-appb-000013
步骤B、向第一反应器中加入化合物B，使化合物B和化合物C反应。
向第一反应器中加入化合物B包括但不限于以下方法：
获取包括有化合物B和有机溶剂的第二混合液；
向第一反应器中滴加第二混合液。
如此，利于化合物B和化合物C高效和充分地发生反应。
本公开实施例关于步骤A中如何添加格氏试剂和亚磷酸二乙酯给出以下示例：
使格氏试剂和亚磷酸二乙酯于有机溶剂中反应，再经酸溶液淬灭反应后处理，包括：向具有格氏试剂和有机溶剂的第三混合液的第二反应器中加入亚磷酸二乙酯，使格氏试剂与亚磷酸二乙酯反应，再经酸溶液淬灭反应后处理。
其中，格氏试剂和有机溶剂的第三混合液可以直接通过使格氏试剂与有机溶剂混合得到，也可以通过以下方法制备得到：
在引发剂和有机溶剂的条件下，使镁粉和芳卤反应，得到包括格氏试剂和有机溶剂的第三混合液。
其中，芳卤的化学结构式如下：
Figure PCTCN2018119922-appb-000014
其中，R 2为氢、C 1-C 6烷基、甲氧基、甲硫基、二甲氨基、氯甲酰基、苯基、苯甲酰基、(4-二甲胺基)苯基、α-萘基、β-萘基或(9-乙基-9H-咔唑)-3-基；
m为R 2在对应苯环上的取代个数，m为1、2或3；
X为氯、溴或碘。
如此，能够省去分离格氏试剂的步骤，以高效地制备酰基膦氧类化合物。
芳卤和镁粉的摩尔比对两者能否充分反应具有重要的影响，基于此，芳卤 与镁粉的摩尔比可以为1:1-2，芳卤与镁粉的摩尔比还可以为1:1-1.2。例如，芳卤和镁粉的摩尔比可以为1:1、1:1.2、1:1.4、1:1.5、1:1.7、1:1.9、1:2等。
引发剂可以选自碘和二溴乙烷中的至少一种。即引发剂选自碘、二溴乙烷、碘和二溴乙烷的混合物。
上述几种引发剂的引发效果好，能够保证芳卤与镁粉充分发生反应。而且，上述几种引发剂的价格低廉，容易获取。
镁粉和芳卤的反应时间可以为2-4小时，例如可以为2小时、2.2小时、2.5小时、2.7小时、2.8小时、2.9小时、3小时、3.1小时、3.2小时、3.3小时、3.4小时、3.5小时、3.7小时、4小时等。如此，能够保证芳卤和镁粉在引发剂的引发作用下充分反应。
在使镁粉和芳卤混合时，可以先向第二反应器中滴加引发剂、芳卤、有机溶剂的混合液，再向第二反应器中滴加芳卤和有机溶剂的混合液。通过分两步滴入，可以使引发剂引发镁粉和芳卤发生反应，随后加入的芳卤继续反应，利于减少引发剂的用量。
芳卤与镁粉之间的化学反应可以参见以下化学方程式：
Figure PCTCN2018119922-appb-000015
可以通过滴加的方式向第二反应器中加入亚磷酸二乙酯，使格氏试剂与亚磷酸二乙酯反应得到反应液，并搅拌1-4小时，然后降温至室温。随后使该反应液滴加至酸溶液中，进行淬灭反应，最后得到化合物C。
本公开实施例中所涉及的室温可以为20℃-30℃，例如可以为20℃、21℃、22℃、23℃、24℃、25℃、26℃、27℃、28℃、29℃、30℃等。具体室温温度根据实际操作环境确定即可。
在本公开实施例中，第一反应器和第二反应器可以为同一个反应器。在制备化合物C和有机溶剂的混合液时，不将格氏试剂和化合物C单独分离出，直接采用对应的混合液进行制备，避免了中间体出料，易于工业化生产。
在化合物B和化合物C反应完毕之后，可经洗涤处理和分离处理，得到酰基膦氧类化合物。
其中，洗涤处理能够洗去混合液中的杂质，洗涤处理可以通过有机溶剂或水进行洗涤。分离处理可以为减压蒸馏、萃取等处理。
