(19)
(11)EP 3 546 443 B1

(12)EUROPEAN PATENT SPECIFICATION

(45)Mention of the grant of the patent:
17.11.2021 Bulletin 2021/46

(21)Application number: 17874733.3

(22)Date of filing:  13.11.2017
(51)International Patent Classification (IPC): 
C07C 68/02(2006.01)
C07C 69/96(2006.01)
(52)Cooperative Patent Classification (CPC):
C07C 68/02
 
C-Sets:
C07C 68/02, C07C 69/96;
(86)International application number:
PCT/KR2017/012791
(87)International publication number:
WO 2018/097529 (31.05.2018 Gazette  2018/22)

(54)

METHOD FOR PRODUCING FLUORINE-CONTAINING DIALKYL CARBONATE COMPOUNDS

VERFAHREN ZUR HERSTELLUNG FLUORHALTIGER DIALKYLCARBONATVERBINDUNGEN

PROCÉDÉ DE PRODUCTION DE COMPOSÉS CARBONATE DE DIALKYLE CONTENANT DU FLUOR


(84)Designated Contracting States:
AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

(30)Priority: 28.11.2016 KR 20160159015

(43)Date of publication of application:
02.10.2019 Bulletin 2019/40

(73)Proprietor: Samhwa Paints Industries Co., Ltd.
Ansan-si, Gyeonggi-do 15619 (KR)

(72)Inventors:
  • HONG, Myeng Chan
    Pyeongtaek-si Gyeonggi-do 17734 (KR)
  • CHOI, Yeong Sup
    Ansan-si Gyeonggi-do 15541 (KR)
  • KWON, Da Eun
    Gunpo-si Gyeonggi-do 15872 (KR)
  • KWAK, Jong Yun
    Seoul 03010 (KR)

(74)Representative: TLIP Limited 
14 King Street
Leeds LS1 2HL
Leeds LS1 2HL (GB)


(56)References cited: : 
EP-A1- 2 903 075
JP-A- H0 640 951
KR-B1- 100 690 010
KR-B1- 100 744 824
WO-A1-2005/123656
JP-A- H06 219 992
KR-B1- 100 690 010
US-A1- 2012 141 870
  
      
    Note: Within nine months from the publication of the mention of the grant of the European patent, any person may give notice to the European Patent Office of opposition to the European patent granted. Notice of opposition shall be filed in a written reasoned statement. It shall not be deemed to have been filed until the opposition fee has been paid. (Art. 99(1) European Patent Convention).


    Description

    [Technical Field]



    [0001] The present invention relates to a method for producing fluorine(F)-containing dialkyl carbonate compounds. More specifically, the present invention relates to a method for producing fluorine-containing dialkyl carbonate compounds by reacting an alkyl chloroformate and an alcohol in the presence of an ether-containing imidazole derivative base.

    [Background Art]



    [0002] A lithium ion secondary battery is a non-aqueous electrolyte and are used by dissolving a lithium (Li) salt in a non-aqueous solvent such as ethylene carbonate, propylene carbonate, dimethyl carbonate or the like. Recent market demands for obtaining lithium ion batteries with higher energy density, higher power, and higher safety lead to the development of new solvents to improve the performance of batteries in electrolytes based only on carbonate. Currently used electrolytes are decomposed at 5V or more, and thus, the performance of the batteries is reduced, and further, safety problems may occur due to a low boiling point and high ignitability of the electrolytes. In order to solve these problems, research and production of linear carbonates containing fluorine atoms have actively proceeded.

    [0003] As a method for synthesizing non-cyclic carbonates containing a fluorine atom, a method of carrying out the reaction by adding a sodium methoxide/methanol solution to a mixed solution of alcohol and a dimethyl carbonate and then heating the mixture at 100°C for 6 hours is disclosed in Patent Document 1 (Mitsui Petrochemical Industries, Ltd. and Sony Corporation) issued in 1997 as a prior art 1. In this method, after completion of the reaction, an aqueous solution of ammonium chloride is added to the mixture to remove sodium methoxide, and the organic layer is washed with water and dried to obtain a product. However, there are disadvantages that sodium methoxide is highly reactive and thus dangerous, and it reacts violently upon contact with water and turns into sodium hydroxide.

