WO2016192611A1 - 肟酯类化合物及其合成方法及应用 - Google Patents

肟酯类化合物及其合成方法及应用 Download PDF

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WO2016192611A1
WO2016192611A1 PCT/CN2016/083963 CN2016083963W WO2016192611A1 WO 2016192611 A1 WO2016192611 A1 WO 2016192611A1 CN 2016083963 W CN2016083963 W CN 2016083963W WO 2016192611 A1 WO2016192611 A1 WO 2016192611A1
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carbon atoms
group
alkyl
compound
alkene
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PCT/CN2016/083963
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French (fr)
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胡海军
吴进
谭玉东
黎水林
黄达
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江苏和成新材料有限公司
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C249/00—Preparation of compounds containing nitrogen atoms doubly-bound to a carbon skeleton
    • C07C249/04—Preparation of compounds containing nitrogen atoms doubly-bound to a carbon skeleton of oximes
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C251/00—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton
    • C07C251/32—Oximes
    • C07C251/62—Oximes having oxygen atoms of oxyimino groups esterified
    • C07C251/64—Oximes having oxygen atoms of oxyimino groups esterified by carboxylic acids
    • C07C251/68—Oximes having oxygen atoms of oxyimino groups esterified by carboxylic acids with at least one of the esterifying carboxyl groups bound to a carbon atom of a six-membered aromatic ring
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C319/00—Preparation of thiols, sulfides, hydropolysulfides or polysulfides
    • C07C319/14—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of sulfides
    • C07C319/20—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of sulfides by reactions not involving the formation of sulfide groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C319/00—Preparation of thiols, sulfides, hydropolysulfides or polysulfides
    • C07C319/22—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of hydropolysulfides or polysulfides
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C323/00—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups
    • C07C323/23—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and nitrogen atoms, not being part of nitro or nitroso groups, bound to the same carbon skeleton
    • C07C323/46—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and nitrogen atoms, not being part of nitro or nitroso groups, bound to the same carbon skeleton having at least one of the nitrogen atoms, not being part of nitro or nitroso groups, further bound to other hetero atoms
    • C07C323/47—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and nitrogen atoms, not being part of nitro or nitroso groups, bound to the same carbon skeleton having at least one of the nitrogen atoms, not being part of nitro or nitroso groups, further bound to other hetero atoms to oxygen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D335/00—Heterocyclic compounds containing six-membered rings having one sulfur atom as the only ring hetero atom
    • C07D335/04—Heterocyclic compounds containing six-membered rings having one sulfur atom as the only ring hetero atom condensed with carbocyclic rings or ring systems
    • C07D335/10—Dibenzothiopyrans; Hydrogenated dibenzothiopyrans
    • C07D335/12—Thioxanthenes
    • C07D335/14—Thioxanthenes with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached in position 9
    • C07D335/16—Oxygen atoms, e.g. thioxanthones
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/46—Polymerisation initiated by wave energy or particle radiation
    • C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light

Definitions

  • the present invention relates to an oxime ester compound, and more particularly to a photoinitiator for a UV curable material and a process for the preparation thereof.
  • UV curing is the process of using ultraviolet light to illuminate a chemically active liquid material, causing it to rapidly polymerize and crosslink and cure it instantaneously.
  • Curing technology was hailed as a new green industry technology for the 21st century in the 1980s. It is an efficient, environmentally friendly, energy-saving, high-quality material surface treatment technology in photocurable coatings, photoresists, Photocuring inks, microelectronics, adhesives, optical disc reproduction, and paper glazing technology have been widely used. In the progress of photocuring technology, the research and development of photoinitiator systems has always occupied a very important position.
  • photoinitiators such as benzoin derivatives, benzil ketals, ⁇ , ⁇ -dialkoxyacetophenones, benzophenones/amines, Mie Ketones, thiazolone/amines, aromatic diazonium salts, triazazines, oxime esters and the like are represented by commercially available Irgacure 369, Darocurel 173, OXE-1 and OXE-2.
  • these photoinitiators have more or less low sensitivity (high polymerization rate and high exposure dose), poor solubility (high transparency and lithography residue), low storage stability, and insufficient short-wavelength sensitivity in practical applications.
  • the specific selectivity to the photopolymerizable monomer is not strong and the like, thereby affecting the performance of the photosensitive material as a whole.
  • the effect of the photoinitiator on the photographic properties of the photopolymerizable composition is not only reflected in the sensitivity of the photoinitiator itself to radiation, but also to its photopolymerizable monomer (or Adaptability between its compositions). Therefore, in determining the formulation of a photopolymerizable composition, it is most desirable to find a photoinitiator having a good effect (e.g., synergistic effect) with the contained polymerizable monomer, which can be further optimized.
  • the photographic properties of the composition is most important factor affecting the photosensitivity of the photocurable composition.
  • photopolymerizable composition on the one hand, it is required to have excellent storage stability; on the other hand, it has high sensitivity to short-wave i-line and g-line, so as to reduce exposure dose, improve exposure efficiency, and thereby shorten production cycle; It is required that the photocured product prepared from the photopolymerizable composition has a fine image pattern, no defects and scum, and the hardness of the photocured film is good. These indicators are particularly important for the performance of filters and photoresists.
  • the photoinitiator used in the composition itself has a very high sensitivity at short wavelengths, and the entire composition
  • the system should be matched very well, that is, the polymerizable components (monomer, resin) in the composition can be optimally used in combination with the photoinitiator in the system. At present, there is very little research on this aspect.
  • the object of the present invention is to provide a good solubility, good thermal stability, high reactivity, low production cost and low price. It is basically odorless, has low migration, and is safe to use (low toxicity) acyl oxime ester compounds.
  • Another object of the present invention is to provide a process for producing the acyl oxime ester compound.
  • Another object of the present invention is to provide the use of the acyl oxime ester compound in a UV curable material.
  • the R 1 is selected from Wherein X 1 is -S-, -SS-, -O-, -NR-, wherein R is hydrogen, an alkane or alkoxy group of 1-8 carbon atoms, a ring of 3-8 carbon atoms An alkyl group; said X' and Y' being the same or different, each independently selected from the group consisting of -S-, -SS-, -O-, -CO-; said cyclic structure
  • One or more -H may be -F, -Cl, -Br, -I, -NO 2 , An alkyl or alkoxy group of 1 to 8 carbon atoms or an alkene group of 2 to 8 carbon atoms, wherein R' 1 and R' 2 are each independently selected from -H, An alkyl group of 1 to 8 carbon atoms, a cycloalkyl group of 3 to 8 carbon atoms, an alkene group of 2 to 8 carbon atoms, and R' 3
  • X 2 is -S-, -SS-, -O-, -NR-, wherein R is hydrogen, an alkane or alkoxy group of 1-8 carbon atoms, a ring of 3-8 carbon atoms Alkyl group; said cyclic structure
  • One or more -H may be -F, -Cl, -Br, -I, -NO 2 , An alkyl or alkoxy group of 1 to 8 carbon atoms or an alkene group of 2 to 8 carbon atoms, wherein R' 1 and R' 2 are each independently selected from -H, An alkyl group of 1 to 8 carbon atoms, a cycloalkyl group of 3 to 8 carbon atoms, an alkene group of 2 to 8 carbon atoms, and R' 3 is selected from -H, an alkyl group of 1 to 8 carbon atoms, 3 a cycloalkyl group of 8 to 8 carbon atoms, an alkene group of 2 to 8 carbon atom
  • the R 2 is selected from -H, an alkyl or alkoxy group of 1 to 20 carbon atoms, a cycloalkyl group of 3 to 8 carbon atoms, an alkene group of 2 to 20 carbon atoms or a group represented by R 1 .
  • the R 1 is selected from Wherein X 1 is -S-, -SS- or -O-, wherein X' and Y' are the same or different, each independently selected from -S-, -O- or -CO-, Ring structure
  • X 1 is -S-, -SS- or -O-, wherein X' and Y' are the same or different, each independently selected from -S-, -O- or -CO-, Ring structure
  • One or more -H may be substituted by -F, -Cl, -NO 2 , -COOR' 1 , -CONR' 2 , -OR' 3 , an alkyl group of 1-8 carbon atoms or an alkoxy group, wherein R' 1 and R' 2 are each independently selected from -H, An alkyl group of 1 to 8 carbon atoms, and R' 3 is selected from -H, an alkyl group of 1 to 8 carbon atoms, and a cycloal
  • the R 1 is selected from
  • the R 3 represents Wherein X 2 is -S-, -SS-, -O-, -NR-, wherein R is an alkane or alkoxy group of 1 to 5 carbon atoms, and 3 to 8 carbon atoms Cycloalkyl, said cyclic structure
  • One or more -H may be substituted by -F, -Cl, -NO 2 , -COOR' 1 , -CONR' 2 , -OR' 3 , an alkyl group of 1 to 5 carbon atoms or an alkoxy group, wherein R' 1 and R' 2 are each independently selected from -H, An alkyl group of 1 to 8 carbon atoms, and R' 3 is selected from the group consisting of -H, an alkyl group of 1 to 5 carbon atoms.
  • the R 3 represents Wherein X 2 is -S-, -SS-, -O-, -NR-, wherein R is an alkane or alkoxy group of 1 to 5 carbon atoms, and 3 to 8 carbon atoms Cycloalkyl, said cyclic structure
  • One or more -H may be substituted by -F, -Cl, -NO 2 , -COOR' 1 , -CONR' 2 , an alkyl group of 1 to 5 carbon atoms or an alkoxy group, wherein R' 1 and R ' 2 are each independently selected from -H, An alkyl group of 1 to 8 carbon atoms.
  • the X 2 is selected from the group consisting of -S-, -O-, -SS- or -NR-, wherein the R is an alkane or alkoxy group of 1 to 5 carbon atoms, A cycloalkyl group of 3 to 6 carbon atoms.
  • the R 3 is preferably selected from
  • the R 2 is selected from -H, an alkyl or alkoxy group of 1 to 20 carbon atoms, a cycloalkyl group of 3 to 8 carbon atoms, 2 to 20 carbons.
  • Alkene olefin group preferably, the R 2 is selected from -H, an alkyl or alkoxy group of 1 to 20 carbon atoms, a cycloalkyl group of 3 to 8 carbon atoms, 2 to 20 carbons.
  • the R 2 is selected from -H, an alkyl or alkoxy group of 1 to 15 carbon atoms, a cycloalkyl group of 3 to 8 carbon atoms, 2 to 15 carbon atoms. Olefin group,
  • the R 2 is selected from -H, an alkyl or alkoxy group of 1 to 15 carbon atoms, a cycloalkyl group of 3 to 8 carbon atoms, 2 to 15 carbon atoms. Olefin group,
  • the R 2 is selected from an alkyl or alkoxy group of 1 to 15 carbon atoms, a cycloalkyl group of 3 to 8 carbon atoms, and an alkene group of 2 to 15 carbon atoms.
  • the compound of Formula I is selected from the group consisting of the compounds of Formulas I-1 to I-10:
  • the R 2 is selected from -H, an alkyl or alkoxy group of 1 to 20 carbon atoms, a cycloalkyl group of 3 to 8 carbon atoms, an alkene group of 2 to 20 carbon atoms or a group represented by R 1 .
  • the invention also provides a preparation method of the acyl oxime ester compound of the formula I, comprising the following steps:
  • intermediate I-A the synthesis of intermediate I-A: starting from benzene, diphenyl sulfide or thioxanthone, and the acid halide compound containing R 2 group, in ferric chloride, aluminum trichloride or
  • the intermediate I-A is synthesized by the acylation reaction under the action of zinc chloride and the like:
  • acyl oxime ester photoinitiator synthesis intermediate I-B and an acid halide or anhydride containing M1 structure, in the presence of pyridine or triethylamine and other acid binding agents, in dichloromethane, dichloroethane or two
  • the compound of the formula I is synthesized as a solvent such as hexacyclic or the like.
