WO2015050292A1 - Procédé de préparation de carbonate à l'aide d'un composé organométallique - Google Patents

Procédé de préparation de carbonate à l'aide d'un composé organométallique Download PDF

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Publication number
WO2015050292A1
WO2015050292A1 PCT/KR2014/000460 KR2014000460W WO2015050292A1 WO 2015050292 A1 WO2015050292 A1 WO 2015050292A1 KR 2014000460 W KR2014000460 W KR 2014000460W WO 2015050292 A1 WO2015050292 A1 WO 2015050292A1
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WIPO (PCT)
Prior art keywords
formula
group
organometallic compound
carbonate
reaction
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PCT/KR2014/000460
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English (en)
Korean (ko)
Inventor
김동백
권오성
이연주
이창훈
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제일모직 주식회사
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Publication of WO2015050292A1 publication Critical patent/WO2015050292A1/fr

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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
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/02—Silicon compounds
    • C07F7/025—Silicon compounds without C-silicon linkages
    • 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
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/02—Silicon compounds
    • C07F7/08—Compounds having one or more C—Si linkages
    • C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C68/00—Preparation of esters of carbonic or haloformic acids
    • 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
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/22—Tin compounds
    • 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
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/22—Tin compounds
    • C07F7/2224—Compounds having one or more tin-oxygen linkages