    [0004] In the method disclosed in Patent Document 2 (Du Pont de Nemours and Company) as a prior art 2, an alcohol and chloroformate are used as reactants, and pyridine is used as a base. The chloroformate is added dropwise by lowering a temperature to -10°C, and when the reaction is completed, 5% HCl is added and the mixture is extracted with ether. Then, the organic layer is washed with 5% NaHCO3, and the product is isolated using a rotary evaporator.

    [0005] In the method disclosed in Patent Document 3 (Daikin industries) as a prior art 3, an alcohol, methyl chloroformate, and diglyme as a solvent, are added, and when the temperature is lowered using ice bath, triethylamine is added dropwise while paying attention to heat generation. When the reaction is completed, the reaction mixture is washed with 1N HCl aqueous solution and the separated organic layer is purified using a 10-stage distillation purification tower to obtain a desired compound.

    [0006] In Patent Document 4 as a prior art 4, chloroformate and an alcohol are reacted in the presence of 1-methylimidazole, and after completion of the reaction, the layers are separated. However, it is not easy to separate the formed 1-methylimidazole salt from the product, and the salt formed during the layer separation is highly viscous, and thus, a longer period of time is required for separation. In addition, when the formed salt is saturated with HCl, it is precipitated as solids, which may cause problems for industrialization.

    [Prior Art Documents]


    [Patent Documents]



    [0007] 

    (Patent Document 1) U.S. Patent No. 5,659,062

    (Patent Document 2) U.S. Patent Publication NO. 2012/0141870

    (Patent Document 3) Korean Patent Publication No. 10-2015-0054951

    (Patent Document 4) Korean Patent No. 10-0690010


    [DETAILED DESCRIPTION OF THE INVENTION]


    [Technical Problem]



    [0008] In the above-mentioned prior arts 1 to 4, there are disadvantages that the separation and purification processes are complicated, the difference in the boiling point between the solvent and the product is small, it is difficult to perform separation, and a longer period of time is required to separate the layers due to viscosity. Further, there is a problem that the temperature should be lowered due to heat generation when a base is added dropwise.

    [0009] In this regard, the present inventors have conducted extensive studies to solve the problems of the prior arts that the separation and purification processes are complicated, high stages of distillation column are required to separate the used solvent and the product, the salt is precipitated during layer separation, and a longer period of time is required to separate the product. As a result, the inventors have found that when an ether-containing imidazole derivative is used as a base and an alkyl chloroformate is reacted with an alcohol, not only the reaction can proceed at room temperature, but also the product can be easily and rapidly separated from the reaction mixture without the formation of solids. Accordingly, an object of the present invention is intended to improve the disadvantages encountered with conventional production methods, thus providing an economical and easy production method.

    [Technical Solution]



    [0010] The present invention relates to a method for producing a fluorine-containing dialkyl carbonate represented by the following Chemical Formula 3, including: reacting an alkyl chloroformate represented by the following Chemical Formula 1 and an alcohol represented by the following Chemical Formula 2 in the presence of an ether-containing imidazole derivative base:



            (Chemical Formula 2)     R2OH



    (wherein, R1 and R2 are each dependently an unsubstituted C1-C20 alkyl group and a fluorine-substituted C1-C20 alkyl group).

    in Reaction Scheme 1, R1 and R2 are each independently as defined in Chemical Formulae 1, 2 and 3.

    [0011] As a composition ratio, it is preferable to use 0.9 to 1.1 moles of the base, 0.9 to 1.1 moles of the alkyl chloroformate, and 0.9 to 1.1 moles of the alcohol. However, the mixing molar ratio is most suitably 1: 1: 1. By-product is HCl, and in order to remove these, base requires a molar ratio of 1. This is because the formed ionic liquid and product may be separated. If the base is used in a molar amount of more than 1, the product and the remaining base may be mixed. If the base is used in a molar amount of less than 1, the reaction is not completed.