本公开实施例提供的酰基膦氧类化合物的制备方法，在有机碱、有机溶剂和路易斯酸的条件下，使化合物B和化合物C反应得到酰基膦氧类化合物。该制备方法没有以二苯基氯化膦为生产原料，并且未涉及氧化操作，其具有安全、环保、易操作、产率高等特点，利于酰基膦氧类化合物的生产。通过该方法制备得到的酰基膦氧类化合物的质量稳定、纯度高、收率高、成本低，利于工业化生产。
另一方面，本公开实施例提供了一种酰基膦氧类化合物，其中，该化合物的化学结构式如下：
Figure PCTCN2018119922-appb-000016
其中，R 1为氢、C 1-C 6烷基、甲氧基、甲硫基、二甲氨基、氯甲酰基、苯基、苯甲酰基、(4-二甲胺基)苯基、α-萘基、β-萘基或(9-乙基-9H-咔唑)-3-基；
R 2与R 1相同；
n为R 1在对应苯环上的取代个数，n为1、2或3；
m为R 2在对应苯环上的取代个数，m为1、2或3。
本公开实施例提供的酰基膦氧类化合物，在有机碱和有机溶剂的条件下，使化合物B和化合物C反应得到，该酰基膦氧类化合物的产品质量稳定、纯度高，其光引发活性较高，可以广泛应用工业生产中。
示例地，该示例提供了一种(2,4,6-三甲基苯甲酰基)二苯基氧化膦(TPO)，其化学结构式如下：
Figure PCTCN2018119922-appb-000017
该TPO通过以下方法制备得到：
在无水无氧、60℃的微回流和搅拌条件下，将75克镁粉和500毫升四氢呋喃的混合液置于烧瓶中。在搅拌条件下，向烧瓶中滴加5克二溴乙烷、20克氯苯和200毫升四氢呋喃的混合液，滴加时间为1小时，以引发镁粉和氯苯反应。然后再向烧瓶中滴加320克氯苯和300毫升四氢呋喃的混合液，滴加时间为3小时。滴加完后在微回流状态下继续搅拌反应3小时，得到包括格氏试剂和四氢呋喃的混合液。
使烧瓶中包括格氏试剂和四氢呋喃的混合液的温度为40℃-50℃，在搅拌条件下向烧瓶中滴加138克亚磷酸二乙酯，滴加时间为30分钟。在微回流状态下继续搅拌反应3小时后，降温至室温。然后在搅拌条件下向烧瓶中缓慢加入500毫升质量浓度为50％的柠檬酸溶液，继续搅拌30分钟，静置分层30分钟。将有机相分离出并在40℃-50℃的条件下减压浓缩得到有机残留(包括二苯基氧化膦)，并回收四氢呋喃。将水相与1升甲苯混合，在室温搅拌30分钟，静置分层30分钟，然后分出甲苯相并与前述分离出的有机残留合并，得到包括二苯基氧化膦(化合物C)、甲苯及氯化氢等杂质的混合液。依次用300毫升质量浓度为10％的碳酸氢钠水溶液和300毫升水洗涤该混合液，并在50℃-60℃的条件下减压蒸馏出约400毫升甲苯，剩余的则为二苯基氧化膦和甲苯的混合液。
在室温及搅拌条件下，将二苯基氧化膦和甲苯的混合液与220克三乙胺于烧瓶中混合，在40℃-50℃的条件下向烧瓶中滴加105克三甲基氯硅烷和100毫升甲苯的混合液，滴加时间为1小时，加完后继续搅拌1小时。然后向烧瓶中滴加185克2,4,6-三甲基苯甲酰氯(化合物B)和200毫升甲苯的混合液，滴加时间为2小时。然后在50℃的条件下搅拌反应2小时，降温至室温。
在室温条件下，用500毫升水洗涤烧瓶中的反应液，洗涤2次。洗涤后，将有机相分离并于40℃-50℃的条件下减压蒸除挥发物。然后向有机相中加入600毫升异丙醚，在55℃-65℃的条件下搅拌打浆2小时，随后在5℃-10℃的 条件下继续搅拌打浆1小时，抽滤，得到滤饼。滤饼用冷的异丙醚洗涤后，在40℃-50℃的条件下减压干燥，得到324克本实施例提供的TPO，其纯度为99.6％，以亚磷酸二乙酯计TPO的收率为93％。
示例地，该示例提供了一种(2,4,6-三甲基苯甲酰基)二(对-甲苯基)氧化膦，其化学结构式如下：
Figure PCTCN2018119922-appb-000018
