WO2023195774A1 - Sel de diphényliodonium pour photoinitiateur et son procédé de préparation - Google Patents

Sel de diphényliodonium pour photoinitiateur et son procédé de préparation Download PDF

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Publication number
WO2023195774A1
WO2023195774A1 PCT/KR2023/004604 KR2023004604W WO2023195774A1 WO 2023195774 A1 WO2023195774 A1 WO 2023195774A1 KR 2023004604 W KR2023004604 W KR 2023004604W WO 2023195774 A1 WO2023195774 A1 WO 2023195774A1
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Prior art keywords
formula
salt
sulfate
anion
iodonium
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PCT/KR2023/004604
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English (en)
Korean (ko)
Inventor
이성권
이순호
이희진
하재성
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이피캠텍 주식회사
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Publication of WO2023195774A1 publication Critical patent/WO2023195774A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C17/00—Preparation of halogenated hydrocarbons
    • C07C17/013—Preparation of halogenated hydrocarbons by addition of halogens
    • C07C17/02—Preparation of halogenated hydrocarbons by addition of halogens to unsaturated hydrocarbons
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C17/00—Preparation of halogenated hydrocarbons
    • C07C17/38—Separation; Purification; Stabilisation; Use of additives
    • C07C17/42—Use of additives, e.g. for stabilisation
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C25/00—Compounds containing at least one halogen atom bound to a six-membered aromatic ring
    • C07C25/18—Polycyclic aromatic halogenated hydrocarbons