Definitions

  • the present invention relates to a method for preparing carbonate ester using an organometallic compound. More specifically, the present invention relates to a method for preparing carbonate ester using an organometallic compound which can produce carbonate ester in high yield, using a specific organometallic compound, carbon dioxide and alcohol, without regenerating and recycling the organometallic compound. will be.
  • Carbonate esters are useful monomers for the production of polycarbonates, and a lot of researches on their preparations have been conducted.
  • carbonate esters have been prepared by reaction with alcohol using phosgene as a carbonyl source, but this method has problems such as the use of chlorine solvents and the treatment of by-product neutral salts, as well as the use of very harmful phosgene. .
  • organometallic compounds compounds of the same type as Sn (R) 2 (OR ') 2 (R, R': different alkyl groups) having a central metal of tin and having two alkyl groups and an alkoxy group are disclosed (Japanese Patent) Application 2010-523783, 2006-548937, 2006-513613, 2006-095140, 2005-511122, 2003-556375, 2001-396545, 2001-396537, etc.).
  • known organometallic compounds have a problem of low reactivity and low yield of carbonate ester production.
  • An object of the present invention is to provide a method for preparing carbonate esters which can synthesize carbonate esters in high yield without using a specific organometallic compound, carbon dioxide and alcohol, without regenerating and recycling the organometallic compound.
  • Another object of the present invention is to provide an organometallic compound for preparing the carbonate ester.
  • One aspect of the present invention relates to a method for producing a carbonate ester.
  • the production method is characterized in that it comprises the step of preparing a carbonic acid ester by reacting the organometallic compound represented by the formula (1), carbon dioxide and alcohol having 1 to 10 carbon atoms:
  • M a is a Group 4 or 14 metal
  • R 1 , R 2 and R 3 are each independently a hydrocarbon group having 1 to 10 carbon atoms
  • a is an integer of 0 to 2
  • n is 1 to Is an integer of 3.
  • M a may be titanium (Ti), tin (Sn) or zirconium (Zr).
  • R 1 , R 2 and R 3 may each independently be a methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group or phenyl group.
  • the reaction can be carried out at a temperature of about 130 to about 230 ° C. and carbon dioxide pressure conditions of about 10 to about 200 bar.
  • Another aspect of the invention relates to an organometallic compound for the production of carbonate esters.
  • the organometallic compound is characterized in that represented by the formula (1).
  • the present invention uses the organometallic compound, carbon dioxide and alcohol for the production of a specific carbonic acid ester, without the regeneration and recycling process of the organic metal compound, the effect of the invention to provide a method for producing a carbonic acid ester can be synthesized in high yield
  • Carbonate ester production method is characterized in that it comprises the step of preparing a carbonic acid ester by simultaneously reacting the organometallic compound, carbon dioxide and alcohol having 1 to 10 carbon atoms represented by the formula (1).
  • M a is a Group 4 or 14 metal of the periodic table, for example, titanium (Ti), tin (Sn) or zirconium (Zr),
  • R 1 , R 2 and R 3 are each independently carbon number It may be a hydrocarbon group of 1 to 10, for example, an alkyl group of 1 to 8 carbon atoms, an aryl group of 6 to 10 carbon atoms, specifically, may be a methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, or phenyl group.
  • a is an integer of 0-2 and n is an integer of 1-3.
  • the organometallic compound of the present invention includes an oxygen (O) -metal (Ma) -oxygen (O) -silicon (Si) -oxygen (O) bond, for example, a metal oxide compound represented by Formula 2 below. And it can be prepared by reacting a silicon alkoxide compound represented by the formula (3).
  • M a , R 1 , R 2 , R 3 and a are as defined in Formula 1.
  • reaction may be carried out in accordance with Scheme 1 below.
  • reaction can be carried out at a temperature of about 150 to about 170 °C and pressure conditions of normal pressure.
  • the molar ratio of the metal oxide compound represented by Chemical Formula 2 and the silicon alkoxide compound represented by Chemical Formula 3 may vary depending on the n value of the organometallic compound to be prepared. 1: about 1 to about 4: about 1, for example about 1: about 1 to about 2: about 1.
  • Metals, alkyl groups (or aryl groups), alkoxy groups (or aryloxy groups), etc. of the prepared organometallic compounds may be ion coupled plasma spectrophotometers (ICP-AES), nuclear magnetic resonance spectroscopy (NMR). ), Etc. can be confirmed.
  • ICP-AES ion coupled plasma spectrophotometers
  • NMR nuclear magnetic resonance spectroscopy
  • Etc. Etc.
  • Alcohol used in the present invention may be represented by the following formula (4).
  • R 4 may be a hydrocarbon group having 1 to 10 carbon atoms, for example, an alkyl group having 1 to 8 carbon atoms or an aryl group having 6 to 10 carbon atoms, and specifically, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group , Hexyl group, or phenyl group.
  • R 4 may be the same hydrocarbon group as R 1 , R 2 and R 3 , for example, may be the same hydrocarbon group as R 3 .
  • the alcohol may include methanol, ethanol, propanol, butanol, pentanol, hexanol, phenol, and the like, but are not limited thereto.
  • Carbonate ester prepared according to the method for producing a carbonic acid ester of the present invention may be represented by the following formula (5).
  • R 5 and R 6 may each independently be a hydrocarbon group having 1 to 10 carbon atoms, for example, an alkyl group having 1 to 8 carbon atoms or an aryl group having 6 to 10 carbon atoms, and specifically, a methyl group, an ethyl group, or a propyl group. , Butyl group, pentyl group, hexyl group or phenyl group.
  • R 5 and R 6 may be derived from the alcohol R 4 in the general formula (4) and R 2 and R 3 of the organometallic compound of the formula (1).
  • the reaction may be carried out by conventional batch reactions, for example, at a temperature of about 130 to about 230 ° C., specifically about 140 to about 190 ° C. and about 10 to about 200 bar, specifically about 40 to about It may be carried out at carbon dioxide pressure conditions of about 150 bar. In the above range, the reaction rate is fast, and carbonate ester can be produced in high yield.
  • Batch reactions are typically carried out in consideration of conversion and reactor volume and are liquid phase processes that do not overheat.
  • the reaction of the present invention is a reaction that does not require a separate solvent using an alcohol having 1 to 10 carbon atoms as a liquid reactant and carbon dioxide and a solid organometallic compound as a gaseous reactant. That is, it may be a homogeneous reaction in which carbon dioxide and an organometallic compound are dissolved and reacted with the alcohol.
  • the reaction may be carried out at a stirring speed of about 300 to about 1,000 rpm, for example, about 400 to about 500 rpm, and a reaction time of about 0.5 to about 24 hours, for example, 1 to 3 hours.
  • the production method can be understood to produce carbonate esters by the reaction shown in Scheme 2 below.
  • the organometallic compound may be used in an amount of about 1 to about 30 moles, for example about 5 to about 15 moles, based on 100 moles of alcohol.
  • Carbonate ester can be manufactured in high yield in the said range.
  • the organometallic compound, carbon dioxide, and alcohol having 1 to 10 carbon atoms are reacted at the same time, so that carbonate ester can be obtained in high yield, and a separate organic metal compound regeneration and recycling process is not required. It is economical.
  • Bu is an n-butyl group.
  • Bu is an n-butyl group.
  • the reaction was performed in the same manner as in Example 1, except that 10.4 g (13.2 mmol) of the organometallic compound represented by Formula 1b was used instead of 7.3 g (13.2 mmol) of the organometallic compound represented by Formula 1a. After the completion of the reaction, the reaction solution was analyzed by gas chromatography. As a result, it was confirmed that di-n-butylcarbonate was obtained in 82.0% yield.
  • Bu is an n-butyl group.
  • Bu is an n-butyl group.
  • the reaction was carried out in the same manner as in Comparative Example 3 except that 4.5 g (13.2 mmol) of titanium butoxide (Ti (OBu) 4 ) was used instead of 7.3 g (13.2 mmol) of the organometallic compound represented by Chemical Formula 1a. .
  • the reaction solution was analyzed by gas chromatography. As a result, it was confirmed that di-n-butylcarbonate was obtained in a 40.0% yield.
  • the organometallic compound of the present invention can be produced in an excellent yield compared to the existing organometallic compounds (Comparative Examples 1 and 2) under the same reaction conditions.
  • the carbonic acid ester can be produced in a better yield than Comparative Example 3, which does not use alcohol together and Comparative Example 4, which uses titanium butoxide (Ti (OBu) 4 ) alone. have.