该(2,4,6-三甲基苯甲酰基)二(对-甲苯基)氧化膦通过以下方法制备得到：
在无水无氧、60℃的微回流和搅拌条件下，将75克镁粉和500毫升四氢呋喃的混合液置于烧瓶中。在搅拌条件下，向烧瓶中滴加5克二溴乙烷、30克对氯甲苯和200毫升四氢呋喃的混合液，滴加时间为1小时，以引发镁粉和对氯甲苯反应。然后再向烧瓶中滴加353克对氯甲苯和300毫升四氢呋喃的混合液，滴加时间为3小时。滴加完后在微回流状态下继续搅拌反应3小时，得到包括格氏试剂和四氢呋喃的混合液。
使烧瓶中包括格氏试剂和四氢呋喃的混合液的温度为40℃-50℃，在搅拌条件下向烧瓶中滴加138克亚磷酸二乙酯，滴加时间为30分钟。在微回流状态下继续搅拌反应3小时后，降温至室温。然后在搅拌条件下向烧瓶中缓慢加入500毫升质量浓度为50％的柠檬酸溶液，继续搅拌30分钟，静置分层30分钟。将有机相分离出并在40℃-50℃的条件下减压浓缩得到有机残留(包括二(对-甲苯基)氧化膦)，并回收四氢呋喃。将水相与1升甲苯混合，在室温搅拌30分钟，静置分层30分钟，然后分出甲苯相并与前述分离出的有机残留合并，得到包括二(对-甲苯基)氧化膦(化合物C)、甲苯及氯化氢等杂质的混合液。依次用300毫升质量浓度为10％的碳酸氢钠水溶液和300毫升水洗涤该混合液，并在50℃-60℃的条件下减压蒸馏出约400毫升甲苯，剩余的则为二(对-甲苯基)氧化膦和甲苯的混合液。
在室温及搅拌条件下，将二(对-甲苯基)氧化膦和甲苯的混合液与220克三 乙胺于烧瓶中混合，在40℃-50℃的条件下向烧瓶中滴加197克三甲基碘硅烷和100毫升甲苯的混合液，滴加时间为1小时，加完后继续搅拌1小时。然后向烧瓶中滴加195克2,4,6-三甲基苯甲酰氯(化合物B)和200毫升甲苯的混合液，滴加时间为2小时。然后在50℃的条件下搅拌反应2小时，降温至室温。
在室温条件下，用500毫升水洗涤烧瓶中的反应液，洗涤2次。洗涤后，将有机相分离并于40℃-50℃的条件下减压蒸除挥发物。然后向有机相中加入600毫升异丙醚，在55℃-65℃的条件下搅拌打浆2小时，随后在5℃-10℃的条件下继续搅拌打浆1小时，抽滤，得到滤饼。滤饼用冷的异丙醚洗涤后，在40℃-50℃的条件下减压干燥，得到346克本实施例提供的(2,4,6-三甲基苯甲酰基)二(对-甲苯基)氧化膦，其纯度为99.7％，以亚磷酸二乙酯计(2,4,6-三甲基苯甲酰基)二(对-甲苯基)氧化膦的收率为92％。
示例地，该示例提供了一种(对-二甲胺基苯甲酰基)二苯基氧化膦，其化学结构式如下：
Figure PCTCN2018119922-appb-000019
该(对-二甲胺基苯甲酰基)二苯基氧化膦通过以下方法制备得到：
在无水无氧、60℃的微回流和搅拌条件下，将75克镁粉和500毫升四氢呋喃的混合液置于烧瓶中。在搅拌条件下，向烧瓶中滴加5克二溴乙烷、20克氯苯和200毫升四氢呋喃的混合液，滴加时间为1小时，以引发镁粉和氯苯反应。然后再向烧瓶中滴加320克氯苯和300毫升四氢呋喃的混合液，滴加时间为3小时。滴加完后在微回流状态下继续搅拌反应3小时，得到包括格氏试剂和四氢呋喃的混合液。
使烧瓶中包括格氏试剂和四氢呋喃的的混合液的温度为40℃-50℃，在搅拌条件下向烧瓶中滴加138克亚磷酸二乙酯，滴加时间为30分钟。在微回流状态下继续搅拌反应3小时后，降温至室温。然后在搅拌条件下向烧瓶中缓慢加入500毫升质量浓度为50％的柠檬酸溶液，继续搅拌30分钟，静置分层30 分钟。将有机相分离出并在40℃-50℃的条件下减压浓缩得到有机残留(包括二苯基氧化膦)，并回收四氢呋喃。将水相与1升甲苯混合，在室温搅拌30分钟，静置分层30分钟，然后分出甲苯相并与前述分离出的有机残留合并，得到包括二苯基氧化膦(化合物C)、甲苯及氯化氢等杂质的混合液。依次用300毫升质量浓度为10％的碳酸氢钠水溶液和300毫升水洗涤该混合液，并在50℃-60℃的条件下减压蒸馏出约400毫升甲苯，剩余的则为二苯基氧化膦和甲苯的混合液。