    [0012] The alkyl chloroformate may be reacted with the alcohol in the presence of the base at a temperature range of 0 to 70°C, and more preferably 10 to 35°C.

    [0013] In addition, the separation of the product from the reactants may be achieved by layer separation. In this way, it is possible not only to avoid the use of sodium methoxide, which is difficult to handle, but also to separate the alcohol, which is difficult to be removed by a distillation method due to the formation of an azeotrope between the alcohol remaining after the reaction and the product. Thus, it is possible to easily separate the alcohol and the reactant by the layer separation due to the imidazole salt formed by the use of the imidazole base, and the separation process may be much more economical.

    [0014] As the base, one or two selected from 1-(methoxymethyl)imidazole, 1-(ethoxymethyl)imidazole, 1-(propoxymethyl)imidazole, 1-(butoxymethyl)imidazole, 1-(2-methoxyethyl)imidazole, 1-(2-ethoxyethyl)imidazole, 1-(2-propoxyethyl)imidazole, 1-(2-butoxyethyl)imidazole, 1-(3-methoxypropyl)imidazole, and 1-(3-ethoxypropyl)imidazole may be used. Among them, 1-(2-ethoxyethyl)imidazole is most preferable, because it enables an easy and rapid layer separation and can be reusable. The reaction time may be less than 6 hours, preferably from 2 to 4 hours.

    [ADVANTAGEOUS EFFECTS]



    [0015] In the present invention, when an alkyl chloroformate and an alcohol are reacted in the presence of an ether-containing imidazole derivative as a base, it has advantages in that the reaction can proceed at room temperature as compared with the prior art, and the product can be easily separated from the reactants. This is, the method for producing alkyl carbonates containing fluorine atoms according to the present invention is a very simple process involving a rapid layer separation so as to remove the solvents, the by-products formed during the reaction, and the formed salts without the formation of solids, and thus has an advantage of obtaining fluorine-containing linear alkyl carbonates. Accordingly, the production method of the present invention can be effectively applied to the production of fluorine-containing dialkyl carbonates used for various applications such as electrolytes of lithium ion secondary batteries, medicines and fine chemicals, pesticides, polar aprotic solvents, synthetic lubricating oils and the like.

    [DETAILED DESCRIPTION OF THE EMBODIMENTS]



    [0016] Hereinafter, the present invention as defined in the claims will be described in more detail by way of Examples.

    Example 1: Preparation of methyl 2,2,2-trifluoroethyl carbonate



    [0017] 100 g of methyl chloroformate and 106 g of 2,2,2-trifluoroethanol were added to a 1000-mL reactor equipped with a stirrer, and the mixture was stirred at room temperature for 30 minutes. 149 g of 1-(2-ethoxyethyl)imidazole was placed in a dropping funnel equipped in the reactor head, then added dropwise for 2 hours and stirred at room temperature for 3 hours. After completion of the reaction, the layers were separated to obtain methyl 2,2,2-trifluoroethyl carbonate as a transparent liquid in a yield of 88%.

    Examples 2 to 4: Preparation of methyl fluoroalkyl carbonate compounds



    [0018] The reaction was carried out in the same manner as in Example 1, except that the type of alcohols was varied. The results are shown in Table 1 below.
    [Table 1]
    ExamplesAlcohol compoundsYield (%)
    2 Hexafluoro-iso-propanol 85
    3 2,2,3,3-tetrafluoropropanol 80
    4 2,2,3,3,3-pentafluoropropanol 90

    Example 5: Preparation of ethyl 2,2,2-trifluoroethyl carbonate



    [0019] 100 g of ethyl chloroformate and 92 g of 2,2,2-trifluoroethanol were added to a 1000-mL reactor equipped with a stirrer, and the mixture was stirred at room temperature for 30 minutes. 129 g of 1-(2-ethoxyethyl)imidazole was placed in a dropping funnel equipped in the reactor head, then added dropwise for 2 hours and stirred at room temperature for 3 hours. After completion of the reaction, the layers were separated to obtain ethyl 2,2,2-trifluoroethyl carbonate as a transparent liquid in a yield of 92%.