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

Abstract

La présente invention concerne un procédé de préparation d'un carbonate qui comprend une étape de préparation d'un carbonate par la mise en réaction d'un composé organométallique représenté par la formule chimique 1 de la description, du dioxyde de carbone et un alcool C1-10. Le procédé de préparation selon l'invention permet de préparer un carbonate à un rendement élevé sans effectuer les processus de régénération et de recyclage d'un composé organométallique.
PCT/KR2014/000460 2013-10-01 2014-01-16 Procédé de préparation de carbonate à l'aide d'un composé organométallique WO2015050292A1 (fr)

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KR1020130117400A KR101627018B1 (ko) 2013-10-01 2013-10-01 유기금속화합물을 이용한 탄산에스테르의 제조방법
KR10-2013-0117400 2013-10-01

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
RU2206571C1 (ru) * 2002-01-16 2003-06-20 Общество с ограниченной ответственностью "Пента-91" Способ получения органометаллоксистаннанов
JP2006176412A (ja) * 2004-12-21 2006-07-06 Asahi Kasei Chemicals Corp 炭酸エステルの製造方法
US7446218B2 (en) * 2002-08-07 2008-11-04 Asahi Kasei Chemicals Corporation Process for producing carbonic ester
JP5069793B2 (ja) * 2008-08-08 2012-11-07 旭化成ケミカルズ株式会社 アルキルスズアルコキシド化合物の製造方法、及び当該化合物を用いた炭酸エステルの製造方法

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3307973A (en) * 1964-01-17 1967-03-07 Glidden Co Dialkylstannoxy organometallic compounds and condensation products
US5034455A (en) * 1988-05-31 1991-07-23 General Electric Company Curable silicone caulk compositions
DE3903145A1 (de) * 1989-02-02 1990-08-09 Wacker Chemie Gmbh Verfahren zur polymerisation polarer verbindungen

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
RU2206571C1 (ru) * 2002-01-16 2003-06-20 Общество с ограниченной ответственностью "Пента-91" Способ получения органометаллоксистаннанов
US7446218B2 (en) * 2002-08-07 2008-11-04 Asahi Kasei Chemicals Corporation Process for producing carbonic ester
JP2006176412A (ja) * 2004-12-21 2006-07-06 Asahi Kasei Chemicals Corp 炭酸エステルの製造方法
JP5069793B2 (ja) * 2008-08-08 2012-11-07 旭化成ケミカルズ株式会社 アルキルスズアルコキシド化合物の製造方法、及び当該化合物を用いた炭酸エステルの製造方法

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KR101627018B1 (ko) 2016-06-03

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