在室温及搅拌条件下，将二苯基氧化膦和甲苯的混合液与220克三乙胺于烧瓶中混合，在40℃-50℃的条件下向烧瓶中滴加148克三甲基溴硅烷和100毫升甲苯的混合液，滴加时间为1小时，加完后继续搅拌1小时。然后向烧瓶中滴加176克对-二甲胺基苯甲酰氯(化合物B)和200毫升甲苯的混合液，滴加时间为2小时。然后在50℃的条件下搅拌反应2小时，降温至室温。
在室温条件下，用500毫升水洗涤烧瓶中的反应液，洗涤2次。洗涤后，将有机相分离并于40℃-50℃的条件下减压蒸除挥发物。然后向有机相中加入600毫升异丙醚，在55℃-65℃的条件下搅拌打浆2小时，随后在5℃-10℃的条件下继续搅拌打浆1小时，抽滤，得到滤饼。滤饼用冷的异丙醚洗涤后，在40℃-50℃的条件下减压干燥，得到318克本实施例提供的(对-二甲胺基苯甲酰基)二苯基氧化膦，其纯度为99.6％，以亚磷酸二乙酯计(对-二甲胺基苯甲酰基)二苯基氧化膦的收率为91％。
示例地，该示例提供了一种(对-甲氧基苯甲酰基)二苯基氧化膦，其化学结构式如下：
Figure PCTCN2018119922-appb-000020
该(对-甲氧基苯甲酰基)二苯基氧化膦通过以下方法制备得到：
在无水无氧、60℃的微回流和搅拌条件下，将75克镁粉和500毫升四氢呋喃的混合液置于烧瓶中。在搅拌条件下，向烧瓶中滴加5克二溴乙烷、20 克氯苯和200毫升四氢呋喃的混合液，滴加时间为1小时，以引发镁粉和氯苯反应。然后再向烧瓶中滴加320克氯苯和300毫升四氢呋喃的混合液，滴加时间为3小时。滴加完后在微回流状态下继续搅拌反应3小时，得到包括格氏试剂和四氢呋喃的混合液。
使烧瓶中包括格氏试剂和四氢呋喃的混合液的温度为40℃-50℃，在搅拌条件下向烧瓶中滴加138克亚磷酸二乙酯，滴加时间为30分钟。在微回流状态下继续搅拌反应3小时后，降温至室温。然后在搅拌条件下向烧瓶中缓慢加入500毫升质量浓度为50％的柠檬酸溶液，继续搅拌30分钟，静置分层30分钟。将有机相分离出并在40℃-50℃的条件下减压浓缩得到有机残留(包括二苯基氧化膦)，并回收四氢呋喃。将水相与1升甲苯混合，在室温搅拌30分钟，静置分层30分钟，然后分出甲苯相并与前述分离出的有机残留合并，得到包括二苯基氧化膦(化合物C)、甲苯及氯化氢等杂质的混合液。依次用300毫升质量浓度为10％的碳酸氢钠水溶液和300毫升水洗涤该混合液，并在50℃-60℃的条件下减压蒸馏出约400毫升甲苯，剩余的则为二苯基氧化膦和甲苯的混合液。
在室温及搅拌条件下，将二苯基氧化膦和甲苯的混合液与220克三乙胺于烧瓶中混合，在40℃-50℃的条件下向烧瓶中滴加105克三甲基氯硅烷和100毫升甲苯的混合液，滴加时间为1小时，加完后继续搅拌1小时。然后向烧瓶中滴加164克对-甲氧基苯甲酰氯(化合物B)和200毫升甲苯的混合液，滴加时间为2小时。然后在50℃的条件下搅拌反应2小时，降温至室温。
在室温条件下，用500毫升水洗涤烧瓶中的反应液，洗涤2次。洗涤后，将有机相分离并于40℃-50℃的条件下减压蒸除挥发物。然后向有机相中加入600毫升异丙醚，在55℃-65℃的条件下搅拌打浆2小时，随后在5℃-10℃的条件下继续搅拌打浆1小时，抽滤，得到滤饼。滤饼用冷的异丙醚洗涤后，在40℃-50℃的条件下减压干燥，得到309克本实施例提供的(对-甲氧基苯甲酰基)二苯基氧化膦，其纯度为99.8％，以亚磷酸二乙酯计(对-甲氧基苯甲酰基)二苯基氧化膦的收率为92％。