    Examples 6 to 8: Preparation of ethyl fluoroalkyl carbonate



    [0020] The reaction was carried out in the same manner as in Example 5, except that the type of alcohol compounds was varied. The results are shown in Table 2 below.
    [Table 2]
    ExamplesAlcohol compoundsYield (%)
    6 Hexafluoro-iso-propanol 85
    7 2,2,3,3-tetrafluoropropanol 85
    8 2,2,3,3,3-pentafluoropropanol 90

    Examples 9 to 14: Preparation of fluorodialkyl carbonate



    [0021] The reaction was carried out in the same manner as in Example 1, except that the molar ratio was varied. The results are shown in Table 3 below.
    [Table 3]
    Exampl esMethyl chloroforma te2,2,2-trifluoroetha nol1-(2-ethoxyethy l) imidazoleYiel d (%)
    9 0.9 1 1 65
    10 1 0.9 1 72
    11 1 1 0.9 70
    12 1.1 1 1 88
    13 1 1.1 1 88
    14 1 1 1.1 60

    Examples 15 to 19: Preparation of fluorodialkyl carbonate



    [0022] The reaction was carried out in the same manner as in Example 1, except that the reaction temperature was varied. The results are shown in Table 4 below.
    [Table 4]
    ExamplesReaction Temperature (°C)Yield (%)
    15 0 45
    16 10 88
    17 35 88
    18 50 85
    19 70 70

    Examples 20 to 24: Preparation of fluorodialkyl carbonate



    [0023] The reaction was carried out in the same manner as in Example 1, except that the reaction time was varied. The results are shown in Table 5 below.
    [Table 5]
    ExamplesReaction Time (h)Yield (%)
    20 0.5 50
    21 1 60
    22 2 80
    23 4 88
    24 6 88



    Claims

    1. A method for producing a dialkyl carbonate represented by the following Chemical Formula 3, comprising:

    reacting an alkyl chloroformate represented by the following Chemical Formula 1 and an alcohol represented by the following Chemical Formula 2 in the presence of a base,

    wherein the base is one or two or more selected from 1-(methoxymethyl)imidazole, 1-(ethoxymethyl)imidazole, 1-(propoxymethyl)imidazole, 1-(butoxymethyl)imidazole, 1-(2-methoxyethyl)imidazole, 1-(2-ethoxyethyl)imidazole, 1-(2-propoxyethyl)imidazole, 1-(2-butoxyethyl)imidazole, 1-(3-methoxypropyl)imidazole, and 1-(3-ethoxypropyl)imidazole:



            (Chemical Formula 2)     R2OH





    (wherein, R1 and R2 are each independently an unsubstituted C1-C20 alkyl group and a fluorine-substituted C1-C20 alkyl group)


     
    2. The method for producing a dialkyl carbonate of claim 1, wherein the reaction temperature is in the range of 10 to 35°C.
     
    3. The method for producing a dialkyl carbonate of claim 1, wherein the separation of the reaction product from the reactants is performed by layer separation.
     
    4. The method for producing a dialkyl carbonate of claim 1, wherein the base is 1-(2-ethoxyethyl)imidazole.
     
    5. The method for producing a dialkyl carbonate of claim 1, wherein the reaction time is less than 6 hours.
     
    6. The method for producing a dialkyl carbonate of claim 1, wherein the mixing molar ratio of the base, the alkyl chloroformate and the alcohol is 1:1:1.
     