  • the R 1 is selected from Wherein X 1 is -S-, -SS-, -O-, -NR-, wherein R is hydrogen, an alkane or alkoxy group of 1-8 carbon atoms, 3-8 carbons a cycloalkyl group of an atom, said X' and Y' being the same or different, each independently selected from the group consisting of -S-, -SS-, -O-, -CO-, said cyclic structure
  • One or more -H may be -F, -Cl, -Br, -I, -NO 2 , An alkyl or alkoxy group of 1 to 8 carbon atoms or an alkene group of 2 to 8 carbon atoms, wherein R' 1 and R' 2 are each independently selected from -H, An alkyl group of 1 to 8 carbon atoms, a cycloalkyl group of 3 to 8 carbon atoms, an alkene group of 2 to 8 carbon atoms, and R'
  • X 2 is -S-, -SS-, -O-, -NR-, wherein R is hydrogen, an alkane or alkoxy group of 1-8 carbon atoms, 3-8 carbons a cycloalkyl group of an atom, the cyclic structure
  • One or more -H may be -F, -Cl, -Br, -I, -NO 2 , An alkyl or alkoxy group of 1 to 8 carbon atoms or an alkene group of 2 to 8 carbon atoms, wherein R' 1 and R' 2 are each independently selected from -H, An alkyl group of 1 to 8 carbon atoms, a cycloalkyl group of 3 to 8 carbon atoms, an alkene group of 2 to 8 carbon atoms, and R' 3 is selected from -H, an alkyl group of 1 to 8 carbon atoms, 3 a cycloalkyl group of 8 to 8 carbon atoms, an alkene group of 2
  • the R 2 is selected from -H, an alkyl or alkoxy group of 1 to 20 carbon atoms, a cycloalkyl group of 3 to 8 carbon atoms, an alkene group of 2 to 20 carbon atoms or a group represented by R 1 .
  • the specific operation of the step a-formation of the intermediate I-A described in the present invention is: adding the starting material (benzene, diphenyl sulfide or thioxanthone) to the organic solvent A under nitrogen protection, stirring and mixing the AlCl 3
  • the ice brine bath is cooled to about -5 ° C, and a mixture of the R 2 group acid halide compound and the organic solution A is added dropwise, and the temperature is controlled at -5 ° C to 5 ° C. After about 2 h, the ice brine bath is removed. After returning to room temperature naturally, the reaction was stirred for 2 to 3 hours, and worked up to give a white solid intermediate.
  • the optimum molar ratio of the acid halide compound of the starting material (benzene, diphenyl sulfide or thioxanthone), AlCl 3 and R 2 groups is 1:1.1:1.05.
  • the organic solvent A described in the present invention is dichloromethane, dichloroethane, chloroform or carbon tetrachloride.
  • the specific operation of the synthesis of the intermediate I-B of the step b described in the present invention is as follows: the intermediate I is added to the organic solvent B, and after stirring uniformly, hydrochloric acid or hydrogen chloride is added at room temperature, methyl nitrite or nitrous acid is added dropwise. The isoamyl ester was stirred at room temperature for 3 to 5 h, concentrated under reduced pressure, and recrystall
  • the organic solvent B described in the present invention is tetrahydrofuran, isopropyl ether or methyl tert-butyl ether, diethyl ether, anisole, dibutyl ether, ethylene glycol diethyl ether and dioxane.
  • step c acyl oxime ester photoinitiator described in the present invention is: adding the intermediate I-B and pyridine or triethylamine to the organic solvent C, stirring uniformly, and cooling to about 0 ° C in an ice brine bath.
  • the mixture of the acid halide compound of the M1 group and the organic solvent C is added dropwise, and the addition is completed in about 1.5 hours, and the reaction is naturally returned to room temperature, and the reaction is stirred for about 2 hours, and then worked up to obtain a pale yellow oily liquid, which is the formula I of the present invention.
  • the organic solvent C described in the present invention is dichloromethane, dichloroethane, chloroform, carbon tetrachloride or dioxane.
  • the invention also provides the use of an oxime ester compound of the formula I in a UV light-curing material.
  • the invention has the beneficial effects that the ultraviolet absorption effect of the oxime ester compound of the invention is substantially similar to the ultraviolet absorption effect of OXE-1 in the case of the same molar concentration, wherein the heat of the oxime ester compound of the invention is similar.
  • the stability is more stable than OXE-1; the oxime ester compound of the present invention has a partial substance knot
  • the structure has a significant red shift with OXE-1 in the ultraviolet absorption spectrum, and has a large absorption at 300-365 nm, and can be used as an activation light source for the LED cold light source.
  • the application properties (sensitivity, sensitivity, of the oxime ester compound of the present invention)
  • the thermal stability and solubility are better than those of the existing OXE-1, and at the same time, the oxime ester compound exhibits a markedly improved overall application performance as compared with the existing similar products.
  • the oxime ester compound of the present invention has excellent storage stability and high photocuring activity, and can be cross-linked and cured at a low exposure dose, and the curing effect is excellent, and the photocuring process does not produce toxic. Hazardous substances are safe to use.
  • the obtained film has a flat edge without defects, no scum, good integrity of the whole pattern, no wrinkles on the surface, and the color filter produced has high optical transparency and no light leakage.
  • the outstanding performance is excellent in the odor property, storage stability, developability, surface wrinkle resistance of the formed film, and safety in use of the photosensitive composition.
  • Figure 1 is a nuclear magnetic 1 H NMR spectrum of (E)-2-((hydroxyimino)-1-(phenyl)oct-1-one (Compound I-1-1-3).
  • Figure 2 is a nuclear magnetic 1 H NMR spectrum of (E)-1-phenyl-2-((4-(phenylhydrazo)benzoyloxy)imino)oct-1-one (Compound I-1-1) .
  • Figure 3 is a nuclear magnetic ⁇ 1 >H NMR spectrum of (E)-2-((hydroxyimino)-1-(4-(phenylhydrazo)phenyl)oct-1-one (Compound I-3-1-3).
  • Figure 4 is a nuclear magnetic ⁇ 1 >H NMR spectrum of (E)-2-((1,4-bis(phenylindenyl)benzoyloxy)imino)oct-1-one (Compound I-3-1).
  • Figure 5 is (E)-2-((1-(phenylhydrazino)benzoyloxy)imino-4-(phenoxy)benzoyloxy)oct-1-one (Compound I-5- 1) Nuclear magnetic 1 H NMR spectrum.
  • Figure 6 is a nuclear magnetic ⁇ 1 >H NMR spectrum of 1-chloro-4-(2-hydroxyimino)octanoate thioxanthone (I-8-1-3).
  • Figure 8 is a nuclear magnetic field of (E)-1-chloro-(2-(3-phenoxybenzoimido))-4-octanoate thioxanthone (Compound I-10-1) 1 H NMR spectrum.
  • Figure 9 is a UV spectrum of (E)-1-phenyl-2-((4-(phenylhydrazo)benzoyloxy)imino)oct-1-one (Compound 1-1-1).
  • Figure 10 is (E)-2-((1,4-bis(phenylindenyl)benzoyloxy)imino)oct-1-one (Compound I-3-1) UV spectrum.
  • Figure 11 is (E)-2-((1-(phenylhydrazino)benzoyloxy)imino-4-(phenoxy)benzoyloxy)oct-1-one (Compound I-5) -1) UV spectrum.
  • Figure 12 is a UV spectrum of (E)-1-chloro-(2-(3-phenylmercaptobenzoimido))-4-octanoate thioxanthone (Compound I-8-1) Figure.
  • Figure 13 is a UV of (E)-1-chloro-(2-(3-phenoxybenzoimido))-4-octanoate thioxanthone (Compound I-10-1) Spectrum.
  • the compounds of the formula I according to the invention are preferably one or more of the following compounds:
  • a three-necked flask was charged with 200 ml of dichloromethane, 100 g of n-octanoic acid and 2 drops of DMF.
  • a reflux condenser, a constant pressure dropping funnel, a drying tube and an alkali tail gas absorption device were placed, and the mixture was heated to reflux, and 165 g of thionyl chloride was slowly added dropwise.
  • a mixture of 30 ml of methylene chloride and the mixture was refluxed for about 1 hour, and the mixture was evaporated to dryness.
  • a three-necked flask was charged with 25.6 g (0.33 mol) of benzene and 100 ml of dichloromethane, cooled to -5 ° C in an ice brine bath, and passed through nitrogen, 48.1 g (0.34 mol) of anhydrous A1C1 3 was added, and a drying tube, a reflux condenser and an off-gas were added.
  • a three-necked flask was charged with 50 g (0.27 mol) of diphenyl sulfide and 200 ml of dichloromethane, cooled to -5 ° C in an ice brine bath, and passed through nitrogen, 39.4 g (0.30 mol) of anhydrous A1C1 3 was added, and a drying tube and a reflux condenser were added.
  • a three-necked flask was charged with 200 ml of dichloromethane, 100 g of n-octanoic acid and 2 drops of DMF.
  • a reflux condenser, a constant pressure dropping funnel, a drying tube and an alkali tail gas absorption device were placed, and the mixture was heated to reflux, and 165 g of thionyl chloride was slowly added dropwise.
  • a mixture of 30 ml of methylene chloride and the mixture was refluxed for about 1 hour, and the mixture was evaporated to dryness.
  • a three-necked flask was charged with 123 g (0.66 mol) of diphenyl sulfide and 350 ml of dichloromethane, cooled to -5 ° C in an ice brine bath, and passed through nitrogen, 97.1 g (0.73 mol) of anhydrous A1C1 3 was added, and a drying tube and a reflux condenser were added.
  • a three-necked flask was charged with 300 ml of a solution of hydrogen chloride in tetrahydrofuran (containing 29 g of HCl) and 31.2 g (0.1 mol) of compound I-3-1-2, and dissolved by stirring at room temperature, and 150 ml of a solution of methyl nitrite in tetrahydrofuran (0.12 mol) was added dropwise at room temperature.
  • a three-necked flask was charged with 50 g (0.27 mol) of diphenyl sulfide and 200 ml of dichloromethane, cooled to -5 ° C in an ice brine bath, and passed through nitrogen, 39.4 g (0.30 mol) of anhydrous A1C1 3 was added, and a drying tube and a reflux condenser were added.
  • a three-necked flask was charged with 200 ml of dichloromethane, 100 g of n-octanoic acid and 2 drops of DMF.
  • a reflux condenser, a constant pressure dropping funnel, a drying tube and an alkali tail gas absorption device were placed, and the mixture was heated to reflux, and 165 g of thionyl chloride was slowly added dropwise.
  • a mixture of 30 ml of methylene chloride and the mixture was refluxed for about 1 hour, and the mixture was evaporated to dryness.
  • a three-necked flask was charged with 123 g (0.66 mol) of diphenyl sulfide and 350 ml of dichloromethane, cooled to -5 ° C in an ice brine bath, and passed through nitrogen, 97.1 g (0.73 mol) of anhydrous A1C1 3 was added, and a drying tube and a reflux condenser were added.
  • a three-necked flask was charged with 300 ml of a solution of hydrogen chloride in tetrahydrofuran (containing 29 g of HCl) and 31.2 g (0.1 mol) of compound I-3-1-2, and dissolved by stirring at room temperature, and 150 ml of a solution of methyl nitrite in tetrahydrofuran (0.12 mol) was added dropwise at room temperature.
  • a three-necked flask was charged with 50 g (0.29 mol) of diphenyl ether and 200 ml of dichloromethane, and the temperature was lowered to -5 ° C in an ice brine bath. Under nitrogen, 42.1 g (0.32 mol) of anhydrous A1C1 3 was added, and a drying tube and a reflux condenser were added. The tail gas is absorbed, and a mixture of 34.1 g (0.30 mol) of chloroacetyl chloride and 50 ml of methylene chloride is slowly dropped. The temperature is controlled at -5 to 5 ° C, and the addition is completed in about 1 hour. The ice brine bath is removed, and the temperature is naturally restored to room temperature.
  • reaction was stirred for 2 to 3 h, and the reaction was monitored by TLC.
  • the organic phase was combined, washed with 3 ⁇ 100 ml of water, and 2% NaHCO3 solution was adjusted. After the separation, the mixture was separated into 100 ml of water, dried over anhydrous MgSO 4 , filtered, and concentrated under reduced pressure to give 48 g of yellow solid, which is compound I-5-1-4.
  • a three-necked flask was charged with 200 ml of dichloromethane, 100 g of n-octanoic acid and 2 drops of DMF.
  • a reflux condenser, a constant pressure dropping funnel, a drying tube and an alkali tail gas absorption device were placed, and the mixture was heated to reflux, and 165 g of thionyl chloride was slowly added dropwise.
  • a mixture of 30 ml of methylene chloride and the mixture was refluxed for about 1 hour, and the mixture was evaporated to dryness.
  • a three-necked flask was charged with 300 ml of a solution of hydrogen chloride in tetrahydrofuran (containing 29 g of HCl) and 38.9 g (0.1 mol) of compound I-8-1-2, dissolved at room temperature, and 150 ml of a solution of methyl nitrite in tetrahydrofuran (0.12 mol) was added dropwise at room temperature.
  • a three-necked flask was charged with 50 g (0.27 mol) of diphenyl sulfide and 200 ml of dichloromethane, cooled to -5 ° C in an ice brine bath, and passed through nitrogen, 39.4 g (0.30 mol) of anhydrous A1C1 3 was added, and a drying tube and a reflux condenser were added.