示例地，该示例提供了一种(对-甲硫基苯甲酰基)二苯基氧化膦，其化学结构式如下：
Figure PCTCN2018119922-appb-000021
该(对-甲硫基苯甲酰基)二苯基氧化膦通过以下方法制备得到：
在无水无氧、60℃的微回流和搅拌条件下，将75克镁粉和500毫升四氢呋喃的混合液置于烧瓶中。在搅拌条件下，向烧瓶中滴加5克二溴乙烷、20克氯苯和200毫升四氢呋喃的混合液，滴加时间为1小时，以引发镁粉和氯苯反应。然后再向烧瓶中滴加320克氯苯和300毫升四氢呋喃的混合液，滴加时间为3小时。滴加完后在微回流状态下继续搅拌反应3小时，得到包括格氏试剂和四氢呋喃的混合液。
使烧瓶中包括格氏试剂和四氢呋喃的混合液的温度为40℃-50℃，在搅拌条件下向烧瓶中滴加138克亚磷酸二乙酯，滴加时间为30分钟。在微回流状态下继续搅拌反应3小时后，降温至室温。然后在搅拌条件下向烧瓶中缓慢加入500毫升质量浓度为50％的柠檬酸溶液，继续搅拌30分钟，静置分层30分钟。将有机相分离出并在40℃-50℃的条件下减压浓缩得到有机残留(包括二苯基氧化膦)，并回收四氢呋喃。将水相与1升甲苯混合，在室温搅拌30分钟，静置分层30分钟，然后分出甲苯相并与前述分离出的有机残留合并，得到包括二苯基氧化膦(化合物C)、甲苯及氯化氢等杂质的混合液。依次用300毫升质量浓度为10％的碳酸氢钠水溶液和300毫升水洗涤该混合液，并在50℃-60℃的条件下减压蒸馏出约400毫升甲苯，剩余的则为二苯基氧化膦和甲苯的混合液。
在室温及搅拌条件下，将二苯基氧化膦和甲苯的混合液与220克三乙胺于烧瓶中混合，在40℃-50℃的条件下向烧瓶中滴加105克三甲基氯硅烷和100毫升甲苯的混合液，滴加时间为1小时，加完后继续搅拌1小时。然后向烧瓶中滴加181克对-甲硫基苯甲酰氯(化合物B)和200毫升甲苯的混合液，滴加时间为2小时。然后在50℃的条件下搅拌反应2小时，降温至室温。
在室温条件下，用500毫升水洗涤烧瓶中的反应液，洗涤2次。洗涤后，将有机相分离并于40℃-50℃的条件下减压蒸除挥发物。然后向有机相中加入 600毫升异丙醚，在55℃-65℃的条件下搅拌打浆2小时，随后在5℃-10℃的条件下继续搅拌打浆1小时，抽滤，得到滤饼。滤饼用冷的异丙醚洗涤后，在40℃-50℃的条件下减压干燥，得到310克本实施例提供的(对-甲硫基苯甲酰基)二苯基氧化膦，其纯度为99.6％，以亚磷酸二乙酯计(对-甲硫基苯甲酰基)二苯基氧化膦的收率为88％。
示例地，该示例提供了一种(对-甲苯基苯甲酰基)二苯基氧化膦，其化学结构式如下：
Figure PCTCN2018119922-appb-000022
该(对-甲苯基苯甲酰基)二苯基氧化膦通过以下方法制备得到：
在无水无氧、60℃的微回流和搅拌条件下，将75克镁粉和500毫升四氢呋喃的混合液置于烧瓶中。在搅拌条件下，向烧瓶中滴加5克二溴乙烷、20克氯苯和200毫升四氢呋喃的混合液，滴加时间为1小时，以引发镁粉和氯苯反应。然后再向烧瓶中滴加320克氯苯和300毫升四氢呋喃的混合液，滴加时间为3小时。滴加完后在微回流状态下继续搅拌反应3小时，得到包括格氏试剂和四氢呋喃的混合液。