Definitions

  • the present invention relates to a high purity diphenyliodonium salt used as a photoinitiator and a method for producing the same.
  • a photoinitiator is a substance that is added to an ultraviolet curable paint and absorbs light and decomposes to produce chemically active atoms or molecules. It refers to a substance that initiates a polymer reaction by absorbing energy from an ultraviolet light source. Photoinitiators are generally used with various compounds containing acrylic or epoxy reactive groups, and representative industrial applications include hard coatings that make plastic surfaces with weak physical properties harder, adhesives that bond materials under UV light, and UV-curable paints. It has a variety of application fields, including use in
  • a substance useful as such a UV photoinitiator is diphenyliodonium salt.
  • Diphenyliodonium salt not only acts as a photoinitiator but also has the advantage of improving adhesive performance and anti-humidity function.
  • diphenyl iodonium salt prepared by conventional methods has a dark brown color, making it difficult to apply in fields that require colorless transparency.
  • the present invention selectively extracts and removes impurities that may affect the color of the final material without affecting the physical characteristics and recovery rate of the diphenyliodonium salt, ultimately producing high-purity diphenyl.
  • the present invention reacts phenyl iodine having an R1 substituent and benzene having an R2 substituent to prepare a diphenyliodonium salt of the following formula (1), by separating the diphenyliodonium sulfate obtained as a reaction intermediate.
  • a method for producing a diphenyliodonium salt of the following formula (1) is provided, which includes the steps of purifying:
  • a - refers to a counter anion other than sulfate
  • R1 and R2 are each independently straight or branched chain alkyl having 1 to 6 carbon atoms.
  • the present invention provides a diphenyliodonium salt of Formula 1 having a purity of 95% or more as measured by anion ion chromatography.
  • the present invention provides diphenyliodonium salts of formula (1) having a Gardner color value of 3 to 8.
  • the present invention provides a purity of 95% or more as measured by anion ion chromatography or a Gardner color value of 3 to 8.
  • a photoinitiator comprising a diphenyliodonium salt of formula (1) is provided.
  • the advantage of the diphenyliodonium salt having a purity of 95% or more or a Gardner color value of 3 to 8 as measured by anion ion chromatography of the present invention is that it does not show color when used as a photoinitiator, so it can be used in fields that require transparency. There is.
  • the method for producing diphenyl iodonium salt of the present invention has the effect of providing diphenyl iodonium salt with high purity, and as a result, it has the advantage of being able to be used in fields where a transparent photoinitiator is required.
  • the diphenyliodonium salt of Formula 1 is conventionally manufactured through a one-pot reaction, and at this time, a side reaction occurs, making it difficult to obtain the final material pure.
  • the present inventors selectively extracted and removed impurities that may affect the color of the final material without affecting the physical characteristics and recovery rate of the diphenyliodonium salt, and ultimately produced a high-purity diphenyliodonium salt.
  • the present invention is not a one-pot reaction, and develops a purification technology that can separate and extract intermediate compounds and selectively dissolve only the molecules that cause color development, thereby preserving the existing physical characteristics of the diphenyliodonium salt and maintaining long-term storage stability. This high diphenyliodonium salt was developed and the present invention was completed.
  • the present invention involves reacting phenyl iodine with an R1 substituent and benzene with an R2 substituent to produce a diphenyl iodonium salt of the following formula (1), which involves the steps of separating and purifying the sulfate of diphenyl iodonium obtained as a reaction intermediate.
  • a method for producing a diphenyliodonium salt of the following formula (1) is provided.
  • a - refers to a counter anion other than sulfate
  • R1 and R2 are each independently straight or branched chain alkyl having 1 to 6 carbon atoms.
  • the counter anion is preferably one selected from the anion group below, which has the advantage of having an excellent photoinitiator role and being applicable to various fields.
  • the method for producing the compound of Formula 1 of the present invention is specifically
  • Step 1 Preparing di(alkylphenyl)iodonium sulfate of Formula 4 by reacting the compound of Formula 2 of Scheme 1 below and the compound of Formula 3 below in the presence of persulfate.
  • Step 2 Separating and purifying di(alkylphenyl)iodonium sulfate of formula 4, and
  • Step 3 It includes preparing a compound of Formula 1 by reacting the purified di(alkylphenyl)iodonium sulfate of Formula 4 with an anionic salt.
  • M is a monovalent cation
  • a - is a counter anion other than sulfate
  • R1 and R2 are each independently straight or branched chain alkyl having 1 to 6 carbon atoms.
  • the anionic salt of step 3 is a metal or non-metal salt of A - .
  • R1 and R2 may each independently be methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, t-butyl, n-pentyl, isopentyl, etc.
  • R1 may be methyl and R2 may be isobutyl.
  • the compound of Formula 1 may be a compound of Formula 5 below.
  • the reaction may proceed in the presence of an acid and a solvent, and the solvent is preferably one or more selected from water and alcohol.
  • the acid can be any acid soluble in water or alcohol without limitation, and includes sulfuric acid-based acids; Carboxylic acids such as acetic acid and citric acid; Nitric acid system; phosphoric acid system; and one or two or more types selected from the group consisting of halogen acids such as hydrochloric acid and hydrofluoric acid.
  • persulfate is used to promote the reaction and prepare sulfate of di(alkylphenyl)iodonium, which is an intermediate.
  • persulfate is preferably ammonium persulfate, potassium persulfate, sodium persulfate, etc. I can hear it.
  • ammonium persulfate, potassium persulfate, and sodium persulfate are used as persulfate, di(alkylphenyl)iodonium ammonium sulfate, di(alkylphenyl)iodonium potassium sulfate, and di(alkylphenyl)iodonium are used, respectively.
  • Sodium sulfate is obtained.
  • the persulfate can be used in the amount of 1.5 to 2 equivalents per equivalent of the compound of Formula 2, and in this case, di(alkylphenyl)iodonium sulfate of Formula 4 can be produced in high yield.
  • Step 1 can be performed at -15°C to 50°C.
  • Step 2 is a step of separating the di(alkylphenyl)iodonium sulfate of Chemical Formula 4 prepared as an intermediate and removing impurities, especially impurities that give color to the final product. Step 2 proceeds with washing using a solvent that dissolves impurities without dissolving di(alkylphenyl)iodonium sulfate of Chemical Formula 4.
  • Solvents that dissolve the impurities include hydrocarbons having 4 to 10 carbon atoms, toluene, acetonitrile, 1,2-dichloroethane, acetone, and alcohols having 3 to 10 carbon atoms.
  • hydrocarbons having 4 to 10 carbon atoms toluene, acetonitrile, 1,2-dichloroethane, acetone, and alcohols having 3 to 10 carbon atoms.