    Ansprüche

    1. Verfahren zum Herstellen eines Dialkylcarbonats, dargestellt durch die folgende chemische Formel 3, umfassend:

    Reagieren eines Alkylchlorformiats, dargestellt durch die folgende chemische Formel 1 und eines Alkohols, dargestellt durch die folgende chemische Formel 2 in der Gegenwart einer Base,

    wobei die Base eine oder zwei oder mehrere ist, ausgewählt aus 1-(Methoxymethyl)-Imidazol, 1-(Ethoxymethyl)-Imidazol, 1-(Propoxymethyl)-Imidazol, 1-(Butoxymethyl)-Imidazol, 1-(2-Methoxyethyl)-Imidazol, 1-(2-Ethoxyethyl)-Imidazol, 1-(2-Propoxyethyl)-Imidazol, 1-(2-Butoxyethyl)-Imidazol, 1-(3-Methoxypropyl)-Imidazol und 1-(3-Ethoxypropyl)-Imidazol:



            (Chemische Formel 2)     R2OH



    (wobei R1 und R2 jeweils unabhängig eine unsubstituierte C1-C20-Alkylgruppe und eine fluorsubstituierte C1-C20-Alkylgruppe sind).


     
    2. Verfahren zum Herstellen eines Dialkylcarbonats nach Anspruch 1, wobei die Reaktionstemperatur im Bereich von 10 bis 35 °C liegt.
     
    3. Verfahren zum Herstellen eines Dialkylcarbonats nach Anspruch 1, wobei die Trennung des Reaktionsprodukts von den Reaktanten durch Schichttrennung durchgeführt wird.
     
    4. Verfahren zum Herstellen eines Dialkylcarbonats nach Anspruch 1, wobei die Base 1-(2-Ethoxyethyl)-Imidazol ist.
     
    5. Verfahren zum Herstellen eines Dialkylcarbonats nach Anspruch 1, wobei die Reaktionszeit weniger als 6 Stunden beträgt.
     
    6. Verfahren zum Herstellen eines Dialkylcarbonats nach Anspruch 1, wobei das molare Mischungsverhältnis der Base, des Alkylchlorformiats und des Alkohols 1:1:1 beträgt.
     


    Revendications

    1. Procédé de production d'un carbonate de dialkyle représenté par la formule chimique 3 suivante, comprenant :

    la réaction d'un chloroformate d'alkyle représenté par la formule chimique 1 suivante et d'un alcool représenté par la formule chimique 2 suivante en présence d'une base,

    ladite base étant une ou deux bases ou plus choisies parmi le 1-(méthoxyméthyl)imidazole, le 1-(éthoxyméthyl)imidazole, le 1-(propoxyméthyl)imidazole, le 1-(butoxyméthyl)imidazole, le 1-(2-méthoxyéthyl)imidazole, le 1-(2-éthoxyéthyl)imidazole, le 1-(2-propoxyéthyl)imidazole, le 1-(2-butoxyéthyl)imidazole, le 1-(3-méthoxypropyl)imidazole et le 1-(3-éthoxypropyl)imidazole :



            (Formule chimique 2)     R2OH



    (dans lesquelles, R1 et R2 représentent chacun indépendamment un groupe C1-C20 alkyle non substitué et un groupe C1-C20 alkyle substitué par du fluor).


     
    2. Procédé de production d'un carbonate de dialkyle selon la revendication 1, la température de réaction se trouvant dans la plage de 10 à 35°C.
     
    3. Procédé de production d'un carbonate de dialkyle selon la revendication 1, la séparation du produit réactionnel des réactifs étant effectuée par séparation de couches.
     
    4. Procédé de production d'un carbonate de dialkyle selon la revendication 1, ladite base étant le 1-(2-éthoxyéthyl)imidazole.
     
    5. Procédé de production d'un carbonate de dialkyle selon la revendication 1, le temps de réaction étant inférieur à 6 heures.
     
    6. Procédé de production d'un carbonate de dialkyle selon la revendication 1, le rapport molaire de mélange de la base, du chloroformate d'alkyle et de l'alcool valant 1:1:1.
     






    Cited references

    REFERENCES CITED IN THE DESCRIPTION



    This list of references cited by the applicant is for the reader's convenience only. It does not form part of the European patent document. Even though great care has been taken in compiling the references, errors or omissions cannot be excluded and the EPO disclaims all liability in this regard.

    Patent documents cited in the description