  • a three-necked flask was charged with 100 ml of dichloromethane, 21 g of 4-(phenylhydrazino)benzoic acid (0.091 mol) and 2 drops of DMF, and placed on a reflux condenser, a constant pressure dropping funnel, a drying tube and an alkali tail gas absorption device, and heated to After refluxing, a mixture of 11.2 g (0.095 mol) of thionyl chloride and 30 ml of dichloromethane was slowly added dropwise, and the mixture was added dropwise over 0.5 h, refluxed for 1 h, concentrated under reduced pressure, and then evaporated.
  • the yellow oily liquid 26 g is the compound I-8-1-6.
  • a three-necked flask was charged with 200 ml of dichloromethane, 100 g of n-octanoic acid and 2 drops of DMF.
  • a reflux condenser, a constant pressure dropping funnel, a drying tube and an alkali tail gas absorption device were placed, and the mixture was heated to reflux, and 165 g of thionyl chloride was slowly added dropwise.
  • a mixture of 30 ml of methylene chloride and the mixture was refluxed for about 1 hour, and the mixture was refluxed for 2 hr, and concentrated under reduced pressure.
  • a three-necked flask was charged with 300 ml of a hydrogen chloride in tetrahydrofuran solution (containing 29 g of HCl) and 38.9 g (0.1 mol) of compound I-10-1-2, and dissolved by stirring at room temperature, and 150 ml of a solution of methyl nitrite in tetrahydrofuran (0.12 mol) was added dropwise at room temperature.
  • a three-necked flask was charged with 50 g (0.29 mol) of diphenyl ether and 200 ml of dichloromethane, and the temperature was lowered to -5 ° C in an ice brine bath. Under nitrogen, 42.1 g (0.32 mol) of anhydrous A1C1 3 was added, and a drying tube and a reflux condenser were added. The tail gas is absorbed, and a mixture of 34.1 g (0.30 mol) of chloroacetyl chloride and 50 ml of methylene chloride is slowly dropped. The temperature is controlled at -5 to 5 ° C, and the addition is completed in about 1 hour. The ice brine bath is removed, and the temperature is naturally restored to room temperature.
  • reaction was stirred for 2 to 3 h, and the reaction was monitored by TLC.
  • the organic phase was combined, washed with 3 ⁇ 100 ml of water, and 2% NaHCO3 solution was adjusted.
  • the mixture was separated, washed with 100 ml of water, dried over anhydrous MgSO 4 , filtered, and concentrated under reduced pressure. After recrystallization, 48 g of yellow solid was obtained as compound I-10-1-4.
  • the pyrolysis properties of the compounds I-1-1, I-3-1, I-5-1, I-8-1 and I-10-1 were measured by a differential thermal-thermogravimetric analyzer. Heating rate: 10 ° C / min.
  • the initial decomposition temperatures of the compounds I-1-1, I-3-1, I-5-1, I-8-1 and I-10-1 were all above 140 °C, and the thermal stability was good.
  • the compounds I-1-1, I-3-1, I-5-1, I-8-1 and I-10-1 are dissolved in acetonitrile, and each is formulated into a solution of a certain molar concentration, which is obtained by using ultraviolet-visible
  • the ultraviolet absorption spectrum of the spectrophotometer was measured and compared. By detecting the spectrum, it can be seen that the UV absorption bands of several compounds synthesized are broader.
  • the polymerization of hydroxyethyl methacrylate initiated by compounds I-1-1, I-3-1, I-5-1, I-8-1 and I-10-1 in the examples was compared by real-time infrared testing. Double bond conversion rate. Acetone was used as a solvent to prepare samples of compounds I-1-1, I-3-1, I-5-1, I-8-1 and I-10-1 at a concentration of 3% of the monomer concentration. On the KBr salt sheet, it was placed in a Nico-let 5700, and the sample was irradiated with an ultraviolet light source to adjust the ultraviolet light intensity of the sample surface to 30 mW/cm 2 .
  • the double bond conversion rate of the monomer was collected by near-infrared real-time, and the real-time infrared parameter was set to a data acquisition interval of 0.3985 s, and each spectral scan was performed once, with a resolution of 4 cm -1 .
  • the characteristic absorption peak of carbon-carbon double bond in the near-infrared spectrum is 1630 cm -1 , and the carbon-carbon double bond becomes a carbon-carbon single bond and the double-bond absorption peak as the photo-curing reaction proceeds.
  • the intensity weakens as the illumination time increases, so the change in the characteristic absorption peak of the carbon-carbon double bond is used to reflect the degree of change in the polymerization reaction.
  • the double bond conversion rate (DC) is calculated by the data processing software in combination with the following formula.
  • Ao and A t are sample time t before and after light curing hydroxyethyl acrylate double bond character in the area of a peak absorption at 1630cm -1 methacrylic acid.
  • the results showed that the compounds I-1-1, I-3-1, I-5-1, I-8-1 and I-10-1 could all initiate the polymerization of hydroxyethyl methacrylate, after 10 min of illumination, It can convert the double bond of acrylic acid to more than 60%.
  • I-5-1, I-8-1 and I-10-1 adding appropriate amount of chain transfer agent and dye, using propylene glycol methyl ether as solvent, and formulating free radical polymerization imaging photosensitive glue 1, 2, 3 4, 5.
  • the above glue was tested for performance as follows.
  • the rotation speed of the centrifugal coater is controlled so that the coating amount (in terms of solid content) coated on the aluminum plate base is 0.5 to 2.5 g/m 2 , and after preliminary drying on a centrifugal coater, the blast is transferred to 100 ° C.
  • the experimental results show that the plates of compounds I-1-1, I-3-1, I-5-1, I-8-1 and I-10-1 can be seen in the case of exposure time of 40 s. More than 3 segments of the continuous adjustment ruler have an accuracy of 6 ⁇ or more. It can be seen that compounds I-1-1, I-3-1, I-5-1, I-8-1 and I-10-1 can achieve better imaging results under certain exposure time and exposure. It is very suitable for use in violet laser imaging systems.

Abstract

本发明提供一种具有通式Ⅰ所示结构的酰基肟酯结构的化合物，所述化合物具有良好的紫外吸收效果，该化合物具有溶解性好、热稳定性和感光活性高且毒性低的特点，应用性能明显优于同类产品，本发明还提供了一种制备所述酰基肟酯结构的化合物的合成方法，所述合成方法具有简单高效，生产过程中不产生污染性废弃物，且产品纯度高，适用于工业化生产的特点。

Description

肟酯类化合物及其合成方法及应用 技术领域
本发明涉及肟酯类化合物，尤其涉及一种用于UV固化材料的光引发剂及其制备方法。
背景技术