  • ether Isopropyl ether, t-butyl methyl ether
  • tetra It can be performed using hydrofuran (tetrahydrofuran, etc.), acetate-based solvents (ethyl acetate, butyl acetate, etc.), etc.
  • the solvent is preferably a hydrocarbon having 4 to 10 carbon atoms.
  • the solvent may be used in an amount of 90 mL to 300 mL per 100 g of di(alkylphenyl)iodonium sulfate of Chemical Formula 4, and the purification step may be performed at once, or the solvent may be divided and repeated two or more times.
  • step 2 is performed at 0 to 50°C, impurities can be easily removed.
  • Step 3 is a step of reacting purified di(alkylphenyl)iodonium sulfate of Formula 4 with a metal or non-metal salt of an anion to finally obtain a useful compound of Formula 1.
  • the metal or non-metal contained in the metal or non-metal salt of the anion may be a Group 1 element including Li, Na, K, etc., or may be a Group 2 element including Be, Mg, Ca, etc. Additionally, it may be an ammonium salt containing nitrogen (N), or a sulfonium salt containing sulfur (S).
  • a - The metal or non-metal salt of the anion can be reacted in an amount of 0.5 to 4 equivalents, preferably 1 to 1.5 equivalents, based on 1 equivalent of di(alkylphenyl)iodonium sulfate of Chemical Formula 4.
  • the metal or non-metal salt of the anion is reacted in the above equivalent weight range, the yield can be increased in the subsequent purification process, and after the reaction is completed, no residue remains, which has the excellent effect of increasing purity.
  • Step 3 may be carried out in a solvent, and the solvent is preferably water, ethyl acetate, butylacetate, toluene, chloroform, dichloromethane, dichloro ethane, tetrahydrofuran, acetonitrile, nitrile-based, ether-based, alcohol-based, It may be one or two or more types selected from carbonate-based solvents, etc.
  • the solvent is preferably water, ethyl acetate, butylacetate, toluene, chloroform, dichloromethane, dichloro ethane, tetrahydrofuran, acetonitrile, nitrile-based, ether-based, alcohol-based, It may be one or two or more types selected from carbonate-based solvents, etc.
  • a step is taken to remove unreacted products, side reactants, and other foreign substances generated in the step of reacting di(alkylphenyl)iodonium sulfate of Chemical Formula 4 with an anionic metal or non-metal salt.
  • a filtration or purification step may be additionally included.
  • a purification process can be performed by washing the organic phase with water.
  • the reaction temperature in step 3 is -50°C or higher and 100°C or lower, preferably -20°C or higher and 50°C or lower, more preferably -10°C or higher and 30°C or lower, and even more preferably -10°C or higher and 15°C or lower. You can.
  • the present invention provides a diphenyliodonium salt of the following formula (1) prepared by including the purification step of the present invention and having a purity of 95% by weight or more as measured by anion ion chromatography.
  • the present invention provides a diphenyliodonium salt of the formula (1) prepared comprising the purification step of the present invention and having a Gardner color value of 3 to 12, preferably 3 to 8, more preferably 3 to 6.
  • a - refers to a counter anion other than sulfate
  • R1 and R2 are each independently straight or branched chain alkyl having 1 to 6 carbon atoms.
  • the counter anion is preferably one selected from the following anion group.
  • the compound of Formula 1 is preferably a compound of Formula 5 below.
  • a - refers to a counter anion, preferably PF 6 , PO 2 F 2 , bis(oxalato)borate (BOB), or bisfluorosulfonylimide (FSI).
  • the raw material when the counter anion in the compound of formula 5 is PF 6 , the raw material can be hardened by acid generation, and when it is PO 2 F 2 , there is an advantage that thermal stability and long-term stability are particularly excellent.
  • the counter anion in the compound of Formula 5 is bisfluorosulfonylimide (FSI)
  • FSI bisfluorosulfonylimide
  • the present invention provides a diphenyliodonium salt of formula (1) having a purity of 95% by weight or more as measured by anion ion chromatography or a Gardner color value of 3 to 12, preferably 3 to 8, and more preferably 3 to 6. It provides a photoinitiator containing a.
  • the diphenyliodonium salt of the present invention has high purity and can be used in fields that require transparency when used as a photoinitiator.
  • it when it is in liquid form, it has the advantage of being easy to mix with other ingredients, having excellent stability depending on the type of counter anion, and being able to be used under various conditions.
  • Analysis method Dissolve 10g of analysis sample in 10g of solvent and analyze by placing the solution in a dedicated analysis container.
  • Example 2-1 It was prepared in the same manner as Example 2-1, except that toluene was used instead of the heptane used in Example 2-1. Obtain 92.8 g (0.19 mol; 87%; Gardner value 2.1) of (4-isobutylphenyl)-p-tolyl-iodonium ammonium sulfate as a colorless, transparent white solid.
  • Example 2-1 It was prepared in the same manner as Example 2-1, except that butylacetate was used instead of the heptane used in Example 2-1. Obtain 83 g (0.18 mol; 82%) of (4-isobutylphenyl)-p-tolyl-iodonium ammonium sulfate, a colorless and transparent white solid.
  • Example 2-1 It was prepared in the same manner as Example 2-1, except that acetone was used instead of the heptane used in Example 2-1. 71 g (0.15 mol; 67%) of (4-isobutylphenyl)-p-tolyl-iodonium ammonium sulfate, a colorless and transparent white solid, is obtained.
  • Example 2-1 95 g (0.20 mol) of (4-isobutylphenyl)-p-tolyl-iodonium ammonium sulfate purified in Example 2-1 was introduced into a 1000 ml flask equipped with a reflux condenser, thermometer, stirrer, and nitrogen supply. Next, 160g of water and 140g of butyl acetate are added and cooled to 10-15°C. Add 55 g (0.29 mol) of potassium hexafluorophosphate in portions so as not to exceed 15°C and stir for 4 hours. After filtering the mixture, the phases are separated and the organic phase is recovered. The organic phase is washed with water and the solvent is removed under vacuum.
  • Analysis is performed by dissolving 0.1 g of the sample in a solution of 45 g of distilled water and 5 g of methanol.
  • Example compound Ion chromatography gardner color value Main peak Retention Time water eluent Example 3 (4-isobutylphenyl)-p-tolyl-iodonium hexafluorophosphate 21.170min 99.78% KOH 6.0
  • Example 4 (4-isobutylphenyl)-p-tolyl-iodonium difluorophosphate 4.697min 99.79% Na 2 CO 3 , NaHCO 3 mixed 4.1
  • Example 5 (4-isobutylphenyl)-p-tolyl-iodonium bisfluorosulfonylimide 25.973min 99.31% KOH 3.6
  • Example 2 98.2 g (0.21 mol; 92%; Gardner value 6.7) of (4-isobutylphenyl)-p-tolyl-iodonium ammonium sulfate prepared in Example 1 was purified in Example 3 and Example 2, omitting the purification process in Example 2. It was prepared in the same way. 95.29 g (4-isobutylphenyl)-p-tolyl-iodonium hexafluorophosphate (yield: 91%) was obtained in the form of a dark brown transparent liquid. The purity is 98% and the Gardner color value is 12.2.
  • the method for producing diphenyl iodonium salt of the present invention has the effect of providing diphenyl iodonium salt with high purity, and the high purity diphenyl iodonium salt can be used in fields that require a transparent photoinitiator.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