使烧瓶中包括格氏试剂和四氢呋喃的混合液的温度为40℃-50℃，在搅拌条件下向烧瓶中滴加138克亚磷酸二乙酯，滴加时间为30分钟。在微回流状态下继续搅拌反应3小时后，降温至室温。然后在搅拌条件下向烧瓶中缓慢加入500毫升质量浓度为50％的柠檬酸溶液，继续搅拌30分钟，静置分层30分钟。将有机相分离出并在40℃-50℃的条件下减压浓缩得到有机残留(包括二苯基氧化膦)，并回收四氢呋喃。将水相与1升甲苯混合，在室温搅拌30分钟，静置分层30分钟，然后分出甲苯相并与前述分离出的有机残留合并，得到包括二苯基氧化膦(化合物C)、甲苯及氯化氢等杂质的混合液。依次用300毫升质量浓度为10％的碳酸氢钠水溶液和300毫升水洗涤该混合液，并在50℃-60℃的条件下减压蒸馏出约400毫升甲苯，剩余的则为二苯基氧化膦和甲苯 的混合液。
在室温及搅拌条件下，将二苯基氧化膦和甲苯的混合液与220克三乙胺于烧瓶中混合，在40℃-50℃的条件下向烧瓶中滴加105克三甲基氯硅烷和100毫升甲苯的混合液，滴加时间为1小时，加完后继续搅拌1小时。然后向烧瓶中滴加208克对-苯基苯甲酰氯(化合物B)和200毫升甲苯的混合液，滴加时间为2小时。然后在50℃的条件下搅拌反应2小时，降温至室温。
在室温条件下，用500毫升水洗涤烧瓶中的反应液，洗涤2次。洗涤后，将有机相分离并于40℃-50℃的条件下减压蒸除挥发物。然后向有机相中加入600毫升异丙醚，在55℃-65℃的条件下搅拌打浆2小时，随后在5℃-10℃的条件下继续搅拌打浆1小时，抽滤，得到滤饼。滤饼用冷的异丙醚洗涤后，在40℃-50℃的条件下减压干燥，得到344克本实施例提供的(对-甲苯基苯甲酰基)二苯基氧化膦，其纯度为99.6％，以亚磷酸二乙酯计(对-甲苯基苯甲酰基)二苯基氧化膦的收率为90％。
示例地，该示例提供了一种(1,4-苯二甲酰基)二(二苯基氧化膦)，其化学结构式如下：
Figure PCTCN2018119922-appb-000023
该(1,4-苯二甲酰基)二(二苯基氧化膦)通过以下方法制备得到：
在无水无氧、60℃的微回流和搅拌条件下，将75克镁粉和500毫升四氢呋喃的混合液置于烧瓶中。在搅拌条件下，向烧瓶中滴加5克二溴乙烷、20克氯苯和200毫升四氢呋喃的混合液，滴加时间为1小时，以引发镁粉和氯苯反应。然后再向烧瓶中滴加320克氯苯和300毫升四氢呋喃的混合液，滴加时间为3小时。滴加完后在微回流状态下继续搅拌反应3小时，得到包括格氏试剂和四氢呋喃的混合液。
使烧瓶中包括格氏试剂和四氢呋喃的混合液的温度为40℃-50℃，在搅拌条件下向烧瓶中滴加138克亚磷酸二乙酯，滴加时间为30分钟。在微回流状态下继续搅拌反应3小时后，降温至室温。然后在搅拌条件下向烧瓶中缓慢加 入500毫升质量浓度为50％的柠檬酸溶液，继续搅拌30分钟，静置分层30分钟。将有机相分离出并在40℃-50℃的条件下减压浓缩得到有机残留(包括二苯基氧化膦)，并回收四氢呋喃。将水相与1升甲苯混合，在室温搅拌30分钟，静置分层30分钟，然后分出甲苯相并与前述分离出的有机残留合并，得到包括二苯基氧化膦(化合物C)、甲苯及氯化氢等杂质的混合液。依次用300毫升质量浓度为10％的碳酸氢钠水溶液和300毫升水洗涤该混合液，并在50℃-60℃的条件下减压蒸馏出约400毫升甲苯，剩余的则为二苯基氧化膦和甲苯的混合液。
在室温及搅拌条件下，将二苯基氧化膦和甲苯的混合液与220克三乙胺于烧瓶中混合，在40℃-50℃的条件下向烧瓶中滴加203克三氟甲磺酸三甲基硅酯和100毫升甲苯的混合液，滴加时间为1小时，加完后继续搅拌1小时。然后向烧瓶中滴加97克1,4-苯二甲酰氯(化合物B)和200毫升甲苯的混合液，滴加时间为2小时。然后在50℃的条件下搅拌反应2小时，降温至室温。