紫外光(UV)固化，简称光固化技术，光固化是利用紫外光照射具有化学活性的液态材料，引发其快速聚合交联，并使其瞬间固化的过程。
固化技术在20世纪80年代就被誉为是一项面向21世纪的绿色工业新技术，该技术是一种高效、环保、节能、优质的材料表面处理技术，在光固化涂料、光刻胶、光固化油墨、微电子、粘和剂、光盘复制、纸张上光技术中得到广泛的应用，在光固化技术进步过程中，光引发剂体系的研究与开发始终占据着十分重要的位置。
1968年Bayer公司开发了第一代紫外光固化木器涂料，首先实现了光固化技术的产业化。随后光固化技术迅猛发展，应用领域不断扩大，形成了一个新的产业。上世纪70、80年代，欧美辐射固化协会成立，推动了光固化技术的研究和发展，在北美、欧洲和日本等发达国家和地区，巴斯夫、拜耳、陶氏等跨国公司纷纷加盟光固化生产，目前已成为了具有一定市场规模的产业。我国从上世纪80年代开始发展光固化技术，由于原料和设备的限制，发展缓慢。进入90年代，紫外光固化技术和设备的引进大大推动了我国光固化产业的发展，进入21世纪，我国光固化产业获得了更加快速的发展，特别是光引发剂已成为世界上最大的生产和出口国，已初步形成一个新的高新产业。如今大力提倡可持续发展，建立和谐社会，并加大了环境的保护，这为我国光固化产业的发展提供了机遇。
当前，关于光引发剂己经有了非常多的报道，例如安息香衍生物、联苯酰缩酮类、α，α一二烷氧基苯乙酮类、二苯甲酮/胺类、米氏酮、噻唑酮/胺类、芳香重氮盐、三氮嗪类、肟酯类等，代表例有可商购的Irgacure369、Darocurel173、OXE-l和OXE-2。然而，这些光引发剂在实际应用中均或多或少地存在感光度低(聚合速率和曝光剂量高)、溶解性差(透明度和光刻残渣多)、贮存稳定性低、短波长灵敏度不足、对可光聚合单体的特定选择性不强等缺陷，从而在整体上影响了感光材料的性能。
作为影响光固化组合物感光性能的最主要因素，光引发剂对可光聚合组合物感光性能的影响不仅体现在光引发剂本身对于辐射的敏感性，还在于它与可光聚合单体(或其组合物)之间的适配性。因此，在确定一种可光聚合组合物的配方时，最优的是寻找一种与内含的可聚合单体之间具有良好效应(例如，协同效应)的光引发剂，从而可以进一步优化组合物的感光性能。
作为优选的可光聚合组合物，一方面要求具有优异的储存稳定性能；另一方面要对短波i线和g线具有高灵敏度，以便降低曝光剂量，提高曝光效率，从而缩短生产周期；再一方面要求由光聚合组合物制备的光固化产品要图像图案精细整，没有缺陷和浮渣，且光固化膜的硬度要好。这些指标对滤光片、光致抗蚀剂的性能尤为重要，而要达到这个效果，首先就要求组合物中使用的光引发剂本身在短波处要具有非常高的感光度，另外整个组合物体系要搭配的非常合理，即组合物中的可聚合成分(单体、树脂)与体系中光引发剂配合使用时能发挥最佳应。目前，针对这方面的研究还非常的少。
现在入们对于光引发剂的效果及其分解产物的毒性、气味和迁移性等特性要求越来越高，开发具有良好的溶解性、低气味或无气味和低迁移性的良好特性的大分子光引发剂将成为未来发展的主要方向。但目前已商业化的大分子光引发剂大多价格昂贵或产品性能有一定缺陷，因此迫切需要价格低廉且性能好的产品来替代。
发明内容
发明目的：为了克服背景技术中现有酰基肟酯类光引发剂应用性能的不足，本发明的目的是提供一种溶解性好、热稳定性好、反应活性高、生产成本低、价格低廉、基本无气味，低迁移性，且使用安全性高(毒性低)的酰基肟酯类化合物。
本发明的另一目的是提供所述酰基肟酯类化合物的制备方法。
本发明的另一目的是提供所述酰基肟酯类化合物在UV光固化材料中的应用。
技术方案：为了达到上述发明目的，本发明提供了一种酰基肟酯类化合物，所述酰基肟酯类光化合物具有通式Ⅰ所示结构：
Figure PCTCN2016083963-appb-000001
其中，
所述R1选自
Figure PCTCN2016083963-appb-000002
其中，所述X1为-S-、-S-S-、-O-、-NR-，其中R为氢、1-8个碳原子的烷烃基或烷氧基、3-8个碳原子的环烷基；所述X‘和Y’相同或不同，各自独立地选自-S-、-S-S-、-O-、-CO-；所述环状结构
Figure PCTCN2016083963-appb-000003
中一个或多个-H可以被-F、-Cl、-Br、-I、-NO2、
Figure PCTCN2016083963-appb-000004
Figure PCTCN2016083963-appb-000005
1-8个碳原子的烷基或烷氧基或2-8个碳原子的烯烃基取代，其中R’1和R’2各自独立地选自-H、
Figure PCTCN2016083963-appb-000006
1-8个碳原子的烷基、3-8个碳原子的环烷基、2-8个碳原子的烯烃基，R’3选自-H、1-8个碳原子的烷基、3-8个碳原子的环烷基、2-8个碳原子的烯烃基或1-8个碳原子的碳链羰基，其中，1-8个碳原子的碳链羰基中羰基在端位，位于连接键处；
所述R3表示
Figure PCTCN2016083963-appb-000007
其中，所述X2为-S-、-S-S-、-O-、-NR-，其中R为氢、1-8个碳原子的烷烃基或烷氧基、3-8个碳原子的环烷基；所述环状结构
Figure PCTCN2016083963-appb-000008
中一个或多个-H可以被-F、-Cl、-Br、-I、-NO2、
Figure PCTCN2016083963-appb-000009
Figure PCTCN2016083963-appb-000010
1-8个碳原子的烷基或烷氧基或2-8个碳原子的烯烃基取代，其中R’1和R’2各自独立地选自-H、
Figure PCTCN2016083963-appb-000011
Figure PCTCN2016083963-appb-000012
1-8个碳原子的烷基、3-8个碳原子的环烷基、2-8个碳原子的烯烃基，R’3选自-H、1-8个碳原子的烷基、3-8个碳原子的环烷基、2-8个碳原子的烯烃基或1-8个碳原子的碳链羰基，其中，1-8个碳原子的碳链羰基中羰基在端位，位于连接键处；
所述R2选自-H、1-20个碳原子的烷基或烷氧基、3-8个碳原子的环烷基、2-20个碳原子的烯烃基或R1所示基团。
在本发明的一些实施方式中，优选地，所述R1选自
Figure PCTCN2016083963-appb-000013
Figure PCTCN2016083963-appb-000014
其中，所述X1为-S-、-S-S-或-O-，其中，所述X‘和Y’相同或不同，各自独立地选自-S-、-O-或-CO-，所述环状结构
Figure PCTCN2016083963-appb-000015
Figure PCTCN2016083963-appb-000016
中一个或多个-H可以被-F、-Cl、-NO2、-COOR′1、-CONR′2、-OR′3、1-8个碳原子的烷基或烷氧基取代，其中R’1和R’2各自独立地选自-H、
Figure PCTCN2016083963-appb-000017
1-8个碳原子的烷基，R’3选自-H、1-8个碳原子的烷基、3-8个碳原子的环烷基。
在本发明的一些实施方式中，优选地，所述R1选自
Figure PCTCN2016083963-appb-000018
Figure PCTCN2016083963-appb-000019
本发明的一些实施方式中，所述R3表示
Figure PCTCN2016083963-appb-000020
其中，所述X2为-S-、-S-S-、-O-、-NR-，其中，所述R为1-5个碳原子的烷烃基或烷氧基、3-8个碳原子的环烷基，所述环状结构
Figure PCTCN2016083963-appb-000021
中一个或多个-H可以被-F、-Cl、-NO2、 -COOR′1、-CONR′2、-OR′3、1-5个碳原子的烷基或烷氧基取代，其中R’1和R’2各自独立地选自-H、
Figure PCTCN2016083963-appb-000022
1-8个碳原子的烷基，R’3选自-H、1-5个碳原子的烷基。
本发明的一些实施方式中，所述R3表示
Figure PCTCN2016083963-appb-000023
其中，所述X2为-S-、-S-S-、-O-、-NR-，其中，所述R为1-5个碳原子的烷烃基或烷氧基、3-8个碳原子的环烷基，所述环状结构
Figure PCTCN2016083963-appb-000024
中一个或多个-H可以被-F、-Cl、-NO2、-COOR′1、-CONR′2、1-5个碳原子的烷基或烷氧基取代，其中R’1和R’2各自独立地选自-H、
Figure PCTCN2016083963-appb-000025
1-8个碳原子的烷基。
本发明的一些实施方式中，所述X2选自-S-、-O-、-S-S-或-NR-，其中，所述R为1-5个碳原子的烷烃基或烷氧基、3-6个碳原子的环烷基。
本发明的一些实施方式中，优选地，所述R3优选自
Figure PCTCN2016083963-appb-000026
Figure PCTCN2016083963-appb-000027
Figure PCTCN2016083963-appb-000028
本发明的一些实施方式中，优选地，所述R2选自-H、1-20个碳原子的烷基或烷氧基、3-8个碳原子的环烷基、2-20个碳原子的烯烃基、
Figure PCTCN2016083963-appb-000029
Figure PCTCN2016083963-appb-000030
本发明的一些实施方式中，优选地，所述R2选自-H、1-15个碳原子的烷基或烷氧基、3-8个碳原子环烷基、2-15个碳原子的烯烃基、
Figure PCTCN2016083963-appb-000031
Figure PCTCN2016083963-appb-000032
本发明的一些实施方式中，优选地，所述R2选自-H、1-15个碳原子的烷基或烷氧基、3-8个碳原子环烷基、2-15个碳原子的烯烃基、
Figure PCTCN2016083963-appb-000033
Figure PCTCN2016083963-appb-000034
本发明的一些实施方式中，优选地，所述R2选自1-15个碳原子的烷基或烷氧基、3-8个碳原子环烷基、2-15个碳原子的烯烃基、
Figure PCTCN2016083963-appb-000035
Figure PCTCN2016083963-appb-000036
本发明的一些实施方式中，通式Ⅰ的化合物选自由通式Ⅰ-1至Ⅰ-10所示化合物组成的组：
Figure PCTCN2016083963-appb-000037
Figure PCTCN2016083963-appb-000038
Figure PCTCN2016083963-appb-000039
以及
Figure PCTCN2016083963-appb-000040
其中，
所述R2选自-H、1-20个碳原子的烷基或烷氧基、3-8个碳原子的环烷基、2-20个碳原子的烯烃基或R1所示基团。
本发明还提供了一种通式Ⅰ所述的酰基肟酯类化合物的制备方法，包含如下步骤：
a、中间体Ⅰ-A的合成：以苯、二苯硫醚或硫杂蒽酮等为起始原料，与含有R2基团的酰卤化合物，在三氯化铁、三氯化铝或氯化锌等作用下，通过付克酰基化反应，合成中间体Ⅰ-A：
Figure PCTCN2016083963-appb-000041
b、中间体Ⅰ-B的合成：中间体I-A在通有氯化氢或加盐酸的情况下与亚硝酸甲酯、亚硝酸乙酯或亚硝酸异戊酯等进行氧化反应，生成酰基肟中间体Ⅰ-B：
Figure PCTCN2016083963-appb-000042
c、酰基肟酯类光引发剂合成：中间体Ⅰ-B与含有M1结构的酰卤或酸酐，在吡啶或三乙胺等缚酸剂存在下，在二氯甲烷、二氯乙烷或二氧六环等做溶剂下合成通式Ⅰ的化合物。
Figure PCTCN2016083963-appb-000043
其中，
所述R1选自
Figure PCTCN2016083963-appb-000044
其中，所述X1为-S-、-S-S-、-O-、-NR-，其中，所述R为氢、1-8个碳原子的烷烃基或烷氧基、3-8个碳原子的环烷基，所述X‘和Y’相同或不同，各自独立地选自-S-、-S-S-、-O-、-CO-，所述环状结构
Figure PCTCN2016083963-appb-000045
中一个或多个-H可以被-F、-Cl、-Br、-I、-NO2、
Figure PCTCN2016083963-appb-000046
Figure PCTCN2016083963-appb-000047
1-8个碳原子的烷基或烷氧基或2-8个碳原子的烯烃基取代，其中R’1和R’2各自独立地选自-H、
Figure PCTCN2016083963-appb-000048
1-8个碳原子的烷基、3-8个碳原子的环烷基、2-8个碳原子的烯烃基，R’3选自-H、1-8个碳原子的烷基、3-8个碳原子的环烷基、2-8个碳原子的烯烃基或1-8个碳原子的碳链羰基，其中，1-8个碳原子的碳链羰基中羰基在端位，位于连接键处；
所述R3表示
Figure PCTCN2016083963-appb-000049
其中，所述X2为-S-、-S-S-、-O-、-NR-，其中，所述R为氢、1-8个碳原子的烷烃基或烷氧基、3-8个碳原子的环烷基，所述环状结构
Figure PCTCN2016083963-appb-000050
中一个或多个-H可以被-F、-Cl、-Br、-I、-NO2、
Figure PCTCN2016083963-appb-000051
Figure PCTCN2016083963-appb-000052
1-8个碳原子的烷基或烷氧基或2-8个碳原子的烯烃基取代，其中R’1和R’2各自独立地选自-H、
Figure PCTCN2016083963-appb-000053
Figure PCTCN2016083963-appb-000054
1-8个碳原子的烷基、3-8个碳原子的环烷基、2-8个碳原子的烯烃基，R’3选自-H、1-8个碳原子的烷基、3-8个碳原子的环烷基、2-8个碳原子的烯烃基或1-8个碳原子的碳链羰基，其中，1-8个碳原子的碳链羰基中羰基在端位，位于连接键处；
所述R2选自-H、1-20个碳原子的烷基或烷氧基、3-8个碳原子的环烷基、2-20个碳原子的烯烃基或R1所示基团。
具体反应路线如下：
Figure PCTCN2016083963-appb-000055