La présente invention concerne un photo-initiateur UV ionique et son procédé de préparation, le photo-initiateur UV ionique comprenant un sel d'iodonium ayant une pureté de 95 % ou plus telle que mesurée par chromatographie par échange d'ions anioniques.
PCT/KR2023/004604 2022-04-06 2023-04-05 Sel de diphényliodonium pour photoinitiateur et son procédé de préparation WO2023195774A1 (fr)

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KR1020220042669A KR20230143709A (ko) 2022-04-06 2022-04-06 광개시제용 디페닐요오도늄 염 및 그의 제조 방법
KR10-2022-0042669 2022-04-06

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2005053869A (ja) * 2003-08-07 2005-03-03 Nippon Soda Co Ltd 硫酸水素ジアリールヨードニウム塩の製造方法
CN101139247A (zh) * 2007-09-05 2008-03-12 武汉工程大学 4,4-双十二烷基苯碘鎓六氟锑酸盐的合成方法
KR20120013152A (ko) * 2010-08-04 2012-02-14 주식회사 엘지화학 양이온성 광개시제를 이용한 고흡수성 수지의 제조 방법 및 고흡수성 수지 제조용 조성물
CN104497277A (zh) * 2014-11-26 2015-04-08 南京凯泰化工科技有限公司 一种自由基光引发剂及其制备方法
CN104628516A (zh) * 2013-11-08 2015-05-20 上海予利化学科技有限公司 阳离子光引发剂4-异丁基苯基-4′-甲基苯基碘鎓六氟磷酸盐的制备方法

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
SG98433A1 (en) 1999-12-21 2003-09-19 Ciba Sc Holding Ag Iodonium salts as latent acid donors

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2005053869A (ja) * 2003-08-07 2005-03-03 Nippon Soda Co Ltd 硫酸水素ジアリールヨードニウム塩の製造方法
CN101139247A (zh) * 2007-09-05 2008-03-12 武汉工程大学 4,4-双十二烷基苯碘鎓六氟锑酸盐的合成方法
KR20120013152A (ko) * 2010-08-04 2012-02-14 주식회사 엘지화학 양이온성 광개시제를 이용한 고흡수성 수지의 제조 방법 및 고흡수성 수지 제조용 조성물
CN104628516A (zh) * 2013-11-08 2015-05-20 上海予利化学科技有限公司 阳离子光引发剂4-异丁基苯基-4′-甲基苯基碘鎓六氟磷酸盐的制备方法
CN104497277A (zh) * 2014-11-26 2015-04-08 南京凯泰化工科技有限公司 一种自由基光引发剂及其制备方法

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