在室温的条件下，用500毫升水洗涤烧瓶中的反应液，洗涤2次。洗涤后，将有机相分离并于40℃-50℃的条件下减压蒸除挥发物。然后向有机相中加入600毫升异丙醚，在55℃-65℃的条件下搅拌打浆2小时，随后在5℃-10℃的条件下继续搅拌打浆1小时，抽滤，得到滤饼。滤饼用冷的异丙醚洗涤后，在40℃-50℃的条件下减压干燥，得到243克本实施例提供的(1,4-苯二甲酰基)二(二苯基氧化膦)，其纯度为99.8％，以亚磷酸二乙酯计(1,4-苯二甲酰基)二(二苯基氧化膦)的收率为91％。
综上，采用本公开实施例提供的酰基膦氧类化合物的制备方法，能够得到产品质量稳定、纯度高、收率高的产品，利于工业化生产。
以上所述仅为本公开的说明性实施例，并不用以限制本公开，凡在本公开的精神和原则之内，所作的任何修改、等同替换、改进等，均应包含在本公开的保护范围之内。

Claims (19)

  1. 一种酰基膦氧类化合物的制备方法，其中，所述方法包括：
    在有机碱及有机溶剂条件下，使化合物B和化合物C反应，得到所述酰基膦氧类化合物；
    其中，所述化合物B的化学结构式如下：
    Figure PCTCN2018119922-appb-100001
    所述化合物C的化学结构式如下：
    Figure PCTCN2018119922-appb-100002
    所述酰基膦氧类化合物的化学结构式如下：
    Figure PCTCN2018119922-appb-100003
    其中，R 1为氢、C 1-C 6烷基、甲氧基、甲硫基、二甲氨基、氯甲酰基、苯基、苯甲酰基、(4-二甲胺基)苯基、α-萘基、β-萘基或(9-乙基-9H-咔唑)-3-基；
    R 2与R 1相同；
    n为R 1在对应苯环上的取代个数，n为1、2或3；
    m为R 2在对应苯环上的取代个数，m为1、2或3。
  2. 根据权利要求1所述的方法，其中，所述方法还包括：在所述化合物B 和所述化合物C构成的反应体系中加入路易斯酸。
  3. 根据权利要求2所述的方法，其中，所述化合物B、所述化合物C、所述有机碱、所述路易斯酸的摩尔比为1:1-2:1-5:0.01-2。
  4. 根据权利要求2或3所述的方法，其中，所述路易斯酸选自三甲基氯硅烷、三甲基溴硅烷、三甲基碘硅烷、三乙基氯硅烷、三丙基氯硅烷、三丁基氯硅烷、叔丁基二甲基氯硅烷、叔丁基二苯基氯硅烷、三甲基氯硅烷-溴化钠、三甲基氯硅烷-碘化钠、甲磺酸三甲基硅酯、甲磺酸叔丁基二甲基硅酯、三氟甲磺酸三甲基硅酯、三氟甲磺酸叔丁基二甲基硅酯中的至少一种。
  5. 根据权利要求1-4任一项所述的方法，其中，所述有机碱选自三乙胺、三丙胺、N,N-二异丙基乙胺、N,N-二甲基苯胺、吡啶、2,6-二甲基吡啶、2-甲基吡啶、3-甲基吡啶、4-甲基吡啶中的至少一种。
  6. 根据权利要求1-5任一项所述的方法，其中，所述有机溶剂选自甲苯、二甲苯、四氢呋喃、2-甲基四氢呋喃、二氧六环、乙二醇二甲醚、甲基叔丁基醚、二氯甲烷、1,2-二氯乙烷、乙腈、N,N-二甲基甲酰胺、N,N-二甲基乙酰胺、N-甲基吡咯烷酮、二甲亚砜、环丁砜中的至少一种。
  7. 根据权利要求1-6任一项所述的方法，其中，所述化合物B和所述化合物C的反应温度为-20℃-150℃，反应时间为1-8小时。
  8. 根据权利要求1-7任一项所述的方法，其中，所述在有机碱及有机溶剂条件下，使化合物B和化合物C反应，包括：
    获取包括所述化合物C和所述有机溶剂的第一混合液，并与所述有机碱在第一反应器中混合；