本发明中所述的步骤a中间体Ⅰ-A合成的具体操作为：氮气保护下，向有机溶剂A中加入起始原料(苯、二苯硫醚或硫杂蒽酮)、AlCl3搅拌混合，冰盐水浴冷却至-5℃左右，滴加R2基团的酰卤化合物与有机溶液A的混合液，温度控制在-5℃～5℃，约2h滴加完毕，撤去冰盐水浴，自然恢复至室温，继续搅拌反应2～3h，后处理得到白色固体中间体I。起始原料(苯、二苯硫醚或硫杂蒽酮)、AlCl3和R2基团的酰卤化合物的最佳摩尔比为1：1.1：1.05。
本发明中所述的有机溶剂A为二氯甲烷、二氯乙烷、氯仿或四氯化碳。
本发明中所述的步骤b中间体Ⅰ-B合成的具体操作为：有机溶剂B中加入中间体I，搅拌均匀后，室温下加入盐酸或通氯化氢，通亚硝酸甲酯或滴加亚硝酸异戊酯，室温搅拌反应3～5h，减压浓缩，重结晶得白色固体中间体Ⅱ。
本发明中所述的有机溶剂B为四氢呋喃、异丙醚或甲基叔丁基醚、乙醚、苯甲醚、丁醚、乙二醇二乙醚及二氧六环。
本发明中所述的步骤c酰基肟酯光引发剂合成的具体操作为：向有机溶剂C中加入中间体Ⅰ-B和吡啶或三乙胺，搅拌均匀，冰盐水浴冷却至0℃左右开始滴加M1基团的酰卤化合物及有机溶剂C的混合液，1.5h左右滴加完毕，自然恢复至室温继续搅拌反应2h左右，后处理，得浅黄色油状液体，即为本发明通式Ⅰ所示的酰基肟酯类化合物
本发明中所述的有机溶剂C为二氯甲烷、二氯乙烷、氯仿、四氯化碳或二氧六环。
本发明还提供了一种通式Ⅰ所述肟酯类化合物在UV光固化材料中的应用。
本发明的有益效果：本发明所述的肟酯类化合物在摩尔浓度相同的情况下，其紫外吸收效果与OXE-1的紫外吸收效果基本相近，其中本发明所述的肟酯类化合物的热稳定性比OXE-1更加稳定；本发明所述的肟酯类化合物有部分的物质结 构在紫外吸收图谱中与OXE-1有明显红移，在300～365nm有较大吸收，可实现LED冷光源作为激活光源使用，本发明所述的肟酯类化合物的应用性能(感光度、热稳定性、溶解性)比现有的OXE-1的应用性能好，同时，相比于现有同类产品，所述的肟酯类化合物在整体上表现出了显著改善的综合应用性能。
另外，本发明所述的肟酯类化合物还具有非常优异的储存稳定性和很高的光固化活性，在低曝光剂量下，就能交联固化且固化效果极佳，光固化过程不产生有毒、有害物质，使用安全性高。制得的膜边缘平整无缺陷，没有浮渣，整个图案完整度好，表面没有折皱，制成的彩色滤光片光学透明度高，不漏光。突出的表现在感光性组合物的气味性、存储稳定性、显影性、成形膜的表面抗折皱性、使用安全性等方面，取得了非常好的技术效果。
附图说明
图1为(E)-2-((羟亚氨基)-1-(苯基)辛-1-酮(化合物Ⅰ-1-1-3)核磁1HNMR谱图。
图2为(E)-1-苯基-2-((4-(苯巯基)苯甲酰氧基)亚氨基)辛-1-酮(化合物Ⅰ-1-1)的核磁1HNMR谱图。
图3为(E)-2-((羟亚氨基)-1-(4-(苯巯基)苯基)辛-1-酮(化合物Ⅰ-3-1-3)的核磁1HNMR谱图。
图4为(E)-2-((1，4-二(苯巯基)苯甲酰氧基)亚氨基)辛-1-酮(化合物Ⅰ-3-1)的核磁1HNMR谱图。
图5为(E)-2-((1-(苯巯基)苯甲酰氧基)亚氨基-4-(苯氧基)苯甲酰氧基)辛-1-酮(化合物Ⅰ-5-1)的核磁1HNMR谱图。
图6为1-氯-4-(2-羟亚胺基)辛酸酯基硫杂蒽酮(Ⅰ-8-1-3)的核磁1HNMR谱图。
图7为(E)-1-氯-(2-(3-苯巯基苯甲酰亚氨酯基))-4-辛酸酯基硫杂蒽酮(化合物Ⅰ-8-1)的核磁1HNMR谱图。
图8为(E)-1-氯-(2-(3-苯氧基苯甲酰亚氨酯基))-4-辛酸酯基硫杂蒽酮(化合物Ⅰ-10-1)的核磁1HNMR谱图。
图9为(E)-1-苯基-2-((4-(苯巯基)苯甲酰氧基)亚氨基)辛-1-酮(化合物Ⅰ-1-1)的UV谱图。
图10为(E)-2-((1，4-二(苯巯基)苯甲酰氧基)亚氨基)辛-1-酮(化合物Ⅰ-3-1) 的UV谱图。
图11为为(E)-2-((1-(苯巯基)苯甲酰氧基)亚氨基-4-(苯氧基)苯甲酰氧基)辛-1-酮(化合物Ⅰ-5-1)的UV谱图。
图12为(E)-1-氯-(2-(3-苯巯基苯甲酰亚氨酯基))-4-辛酸酯基硫杂蒽酮(化合物Ⅰ-8-1)的UV谱图。
图13为(E)-1-氯-(2-(3-苯氧基苯甲酰亚氨酯基))-4-辛酸酯基硫杂蒽酮(化合物Ⅰ-10-1)的UV谱图。
具体实施方式
本发明通式Ⅰ的化合物优选如下化合物中的一种或多种：
Figure PCTCN2016083963-appb-000056
Figure PCTCN2016083963-appb-000057
Figure PCTCN2016083963-appb-000058
Figure PCTCN2016083963-appb-000059
Figure PCTCN2016083963-appb-000060
Figure PCTCN2016083963-appb-000061
Figure PCTCN2016083963-appb-000062
Figure PCTCN2016083963-appb-000063
Figure PCTCN2016083963-appb-000064
Figure PCTCN2016083963-appb-000065
实施例1
正辛酰氯(Ⅰ-1-1-1)的制备
Figure PCTCN2016083963-appb-000066
三口烧瓶，加入二氯甲烷200ml、正辛酸100g以及2滴DMF，搭上回流冷凝管、恒压滴液漏斗、干燥管及碱液尾气吸收装置，加热至回流，缓慢滴加165g氯化亚砜及30ml二氯甲烷混合液，约1h滴加完毕，回流2h，减压浓缩，加入新鲜二氯甲烷100ml再次减压浓缩，得浅黄色溶液114g，即为化合物Ⅰ-1-1-1。
1-(苯基)辛-1-酮(化合物Ⅰ-1-1-2)的制备
Figure PCTCN2016083963-appb-000067
三口烧瓶，加入25.6g(0.33mol)苯和100ml二氯甲烷，冰盐水浴降温至-5℃，通氮气，加入48.1g(0.34mol)无水A1C13，加干燥管、回流冷凝管及尾气吸收，缓慢滴56g(0.35mol)的正辛酰氯(Ⅰ-1-1-1)和50ml二氯甲烷的混合液，控制温度在-5～5℃，约1h滴加完毕，撤去冰盐水浴，自然恢复至室温，继续搅拌反应2～3h，TLC监控反应完全。将反应液慢倒入10％的冰的稀盐酸中，搅拌30min后分液，100ml二氯甲烷萃取水相，合并有机相，3×100ml水洗涤，2％NaHCO3溶液调至中性后分液，100ml水洗1次，无水MgSO4干燥，过滤，减压浓缩，然后过硅胶柱得黄色油状液体57g，即为化合物Ⅰ-1-1-2，MS：m/z＝204.2。
(E)-2-((羟亚氨基)-1-(苯基)辛-1-酮(化合物Ⅰ-1-1-3)的制备
Figure PCTCN2016083963-appb-000068
三口烧瓶，加入5g(24.5mmol)化合物Ⅰ-1-1-2和30ml四氢呋喃溶液，室温搅拌溶解，通入HCl气体，室温下滴加4.3g(36.8mmol)亚硝酸异戊酯，TLC监控至反应完全后，加入50ml二氯甲烷，2％NaHCO3溶液调至中性后分液，3×50ml水洗涤，无水MgSO4干燥，过滤后减压浓缩，得红棕色油状液体6g，即为化合物Ⅰ-1-1-3，MS：m/z＝233.1。
1HNMR(300MHz，CDCl3)，0.85～0.88(t，J＝6.8Hz，3H)，2.74～2.76(t，J＝6.4Hz，2H)，1.26-1.31(m，6H)，1.54-1.56(m，2H)，8.65(br，1H)，7.41-7.45(d，J＝9.2Hz，2H)，7.52-7.56(m，1H)，7.75-7.79(d，J＝9.2Hz，2H)，如图1所示。
2-氯-1-(4-(苯巯基)苯基)乙酮(化合物Ⅰ-1-1-4)的制备
Figure PCTCN2016083963-appb-000069
三口烧瓶，加入50g(0.27mol)二苯硫醚和200ml二氯甲烷，冰盐水浴降温至-5℃，通氮气，加入39.4g(0.30mol)无水A1C13，加干燥管、回流冷凝管及尾气吸收，缓慢滴31.8g(0.28mol)的氯乙酰氯和50ml二氯甲烷的混合液，控制温度在-5～5℃，约1h滴加完毕，撤去冰盐水浴，自然恢复至室温，继续搅拌反应2～3h，TLC监控反应完全。将反应液缓慢倒入10％的冰的稀盐酸中，PH＝4，搅拌30min后分液，100ml二氯甲烷萃取水相，合并有机相，3×100ml水洗涤，2％NaHCO3溶液调至中性后分液，100ml水洗1次，无水MgSO4干燥，过滤，减压浓缩，重结晶后得到45g黄色固体，即为化合物Ⅰ-1-1-4.
4-苯巯基苯甲酸(化合物Ⅰ-1-1-5)的制备
Figure PCTCN2016083963-appb-000070
在三口瓶中，加入冷却的25％NaOH溶液(1)，NaClO溶液(10％)(1)，三甲基苄基溴化铵，控温0℃～5℃，控温缓慢滴45g(0.17mol)的2-氯-1-(4-(苯巯基)苯基)已酮(化合物Ⅰ-1-4)和200ml二氯甲烷的混合液，约2h滴加完毕，撤去冰盐水浴，自然恢复至室温，继续搅拌反应2～3h，TLC监控反应完全。加入亚硫酸氢钠，搅拌30min后加入200ml二氯甲烷萃和10％的盐酸，PH＝3，分液，再用150ml二氯甲烷萃取水相，合并有机相，3×100ml水洗涤至中性后分液，无水MgSO4干燥，过滤，减压浓缩，重结晶后得到30g黄色固体，即为化合物Ⅰ-1-1-5.
4-(苯巯基)苯甲酰氯(化合物Ⅰ-1-1-6)的制备
Figure PCTCN2016083963-appb-000071
三口烧瓶，加入二氯甲烷100ml、4-(苯巯基)苯甲酸(Ⅰ-1-1-5)21g(0.091mol)以及2滴DMF，搭上回流冷凝管、恒压滴液漏斗、干燥管及碱液尾气吸收装置，加热至回流，缓慢滴加11.2g(0.095mol)氯化亚砜及30ml二氯甲烷混合液，约0.5h滴加完毕，回流1h，减压浓缩，加入新鲜二氯甲烷100ml再次减压浓缩，得棕黄色油状液体26g，即为化合物Ⅰ-1-1-6。
(E)-1-苯基-2-((4-(苯巯基)苯甲酰氧基)亚氨基)辛-1-酮(化合物Ⅰ-1-1)的制备
Figure PCTCN2016083963-appb-000072
加入23.3g(0.10mol)化合物Ⅰ-1-1-3和100ml二氯甲烷，降温至0℃左右后加入11.7g(0.15mol)吡啶，控温滴加27.2g(0.11mol)化合物Ⅰ-1-1-6及50ml二氯甲烷，滴加完毕后控温0℃-5℃反应3h，反应完毕，加入100ml H20，加入饱和NaHCO3溶液洗至pH＝5左右，3×100ml水洗至中性，无水MgSO4干燥，过滤，减压浓缩得橙黄色油状液体42.5g，无水乙醇重结晶，得到29g浅黄色固体，收率为收率68％，即为化合物Ⅰ-1-1。
1HNMR(300MHz，CDCl3)，0.83～0.85(t，J＝6.9Hz，3H)，1.27-1.30(t，J＝7.2Hz，4H)，1.41(s，J＝6.2Hz，2H)，1.60-1.70(m，2H)，2.88-2.93(t，J＝8.1Hz，2H)，7.24-7.28(d，J＝8.7Hz，2H)，7.44-7.66(m，7H)，7.96-7.98(m，2H)，8.06～8.09(d，J＝8.7Hz，2H)，如图2所示。
实施例2
正辛酰氯(Ⅰ-3-1-1)的制备
Figure PCTCN2016083963-appb-000073
三口烧瓶，加入二氯甲烷200ml、正辛酸100g以及2滴DMF，搭上回流冷凝管、恒压滴液漏斗、干燥管及碱液尾气吸收装置，加热至回流，缓慢滴加165g氯化亚砜及30ml二氯甲烷混合液，约1h滴加完毕，回流2h，减压浓缩，加入新鲜二氯甲烷100ml再次减压浓缩，得浅黄色溶液114g，即为化合物Ⅰ-3-1-1。
1-(4-(苯巯基)苯基)辛-1-酮(化合物Ⅰ-3-1-2)的制备
Figure PCTCN2016083963-appb-000074
三口烧瓶，加入123g(0.66mol)二苯硫醚和350ml二氯甲烷，冰盐水浴降温至-5℃，通氮气，加入97.1g(0.73mol)无水A1C13，加干燥管、回流冷凝管及尾气吸收，缓慢滴113g(0.69mol)的正辛酰氯(Ⅰ-3-1-1)和50ml二氯甲烷的混合液，控制温度在-5～5℃，约2h滴加完毕，撤去冰盐水浴，自然恢复至室温，继续搅拌反应2～3h，TLC监控反应完全。将反应物缓慢倒入200ml 10％的冰的稀盐酸中，搅拌30min后分液，100ml二氯甲烷萃取水相，合并有机相，3×100ml水洗涤，2％NaHCO3溶液调至中性后分液，100ml水洗1次，无水MgSO4干燥，过滤，减压浓缩，重结晶得白色固体175g，即为化合物Ⅰ-3-1-2，产率85％。MP：31-32℃；MS：m/z＝312.15。
(E)-2-((羟亚氨基)-1-(4-(苯巯基)苯基)辛-1-酮(化合物Ⅰ-3-1-3)的制备
Figure PCTCN2016083963-appb-000075
三口烧瓶，加入300ml氯化氢的四氢呋喃溶液(含29gHCl)和31.2g(0.1mol)化合物Ⅰ-3-1-2，室温搅拌溶解，室温下滴加150ml亚硝酸甲酯的四氢呋喃溶液(0.12mol)，至反应完全后，减压浓缩，得橙红色油状液体40g，加入250ml二氯甲烷，3×100ml水洗涤，无水MgSO4干燥，过滤后减压浓缩，得红棕色油状液体34g，加入120ml石油醚，搅拌下加热溶解完全，缓慢降温至-5℃，析出白 色固体，抽滤，石油醚洗滤饼，得白色固体18.7g，即为化合物Ⅰ-3-1-3，产率55％。
1HNMR(300MHz，CDCl3)，0.88(t，J＝6.6Hz，3H)，2.73(t，J＝7.5Hz，2H)，1.29-1.36(m，6H)，1.50-1.58(m，2H)，8.73(br，1H)，7.18-7.28(d，J＝4.2Hz，2H)，7.39-7.44(m，3H)，7.50-7.53(m，2H)，7.78-7.87(d，J＝8.7Hz，2H)，如图3所示。
2-氯-1-(4-(苯巯基)苯基)乙酮(化合物Ⅰ-3-1-4)的制备
Figure PCTCN2016083963-appb-000076
三口烧瓶，加入50g(0.27mol)二苯硫醚和200ml二氯甲烷，冰盐水浴降温至-5℃，通氮气，加入39.4g(0.30mol)无水A1C13，加干燥管、回流冷凝管及尾气吸收，缓慢滴31.8g(0.28mol)的氯乙酰氯和50ml二氯甲烷的混合液，控制温度在-5～5℃，约1h滴加完毕，撤去冰盐水浴，自然恢复至室温，继续搅拌反应2～3h，TLC监控反应完全。将反应液缓慢倒入10％的冰的稀盐酸中，PH＝4，搅拌30min后分液，100ml二氯甲烷萃取水相，合并有机相，3×100ml水洗涤，2％NaHCO3溶液调至中性后分液，100ml水洗1次，无水MgSO4干燥，过滤，减压浓缩，重结晶后得到45g黄色固体，即为化合物Ⅰ-3-1-4.
4-苯巯基苯甲酸(化合物Ⅰ-3-1-5)的制备
Figure PCTCN2016083963-appb-000077
在三口瓶中，加入冷却的25％NaOH溶液，NaClO溶液(10％)，三甲基苄基溴化铵，控温0℃～5℃，控温缓慢滴45g(0.17mol)的2-氯-1-(4-(苯巯基)苯基)已酮(化合物Ⅰ-3-1-4)的和200ml二氯甲烷的混合液，约2h滴加完毕，撤去冰盐水浴，自然恢复至室温，继续搅拌反应2～3h，TLC监控反应完全。加入亚硫酸氢钠，搅拌30min后加入200ml二氯甲烷萃和10％的盐酸，PH＝3，分液，再用150ml二氯甲烷萃取水相，合并有机相，3×100ml水洗涤至中性后分液，无水MgSO4干燥，过滤，减压浓缩，重结晶后得到30g黄色固体，即为化合物Ⅰ-3-1-5.
4-(苯巯基)苯甲酰氯(化合物Ⅰ-3-1-6)的制备
Figure PCTCN2016083963-appb-000078
三口烧瓶，加入二氯甲烷100ml、4-(苯巯基)苯甲酸(Ⅰ-3-1-5)21g(0.091mol)以及2滴DMF，搭上回流冷凝管、恒压滴液漏斗、干燥管及碱液尾气吸收装置，加热至回流，缓慢滴加11.2g(0.095mol)氯化亚砜及30ml二氯甲烷混合液，约0.5h滴加完毕，回流1h，减压浓缩，加入新鲜二氯甲烷100ml再次减压浓缩，得棕黄色油状液体26g，即为化合物Ⅰ-3-1-6。
(E)-2-((1，4-二(苯巯基)苯甲酰氧基)亚氨基)辛-1-酮(化合物Ⅰ-3-1)的制备
Figure PCTCN2016083963-appb-000079
加入34.1g(0.10mol)化合物Ⅰ-3-1-3和100ml二氯甲烷，降温至0℃左右后加入11.7g(0.15mol)吡啶，控温滴加27.2g(0.11mol)化合物Ⅰ-3-1-6及50ml二氯甲烷，滴加完毕后控温0℃-5℃反应3h，反应完毕，加入100ml H20，，加入饱和NaHCO3溶液洗至pH＝5左右，3×100ml水洗至中性，无水MgSO4干燥，过滤，减压浓缩得橙黄色油状液体50g，无水乙醇重结晶，得到41g浅黄色固体，收率为收率75％，即为化合物Ⅰ-3-1。
1HNMR(300MHz，CDCl3)，0.84～0.86(t，J＝6.9Hz，3H)，1.25-1.28(t，J＝7.2Hz，4H)，1.38(s，J＝6.2Hz，2H)，1.59-1.64(m，2H)，2.84-2.89(t，J＝8.1Hz，2H)，7.20-7.28(d，J＝8.7Hz，2H)，7.42-7.45(m，5H)，7.53-7.56(m，4H)，7.93～7.96(d，J＝8.7Hz，2H)，8.03～8.06(d，J＝8.5Hz，2H)，如图4所示。
实施例3
正辛酰氯(Ⅰ-5-1-1)的制备
Figure PCTCN2016083963-appb-000080
三口烧瓶，加入二氯甲烷200ml、正辛酸100g以及2滴DMF，搭上回流冷凝管、恒压滴液漏斗、干燥管及碱液尾气吸收装置，加热至回流，缓慢滴加165g氯化亚砜及30ml二氯甲烷混合液，约1h滴加完毕，回流2h，减压浓缩，加入新鲜二氯甲烷100ml再次减压浓缩，得浅黄色溶液114g，即为化合物Ⅰ-5-1-1。
1-(4-(苯巯基)苯基)辛-1-酮(化合物Ⅰ-5-1-2)的制备
Figure PCTCN2016083963-appb-000081
三口烧瓶，加入123g(0.66mol)二苯硫醚和350ml二氯甲烷，冰盐水浴降温至-5℃，通氮气，加入97.1g(0.73mol)无水A1C13，加干燥管、回流冷凝管及尾气吸收，缓慢滴113g(0.69mol)的正辛酰氯(Ⅰ-5-1-1)和50ml二氯甲烷的混合液，控制温度在-5～5℃，约2h滴加完毕，撤去冰盐水浴，自然恢复至室温，继续搅拌反应2～3h，TLC监控反应完全。将反应物缓慢倒入200ml 10％的冰的稀盐酸中，搅拌30min后分液，100ml二氯甲烷萃取水相，合并有机相，3×100ml水洗涤，2％NaHCO3溶液调至中性后分液，100ml水洗1次，无水MgSO4干燥，过滤，减压浓缩，重结晶得白色固体175g，即为化合物Ⅰ-5-1-2，产率85％。MP：31-32℃；MS：m/z＝312.15。
(E)-2-((羟亚氨基)-1-(4-(苯巯基)苯基)辛-1-酮(化合物Ⅰ-5-1-3)的制备
Figure PCTCN2016083963-appb-000082
三口烧瓶，加入300ml氯化氢的四氢呋喃溶液(含29gHCl)和31.2g(0.1mol)化合物Ⅰ-3-1-2，室温搅拌溶解，室温下滴加150ml亚硝酸甲酯的四氢呋喃溶液(0.12mol)，至反应完全后，减压浓缩，得橙红色油状液体40g，加入250ml二氯甲烷，3×100ml水洗涤，无水MgSO4干燥，过滤后减压浓缩，得红棕色油状液体34g，加入120ml石油醚，搅拌下加热溶解完全，缓慢降温至-5℃，析出白色固体，抽滤，石油醚洗滤饼，得白色固体18.7g，即为化合物Ⅰ-5-1-3，产率55％。
1HNMR(300MHz，CDCl3)，0.88(t，J＝6.6Hz，3H)，2.73(t，J＝7.5Hz，2H)，1.29-1.36(m，6H)，1.50-1.58(m，2H)，8.73(br，1H)，7.18-7.28(d，J＝4.2Hz，2H)，7.39-7.44(m，3H)，7.50-7.53(m，2H)，7.78-7.87(d，J＝8.7Hz，2H)。
2-氯-1-(4-(苯氧基)苯基)乙酮(化合物Ⅰ-5-1-4)的制备
Figure PCTCN2016083963-appb-000083
三口烧瓶，加入50g(0.29mol)二苯醚和200ml二氯甲烷，冰盐水浴降温至-5℃，通氮气，加入42.1g(0.32mol)无水A1C13，加干燥管、回流冷凝管及尾气吸收，缓慢滴34.1g(0.30mol)的氯乙酰氯和50ml二氯甲烷的混合液，控制温度在-5～5℃，约1h滴加完毕，撤去冰盐水浴，自然恢复至室温，继续搅拌反应2～3h，TLC监控反应完全。将反应液缓慢倒入10％的冰的稀盐酸中，PH＝4，搅拌30min 后分液，100ml二氯甲烷萃取水相，合并有机相，3×100ml水洗涤，2％NaHCO3溶液调至中性后分液，100ml水洗1次，无水MgSO4干燥，过滤，减压浓缩，重结晶后得到48g黄色固体，即为化合物Ⅰ-5-1-4.
4-苯氧基苯甲酸(化合物Ⅰ-5-1-5)的制备
Figure PCTCN2016083963-appb-000084
在三口瓶中，加入冷却的25％NaOH溶液，NaClO溶液(10％)，三甲基苄基溴化铵，控温0℃～5℃，控温缓慢滴45g(0.18mol)的Ⅰ-5-1-4和200ml二氯甲烷的混合液，约2h滴加完毕，撤去冰盐水浴，自然恢复至室温，继续搅拌反应2～3h，TLC监控反应完全。加入亚硫酸氢钠，搅拌30min后加入200ml二氯甲烷萃和10％的盐酸，PH＝3，分液，再用150ml二氯甲烷萃取水相，合并有机相，3×100ml水洗涤至中性后分液，无水MgSO4干燥，过滤，减压浓缩，重结晶后得到29g黄色固体，即为化合物Ⅰ-5-1-5.
4-(苯氧基)苯甲酰氯(化合物Ⅰ-5-1-6)的制备
Figure PCTCN2016083963-appb-000085
三口烧瓶，加入二氯甲烷100ml、4-苯氧基苯甲酸(Ⅰ-5-1-5)20g(0.093mol)以及2滴DMF，搭上回流冷凝管、恒压滴液漏斗、干燥管及碱液尾气吸收装置，加热至回流，缓慢滴加16.7g(0.14mol)氯化亚砜及30ml二氯甲烷混合液，约0.5h滴加完毕，回流1h，减压浓缩，加入新鲜二氯甲烷100ml再次减压浓缩，得黄色油状液体23g，即为化合物Ⅰ-5-1-6。
(E)-2-((1-(苯巯基)苯甲酰氧基)亚氨基-4-(苯氧基)苯甲酰氧基)辛-1-酮(化合物Ⅰ-5-1)的制备
Figure PCTCN2016083963-appb-000086
加入34.1g(0.10mol)化合物Ⅰ-5-1-3和100ml二氯甲烷，降温至0℃左右后加入11.7g(0.15mol)吡啶，控温滴加25.5g(0.11mol)化合物Ⅰ-5-1-6及50ml二氯 甲烷，滴加完毕后控温0℃-5℃反应3h，反应完毕，加入100ml H20，，加入饱和NaHCO3溶液洗至pH＝5左右，3×100ml水洗至中性，无水MgSO4干燥，过滤，减压浓缩得橙黄色油状液体48g，无水乙醇重结晶，得到39g浅黄色固体，收率为收率73％，即为化合物Ⅰ-5-1。
1HNMR(300MHz，CDCl3)，0.83～0.85(t，J＝6.9Hz，3H)，1.24-1.27(t，J＝7.2Hz，4H)，1.38(s，J＝6.2Hz，2H)，1.56-1.64(m，2H)，2.84-2.89(t，J＝8.1Hz，2H)，7.02-7.08(m，4H)，7.19-7.25(m，3H)，7.39-7.41(m，5H)，7.51～7.53(d，J＝5.7Hz，2H)，7.91～7.94(s，J＝8.5Hz，1H)，8.03～8.06(m，3H)，如图5所示。
实施例4
正辛酰氯(化合物Ⅰ-8-1-1)的制备
Figure PCTCN2016083963-appb-000087
三口烧瓶，加入二氯甲烷200ml、正辛酸100g以及2滴DMF，搭上回流冷凝管、恒压滴液漏斗、干燥管及碱液尾气吸收装置，加热至回流，缓慢滴加165g氯化亚砜及30ml二氯甲烷混合液，约1h滴加完毕，回流2h，减压浓缩，加入新鲜二氯甲烷100ml再次减压浓缩，得浅黄色溶液114g，即为化合物Ⅰ-8-1-1。
1-氯-4-辛酸酯基硫杂蒽酮(化合物Ⅰ-8-1-2)的制备
Figure PCTCN2016083963-appb-000088
加入5.24g(0.02mol)化合物1-氯-4-羟基硫杂蒽酮和50ml二氯甲烷，降温至0℃左右后加入2.37g(0.03mol)吡啶，控温滴加3.56g(0.022mol)化合物Ⅰ-8-1-1及20ml二氯甲烷，滴加完毕后自然升温反应3h，TLC板跟踪至反应完毕，加入30ml H20，搅拌30min后分液，加入饱和NaHCO3溶液100ml洗至pH＝10左右，水洗涤至中性，再加入2％稀盐酸调至pH＝4左右，3×100ml水洗至中性，无水MgSO4干燥，过滤，减压浓缩得棕黄色固体，乙醇重结晶得6.5g，收率84％，即为化合物Ⅰ-8-1-2。
1-氯-4-(2-羟亚胺基)辛酸酯基硫杂蒽酮(Ⅰ-8-1-3)的制备
Figure PCTCN2016083963-appb-000089
三口烧瓶，加入300ml氯化氢的四氢呋喃溶液(含29gHCl)和38.9g(0.1mol)化合物Ⅰ-8-1-2，室温搅拌溶解，室温下滴加150ml亚硝酸甲酯的四氢呋喃溶液(0.12mol)，至反应完全后，减压浓缩，得橙红色油状液体49g，加入250ml二氯甲烷，3×100ml水洗涤，无水MgSO4干燥，过滤后减压浓缩，得红棕色油状液体41g，加入120ml石油醚，搅拌下加热溶解完全，缓慢降温至-5℃，析出土黄色固体，抽滤，石油醚洗滤饼，得土黄色固体26.7g，即为化合物Ⅰ-8-1-3，产率64％。
1HNMR(300MHz，CDCl3)，0.85～0.88(t，J＝7.3Hz，3H)，2.71～2.75(t，J＝9.4Hz，2H)，1.30-1.36(m，6H)，1.50-1.57(m，2H)，11.24(br，1H)，7.21(s，J＝7.2Hz，1H)，7.26～7.31(s，J＝7.2Hz，1H)，7.46(s，J＝8.1Hz，1H)，7.54-7.57(d，J＝8.9Hz，2H)，8.24-8.26(s，J＝7.2Hz，1H)，如图6所示。
2-氯-1-(4-(苯巯基)苯基)乙酮(化合物Ⅰ-8-1-4)的制备
Figure PCTCN2016083963-appb-000090
三口烧瓶，加入50g(0.27mol)二苯硫醚和200ml二氯甲烷，冰盐水浴降温至-5℃，通氮气，加入39.4g(0.30mol)无水A1C13，加干燥管、回流冷凝管及尾气吸收，缓慢滴31.8g(0.28mol)的氯乙酰氯和50ml二氯甲烷的混合液，控制温度在-5～5℃，约1h滴加完毕，撤去冰盐水浴，自然恢复至室温，继续搅拌反应2～3h，TLC监控反应完全。将反应液缓慢倒入10％的冰的稀盐酸中，PH＝4，搅拌30min后分液，100ml二氯甲烷萃取水相，合并有机相，3×100ml水洗涤，2％NaHCO3溶液调至中性后分液，100ml水洗1次，无水MgSO4干燥，过滤，减压浓缩，重结晶后得到45g黄色固体，即为化合物Ⅰ-8-1-4.