    向所述第一反应器中加入所述化合物B，使所述化合物B和所述化合物C反应。
  9. 根据权利要8所述的方法，其特征在于，所述向所述第一反应器中加入 所述化合物B，包括：
    获取包括有所述化合物B和所述有机溶剂的第二混合液；
    向所述第一反应器中滴加所述第二混合液。
  10. 根据权利要求8或9所述的方法，其中，所述获取包括所述化合物C和所述有机溶剂的第一混合液，包括：
    使格氏试剂和亚磷酸二乙酯于所述有机溶剂中反应，再经酸溶液淬灭反应后处理，得到包括所述化合物C和所述有机溶剂的所述第一混合液；
    所述格氏试剂的化学结构式如下：
    Figure PCTCN2018119922-appb-100004
    其中，R 2为氢、C 1-C 6烷基、甲氧基、甲硫基、二甲氨基、氯甲酰基、苯基、苯甲酰基、(4-二甲胺基)苯基、α-萘基、β-萘基或(9-乙基-9H-咔唑)-3-基；
    m为R 2在对应苯环上的取代个数，m为1、2或3；
    X为氯、溴或碘。
  11. 根据权利要求10所述的方法，其中，所述亚磷酸二乙酯与所述格氏试剂的摩尔比为1:3-5。
  12. 根据权利要求10或11所述的方法，其中，所述酸溶液选自盐酸溶液、氢溴酸溶液、氢碘酸溶液、硫酸溶液、醋酸溶液、草酸溶液、柠檬酸溶液中的至少一种。
  13. 根据权利要求10-12任一项所述的方法，其中，所述格氏试剂和所述亚磷酸二乙酯的反应温度为-20℃-150℃，反应时间为1-4小时。
  14. 根据权利要求10-13任一项所述的方法，其中，所述使格氏试剂和亚磷酸二乙酯于所述有机溶剂中反应，再经酸溶液淬灭反应后处理，包括：
    向具有所述格氏试剂和所述有机溶剂的第三混合液的第二反应器中加入所述亚磷酸二乙酯，使所述格氏试剂与所述亚磷酸二乙酯反应，再经所述酸溶液 淬灭反应后处理。
  15. 根据权利要求14所述的方法，其中，所述格氏试剂和所述有机溶剂的第三混合液通过以下方法制备得到：
    在引发剂和所述有机溶剂的条件下，使镁粉和芳卤反应，得到包括所述格氏试剂和所述有机溶剂的第三混合液；
    其中，所述芳卤的化学结构式如下：
    Figure PCTCN2018119922-appb-100005
    其中，R 2为氢、C 1-C 6烷基、甲氧基、甲硫基、二甲氨基、氯甲酰基、苯基、苯甲酰基、(4-二甲胺基)苯基、α-萘基、β-萘基或(9-乙基-9H-咔唑)-3-基；
    m为R 2在对应苯环上的取代个数，m为1、2或3；
    X为氯、溴或碘。
  16. 根据权利要求15所述的方法，其中，所述芳卤与所述镁粉的摩尔比为1:1-2。
  17. 根据权利要求15或16所述的方法，其中，所述引发剂选自碘和二溴乙烷中的至少一种。
  18. 根据权利要求15-17任一项所述的方法，其中，所述镁粉和所述芳卤的反应时间为2-4小时。
  19. 一种酰基膦氧类化合物，其中，所述酰基膦氧类化合物的化学结构式如下：
    Figure PCTCN2018119922-appb-100006
    其中，R 1为氢、C 1-C 6烷基、甲氧基、甲硫基、二甲氨基、氯甲酰基、苯基、苯甲酰基、(4-二甲胺基)苯基、α-萘基、β-萘基或(9-乙基-9H-咔唑)-3-基；
    R 2与R 1相同；
    n为R 1在对应苯环上的取代个数，n为1、2或3；
    m为R 2在对应苯环上的取代个数，m为1、2或3。
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