4-苯巯基苯甲酸(化合物Ⅰ-8-1-5)的制备
Figure PCTCN2016083963-appb-000091
在三口瓶中，加入冷却的25％NaOH溶液，NaClO溶液(10％)，三甲基苄基溴化铵，控温0℃～5℃，控温缓慢滴45g(0.17mol)的Ⅰ-8-1-4和200ml二氯甲烷的混合液，约2h滴加完毕，撤去冰盐水浴，自然恢复至室温，继续搅拌反应 2～3h，TLC监控反应完全。加入亚硫酸氢钠，搅拌30min后加入200ml二氯甲烷萃和10％的盐酸，PH＝3，分液，再用150ml二氯甲烷萃取水相，合并有机相，3×100ml水洗涤至中性后分液，无水MgSO4干燥，过滤，减压浓缩，重结晶后得到30g黄色固体，即为化合物Ⅰ-8-1-5.
4-(苯巯基)苯甲酰氯(化合物Ⅰ-8-1-6)的制备
Figure PCTCN2016083963-appb-000092
三口烧瓶，加入二氯甲烷100ml、4-(苯巯基)苯甲酸21g(0.091mol)以及2滴DMF，搭上回流冷凝管、恒压滴液漏斗、干燥管及碱液尾气吸收装置，加热至回流，缓慢滴加11.2g(0.095mol)氯化亚砜及30ml二氯甲烷混合液，约0.5h滴加完毕，回流1h，减压浓缩，加入新鲜二氯甲烷100ml再次减压浓缩，得棕黄色油状液体26g，即为化合物Ⅰ-8-1-6。
(E)-1-氯-(2-(3-苯巯基苯甲酰亚氨酯基))-4-辛酸酯基硫杂蒽酮(化合物Ⅰ-8-1)的制备
加入8.36g(0.02mol)化合物Ⅰ-8-1-3和50ml二氯甲烷，降温至0℃左右后加入2.37g(0.03mol)吡啶，控温滴加5.45g(0.022mol)化合物Ⅰ-8-1-6及20ml二氯甲烷，滴加完毕后自然升温反应3h，反应完毕，加入30ml H20，搅拌30min后分液，加入饱和NaHCO3溶液100ml洗至pH＝10左右，水洗涤至中性，再加入2％稀盐酸调至pH＝4左右，3×100ml水洗至中性，无水MgSO4干燥，过滤，减压浓缩得土黄色固体，乙醇重结晶得10g，收率80％，即为化合物Ⅰ-8-1。
1HNMR(300MHz，CDCl3)，0.85～0.88(t，J＝6.4Hz，3H)，2.83～2.85(t，J＝8.5Hz，2H)，1.30-1.33(m，4H)，1.43-1.47(m，2H)，1.63～1.68(m，2H)，7.36～7.38(d，J＝7.4Hz，2H)，7.44～7.50(m，6H)，7.54～7.58(m，4H)，8.12～8.15(d，J＝9.2Hz，2H)，8.43～8.45(s，J＝8.4Hz，1H)，如图7所示。
实施例5
正辛酰氯(化合物Ⅰ-10-1-1)的制备
Figure PCTCN2016083963-appb-000094
三口烧瓶，加入二氯甲烷200ml、正辛酸100g以及2滴DMF，搭上回流冷凝管、恒压滴液漏斗、干燥管及碱液尾气吸收装置，加热至回流，缓慢滴加165g氯化亚砜及30ml二氯甲烷混合液，约1h滴加完毕，回流2h，减压浓缩，加入新鲜二氯甲烷100ml再次减压浓缩，得浅黄色溶液114g，即为化合物Ⅰ-10-1-1。
1-氯-4-辛酸酯基硫杂蒽酮(化合物Ⅰ-10-1-2)的制备
Figure PCTCN2016083963-appb-000095
加入5.24g(0.02mol)化合物1-氯-4-羟基硫杂蒽酮和50ml二氯甲烷，降温至0℃左右后加入2.37g(0.03mol)吡啶，控温滴加3.56g(0.022mol)化合物Ⅰ-10-1-1及20ml二氯甲烷，滴加完毕后自然升温反应3h，TLC板跟踪至反应完毕，加入30ml H20，搅拌30min后分液，加入饱和NaHCO3溶液100ml洗至pH＝10左右，水洗涤至中性，再加入2％稀盐酸调至pH＝4左右，3×100ml水洗至中性，无水MgSO4干燥，过滤，减压浓缩得棕黄色固体，乙醇重结晶得6.5g，收率84％，即为化合物Ⅰ-10-1-2。
1-氯-4-(2-羟亚胺基)辛酸酯基硫杂蒽酮(Ⅰ-10-1-3)的制备
Figure PCTCN2016083963-appb-000096
三口烧瓶，加入300ml氯化氢的四氢呋喃溶液(含29gHCl)和38.9g(0.1mol)化合物Ⅰ-10-1-2，室温搅拌溶解，室温下滴加150ml亚硝酸甲酯的四氢呋喃溶液(0.12mol)，至反应完全后，减压浓缩，得橙红色油状液体49g，加入250ml二氯甲烷，3×100ml水洗涤，无水MgSO4干燥，过滤后减压浓缩，得红棕色油状液体41g，加入120ml石油醚，搅拌下加热溶解完全，缓慢降温至-5℃，析出棕土黄色固体，抽滤，石油醚洗滤饼，得土黄色固体26.7g，即为化合物Ⅰ-10-1-3，产率64％。
1HNMR(300MHz，CDCl3)，0.85～0.88(t，J＝7.3Hz，3H)，2.71～2.75(t，J＝9.4Hz，2H)，1.30-1.36(m，6H)，1.50-1.57(m，2H)，11.24(br，1H)，7.21(s，J＝7.2Hz，1H)，7.26～7.31(s，J＝7.2Hz，1H)，7.46(s，J＝8.1Hz，1H)，7.54-7.57(d，J＝8.9 Hz，2H)，8.24-8.26(s，J＝7.2Hz，1H)。
2-氯-1-(4-(苯氧基)苯基)乙酮(化合物Ⅰ-10-1-4)的制备
Figure PCTCN2016083963-appb-000097
三口烧瓶，加入50g(0.29mol)二苯醚和200ml二氯甲烷，冰盐水浴降温至-5℃，通氮气，加入42.1g(0.32mol)无水A1C13，加干燥管、回流冷凝管及尾气吸收，缓慢滴34.1g(0.30mol)的氯乙酰氯和50ml二氯甲烷的混合液，控制温度在-5～5℃，约1h滴加完毕，撤去冰盐水浴，自然恢复至室温，继续搅拌反应2～3h，TLC监控反应完全。将反应液缓慢倒入10％的冰的稀盐酸中，PH＝4，搅拌30min后分液，100ml二氯甲烷萃取水相，合并有机相，3×100ml水洗涤，2％NaHCO3溶液调至中性后分液，100ml水洗1次，无水MgSO4干燥，过滤，减压浓缩，重结晶后得到48g黄色固体，即为化合物Ⅰ-10-1-4.
4-苯氧基苯甲酸(化合物Ⅰ-10-1-5)的制备
Figure PCTCN2016083963-appb-000098
在三口瓶中，加入冷却的25％NaOH溶液，NaClO溶液(10％)，三甲基苄基溴化铵，控温0℃～5℃，控温缓慢滴45g(0.18mol)的Ⅰ-10-1-4和200ml二氯甲烷的混合液，约2h滴加完毕，撤去冰盐水浴，自然恢复至室温，继续搅拌反应2～3h，TLC监控反应完全。加入亚硫酸氢钠，搅拌30min后加入200ml二氯甲烷萃和10％的盐酸，PH＝3，分液，再用150ml二氯甲烷萃取水相，合并有机相，3×100ml水洗涤至中性后分液，无水MgSO4干燥，过滤，减压浓缩，重结晶后得到29g黄色固体，即为化合物Ⅰ-10-1-5.
4-(苯氧基)苯甲酰氯(化合物Ⅰ-10-1-6)的制备
Figure PCTCN2016083963-appb-000099
三口烧瓶，加入二氯甲烷100ml、4-苯氧基苯甲酸(Ⅰ-10-1-5)20g(0.093mol)以及2滴DMF，搭上回流冷凝管、恒压滴液漏斗、干燥管及碱液尾气吸收装置，加热至回流，缓慢滴加16.7g(0.14mol)氯化亚砜及30ml二氯甲烷混合液，约0.5h滴加完毕，回流1h，减压浓缩，加入新鲜二氯甲烷100ml再次减压浓缩，得黄色油状液体23g，即为化合物Ⅰ-10-1-6。
(E)-1-氯-(2-(3-苯氧基苯甲酰亚氨酯基))-4-辛酸酯基硫杂蒽酮(化合物Ⅰ-10-1)的制备
Figure PCTCN2016083963-appb-000100
加入8.36g(0.02mol)化合物Ⅰ-10-1-3和50ml二氯甲烷，降温至0℃左右后加入2.37g(0.03mol)吡啶，控温滴加5.1g(0.022mol)化合物Ⅰ-10-1-6及20ml二氯甲烷，滴加完毕后自然升温反应3h，反应完毕，加入30ml H20，搅拌30min后分液，加入饱和NaHCO3溶液100ml洗至pH＝10左右，水洗涤至中性，再加入2％稀盐酸调至pH＝4左右，3×100ml水洗至中性，无水MgSO4干燥，过滤，减压浓缩得土黄色固体，乙醇重结晶得10g，收率80％，即为化合物Ⅰ-10-1。
1HNMR(300MHz，CDCl3)，0.86～0.88(t，J＝6.5Hz，3H)，2.65～2.70(t，J＝8.5Hz，2H)，1.30～1.40(m，6H)，1.49～1.57(m，2H)，7.13～7.22(m，4H)，7.36(s，J＝7.4Hz，1H)，7.42～7.55(m，5H)，7.58～7.61(m，2H)，8.25～8.28(d，J＝7.9Hz，2H)，8.43～8.46(s，J＝8.4Hz，1H)，如图8所示。
应用实施例1
检测了化合物Ⅰ-1-1、Ⅰ-3-1、Ⅰ-5-1、Ⅰ-8-1及Ⅰ-10-1在常用的有机溶剂，如乙酸乙酯、乙二醇单乙醚、丙二醇甲醚、丙二醇甲醚醋酸酯中的溶解性。分别取五份等量的化合物Ⅰ-1-1、Ⅰ-3-1、Ⅰ-5-1、Ⅰ-8-1及Ⅰ-10-1置于五个试样瓶中，分别用乙二醇单乙醚、丙二醇甲醚醋酸酯溶解，通过TLC检测光引发剂在溶液中的稳定性。结果显示均具有一定的溶解性，且此类光引发剂在有机溶剂中的稳定性比较好，避光条件下在常用溶剂中均能保持20天以上不发生分解。
应用实施例2
利用差热-热重分析仪测定化合物Ⅰ-1-1、Ⅰ-3-1、Ⅰ-5-1、Ⅰ-8-1及Ⅰ-10-1的热解性能。升温速度：10℃/min。检测了化合物Ⅰ-1-1、Ⅰ-3-1、Ⅰ-5-1、Ⅰ-8-1及Ⅰ-10-1初始分解温度均在140℃以上，热稳定性较好。
应用实施例3
将化合物Ⅰ-1-1、Ⅰ-3-1、Ⅰ-5-1、Ⅰ-8-1及Ⅰ-10-1溶解在乙腈中，分别配成一定摩尔浓度的溶液，通过用紫外-可见分光光度计测其紫外吸收谱图，进行比较。通过检测谱图可以看出所合成的几种化合物紫外吸收谱带较宽泛，在
300～365nm均有较大吸收，如图9、图10、图11、图12及图13所示。
应用实施例4
利用实时红外测试手段，比较了实施例中化合物Ⅰ-1-1、Ⅰ-3-1、Ⅰ-5-1、Ⅰ-8-1及Ⅰ-10-1引发甲基丙烯酸羟乙酯聚合的双键转化率。以丙酮为溶剂，配制化合物Ⅰ-1-1、Ⅰ-3-1、Ⅰ-5-1、Ⅰ-8-1及Ⅰ-10-1的浓度为单体浓度的3％的试样，涂于KBr盐片上，然后放入Nico-let5700中，用紫外光点光源照射样品，调节样品表面的紫外光光强为30mW/cm2。单体的双键转化率用近红外实时采集，实时红外参数设置为数据采集间隔0.3985s，每个光谱扫描1次，分辨率为4cm-1。甲基丙烯酸羟乙酯在近红外谱图中碳碳双键的特征吸收峰在1630cm-1处，随着光固化反应的进行，碳碳双键变成碳碳单键，双键的吸收峰强度随光照时间增加而变弱，所以利用碳碳双键的特征吸收峰的变化来反映其聚合反应的变化程度。双键转化率(DC)由数据处理软件结合下式计算得到。
DC(％)＝[1-(At/Ao)]×100％
式中Ao和At分别为样品在固化前和光照后t时刻在1630cm-1处甲基丙烯酸羟乙酯双键特征吸收峰的面积。检测结果显示化合物Ⅰ-1-1、Ⅰ-3-1、Ⅰ-5-1、Ⅰ-8-1及Ⅰ-10-1均可以引发甲基丙烯酸羟乙酯聚合，在光照l0min之后，均能使丙烯酸双键的转化率达60％以上。
应用实施例5
用聚乙烯吡咯烷酮(MW＝40000)与聚甲基丙烯酸酯树脂(Mn＝50000)作成膜树脂，2-羟丁基丙烯酸酯作聚合单体，分别加入化合物Ⅰ-1-1、Ⅰ-3-1、Ⅰ-5-1、Ⅰ-8-1及Ⅰ-10-1，加入适量的链转移剂和染料，用丙二醇甲醚作溶剂，配成自由基聚合成像感光胶液1、2、3、4、5。将以上胶液按以下方法进行性能测试。将感光胶液1～5用离心机旋涂在预先处理好的并满足下列条件的PS铝版基上，铝板基尺寸：1030mm×800mm；铝板基厚度：0.28～0.3mm；砂目规格：Ra＝0.5～0.6μm，Rh＝0.3～0.35μm；阳极氧化膜重量：3～3.5g/m2。控制离心涂布机的转速，使涂在铝版基上的涂布量(以固含量计)为0.5～2.5g/m2，在离心涂布机上初步干燥后，转移到100℃的鼓风干燥机中干燥3min，得紫激光CTP原版。将原版经紫激光曝光，用Ugra测试条做掩膜测试版材的感光性能。曝光后，用1％NaOH水溶液显影。曝光区，可光聚合化合物在引发剂存在下发生聚合反应，显影液中不溶，而非曝光区是可溶的，于是得到阴图。通过曝光显影，从得到的图像的的连续调梯尺评价感度，从微线条测试块区域评价精度，从而评价感光组合物感光性能的优劣。实验结果显示在曝光时间均为40s的情况下，化合物Ⅰ-1-1、Ⅰ-3-1、Ⅰ-5-1、Ⅰ-8-1及Ⅰ-10-1的版材均能显到连续调梯尺的3段以上，精度在6μ以上。由此可见，化合物Ⅰ-1-1、Ⅰ-3-1、Ⅰ-5-1、Ⅰ-8-1及Ⅰ-10-1在一定曝光时间及曝光量下，能达到较好的成像效果，可很好的适用于紫激光成像体系中。

Claims (9)

  1. 一种酰基肟酯类化合物，所述酰基肟酯类光化合物具有通式Ⅰ所示结构：
    Figure PCTCN2016083963-appb-100001
    其中，
    所述R1选自
    Figure PCTCN2016083963-appb-100002
    其中，所述X1为-S-、-S-S-、-O-或-NR-，其中R为氢、1-8个碳原子的烷烃基或烷氧基、3-8个碳原子的环烷基；所述X‘和Y’相同或不同，各自独立地选自-S-、-S-S-、-O-、-CO-；所述环状结构
    Figure PCTCN2016083963-appb-100003
    中一个或多个-H可以被-F、-Cl、-Br、-I、-NO2、-COOR′1、-CONR′2、-OR′3、
    Figure PCTCN2016083963-appb-100004
    Figure PCTCN2016083963-appb-100005
    1-8个碳原子的烷基或烷氧基或2-8个碳原子的烯烃基取代，其中R’1和R’2各自独立地选自-H、
    Figure PCTCN2016083963-appb-100006
    1-8个碳原子的烷基、3-8个碳原子的环烷基、2-8个碳原子的烯烃基，R’3选自-H、1-8个碳原子的烷基、3-8个碳原子的环烷基、2-8个碳原子的烯烃基或1-8个碳原子的碳链羰基，其中，1-8个碳原子的碳链羰基中羰基在端位，位于连接键处；
    所述R3表示
    Figure PCTCN2016083963-appb-100007
    其中，所述X2为-S-、-S-S-、-O-或-NR-，其中R为氢、1-8个碳原子的烷烃基或烷氧基、3-8个碳原子的环烷基，所述环状结构
    Figure PCTCN2016083963-appb-100008
    中一个或多个-H可以被-F、-Cl、-Br、-I、-NO2、-COOR′1、-CONR′2、-OR′3、
    Figure PCTCN2016083963-appb-100009
    1-8个碳原子的烷基或烷氧基或2-8个 碳原子的烯烃基取代，其中R’1和R’2各自独立地选自-H、
    Figure PCTCN2016083963-appb-100010
    Figure PCTCN2016083963-appb-100011
    1-8个碳原子的烷基、3-8个碳原子的环烷基、2-8个碳原子的烯烃基；R’3选自-H、1-8个碳原子的烷基、3-8个碳原子的环烷基、2-8个碳原子的烯烃基或1-8个碳原子的碳链羰基，其中，1-8个碳原子的碳链羰基中羰基在端位，位于连接键处；
    所述R2选自-H、1-20个碳原子的烷基或烷氧基、3-8个碳原子的环烷基、2-20个碳原子的烯烃基或与R1所示基团相同。
  2. 根据权利要求1所述的酰基肟酯类化合物，其特征在于，所述R1选自
    Figure PCTCN2016083963-appb-100012
    其中，所述X1为-S-、-S-S-或-O-，其中，所述X‘和Y’相同或不同，各自独立地选自-S-、-O-或-CO-；所述环状结构
    Figure PCTCN2016083963-appb-100013
    中一个或多个-H可以被-F、-Cl、-NO2、-COOR′1、-CONR′2、-OR′3、1-8个碳原子的烷基或烷氧基取代，其中R’1和R’2各自独立地选自-H、
    Figure PCTCN2016083963-appb-100014
    1-8个碳原子的烷基，R’3选自-H、1-8个碳原子的烷基、3-8个碳原子的环烷基。
  3. 根据权利要求2所述的酰基肟酯类化合物，其特征在于，所述R1选自
    Figure PCTCN2016083963-appb-100015
  4. 根据权利要求1所述的酰基肟酯类化合物，其特征在于，所述R3表示
    Figure PCTCN2016083963-appb-100016
    其中，所述X2为-S-、-S-S-、-O-、-NR-，其中，所述R为1-5个碳原子的烷烃基或烷氧基、3-8个碳原子的环烷基，所述环状结构
    Figure PCTCN2016083963-appb-100017
    中一个或多个-H可以被-F、-Cl、-NO2、-COOR′1、-CONR′2、-OR′3、1-5个碳原子的烷基或烷氧基取代，其中R’1和R’2各自独立地选自-H、
    Figure PCTCN2016083963-appb-100018
    Figure PCTCN2016083963-appb-100019
    1-8个碳原子的烷基，R’3选自-H、1-5个碳原子的烷基。
  5. 根据权利要求4所述的肟酯类化合物，其特征在于，所述R3优选自
    Figure PCTCN2016083963-appb-100020
  6. 根据权利要求1所述的酰基肟酯类化合物，其特征在于，所述R2选自-H、1-20个碳原子的烷基或烷氧基、3-8个碳原子的环烷基、2-20个碳原子的烯烃基、
    Figure PCTCN2016083963-appb-100021
  7. 根据权利要求1-6中任一项所述的酰基肟酯类化合物，其特征在于，通式Ⅰ的化合物选自由通式Ⅰ-1至Ⅰ-10所示化合物组成的组：
    Figure PCTCN2016083963-appb-100022
    Figure PCTCN2016083963-appb-100023
    Figure PCTCN2016083963-appb-100024
  8. 一种通式Ⅰ所述的酰基肟酯类化合物的制备方法，包含如下步骤：
    a、中间体Ⅰ-A的合成：以苯、二苯硫醚或硫杂蒽酮为起始原料，与含有R2基团的酰卤化合物，在三氯化铁、三氯化铝或氯化锌作用下，通过付克酰基化反应，合成中间体Ⅰ-A：
    Figure PCTCN2016083963-appb-100025
    b、中间体Ⅰ-B的合成：中间体I-A在通有氯化氢或加盐酸的情况下与亚硝酸甲酯、亚硝酸乙酯或亚硝酸异戊酯进行氧化反应，生成酰基肟中间体Ⅰ-B：
    Figure PCTCN2016083963-appb-100026
    c、酰基肟酯类光引发剂合成：中间体Ⅰ-B与含有M1结构的酰卤或酸酐，在吡啶或三乙胺等缚酸剂存在下，在二氯甲烷、二氯乙烷或二氧六环溶剂下合成通式Ⅰ的化合物；
    Figure PCTCN2016083963-appb-100027
    其中，
    所述R1选自
    Figure PCTCN2016083963-appb-100028
    其中，所述X1为-S-、-S-S-、-O-或-NR-，其中R为氢、1-8个碳原子的烷烃基或烷氧基、3-8个碳原子的环烷基；所述X‘和Y’相同或不同，各自独立地选自-S-、-S-S-、-O-或-CO-； 所述环状结构
    Figure PCTCN2016083963-appb-100029
    中一个或多个-H可以被-F、-Cl、-Br、-I、-NO2、-COOR′1、-CONR′2、-OR′3、
    Figure PCTCN2016083963-appb-100030
    Figure PCTCN2016083963-appb-100031
    1-8个碳原子的烷基或烷氧基或2-8个碳原子的烯烃基取代，其中R’1和R’2各自独立地选自-H、
    Figure PCTCN2016083963-appb-100032
    1-8个碳原子的烷基、3-8个碳原子的环烷基、2-8个碳原子的烯烃基，R’3选自-H、1-8个碳原子的烷基、3-8个碳原子的环烷基、2-8个碳原子的烯烃基或1-8个碳原子的碳链羰基，其中，1-8个碳原子的碳链羰基中羰基在端位，位于连接键处；
    所述R3表示
    Figure PCTCN2016083963-appb-100033
    其中，所述X2为-S-、-S-S-、-O-或-NR-，其中R为氢、1-8个碳原子的烷烃基或烷氧基、3-8个碳原子的环烷基；所述环状结构
    Figure PCTCN2016083963-appb-100034
    中一个或多个-H可以被-F、-Cl、-Br、-I、-NO2、-COOR′1、-CONR′2、-OR′3、
    Figure PCTCN2016083963-appb-100035
    1-8个碳原子的烷基或烷氧基或2-8个碳原子的烯烃基取代，其中R’1和R’2各自独立地选自-H、
    Figure PCTCN2016083963-appb-100036
    Figure PCTCN2016083963-appb-100037
    1-8个碳原子的烷基、3-8个碳原子的环烷基、2-8个碳原子的烯烃基，R’3选自-H、1-8个碳原子的烷基、3-8个碳原子的环烷基、2-8个碳原子的烯烃基或1-8个碳原子的碳链羰基，其中，1-8个碳原子的碳链羰基中羰基在端位，位于连接键处；
    所述R2选自-H、1-20个碳原子的烷基或烷氧基、3-8个碳原子的环烷基、2-20个碳原子的烯烃基或R1所示基团。
  9. 一种权利要求1-7中任一项所述酰基肟酯类化合物在UV光固化材料中的应用。
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