TW201006795A - Process for producing diphenyl carbonate - Google Patents

Abstract

A process is provided by which diphenyl carbonate can be produced in high yield by a simple procedure without the need of using any toxic compound, e.g., phosgene. The process for diphenyl carbonate production is characterized by subjecting phenol and at least one fluorinated carbonate selected from a group consisting of compounds represented by formula (1), compounds represented by formula (2), and compounds represented by formula (3) to transesterification to thereby obtain diphenyl carbonate. In the formulae, R1 represents CX1Y1R4; R2 represents H or CX2Y2R5; R3 represents H or CX3Y3R6; R7 represents perfluoroalkylene; X1 to X3 each represents H, F, or Rf; Y1 to Y3 each represents F or Rf; R4 to R6 each represents F, Rf, ORf, or alkyl; and Rf represents fluoroalkyl.

Description

201006795 VI. Description of the Invention: [Technical Field] The present invention relates to a method for producing diphenyl carbonate. [Prior Art] Polycarbonate is used as an engineering plastics for heat resistance, impact resistance, transparency, and the like. It is widely used in many fields of engineering, and diphenyl carbonate is a compound of the polycarbonate. It is industrially useful as a method for producing diphenyl carbonate. For example, the following method is known. (1) A method of phenol and phosgene at the interface in the presence of a base catalyst (phosgene method). (ii) A method of transesterifying a dialkyl carbonate such as dinonyl carbonate with phenol in the presence of a catalyst (transesterification method). However, the method of (1) uses toxic phosgene; it is necessary to wash and remove inorganic salts such as sodium chloride produced by the reaction by-product; and use a solvent such as dioxane, so there is a need for complicated processes such as purification and solvent recovery after the reaction. . Further, in the method of (U), the transesterification reaction of dialkyl carbonate with phenol is slow, and the conversion rate and selectivity are low (refer to the patent document 丨). - As a method of improving the problem of the method of (U), the following method is known. t (iii) A method of using a modified catalyst and using a solvent in the transesterification reaction of a dialkyl acid ester with phenol (refer to Patent Document 2). (iv) in the transesterification reaction of dialkyl carbonate with phenol, the multistage reactor is combined with the steaming tower, and the low boiling component separated by the transesterification reaction is removed from the reaction system to the outside of the system. This method of shifting the equilibrium to the product side by 141334.doc 201006795 and extracting the yield of the target (refer to Patent Document 3) ^ However, in the method of (111), the yield is 31% insufficient and then necessary Remove solvents and other issues. Further, in the method (IV), there is a problem that the reaction process is very complicated and the investment in the manufacturing equipment becomes large. Further, as a method for producing polycarbonate, the following method is known. (V) A method of producing a poly-carbonate by reacting a fluorine-containing carbonate with a double-phase A in the presence of a base catalyst (NaOCH3 or the like) (see Patent Document 4). However, the method of producing diphenyl carbonate by the method of (ν) is still unknown. [PRIOR ART DOCUMENT] [Patent Document 1] Japanese Patent Laid-Open Publication No. SHO-62-246533 [Patent Document 2] Japanese Patent Laid-Open Publication No. Hei. [Patent Document 4] Japanese Laid-Open Patent Publication No. SHO 55-102626 [Draft] [Problems to be Solved by the Invention] The present invention provides a process for producing a diphenyl carbonate by a simple process and a high yield. It is not necessary to use a method of toxic compounds such as phosgene. [Means for Solving the Problem] The method for producing diphenyl carbonate of the present invention is represented by a compound represented by the following formula (1), a compound represented by the following formula (2), and the following formula (3). At least one of the fluorine-containing carbonates in the group of the compounds, 141334.doc 201006795 A method of transesterification with phenol to obtain diphenyl carbonate: [Chemical Formula 1] (1) wherein CfY is represented by R4 The two R1s may be the same or different, and R2 is a hydrogen atom or a group represented by CX2Y2R5, and two r2 phases are

Similarly, R3 is a hydrogen atom or a group represented by cx3y3r>, and two R3s may be the same or different. 'Χι~χ3 are respectively a hydrogen atom, a fluorine atom or Rf, and Y1 to Y3 are respectively fluorine atoms or R4. R6 is a fluorine atom, Rf, (10)f or a carbon number 6 burnt group, and Rf is a carbon number of 4 (where etheric oxygen); [Chemical 2]

八T (2) Ma is based on CX Υ»,

The group represented by CX2Y2R5, the 3 虱 atomic WR is a hydrogen atom or a CX3Y3 6 group, and R7 is a carbon number i~5 of the perfluoro group. X) X3 八别 U 申基 (which may include _ oxygen ), X~X is a hydrogen atom, fluorine

Rf, R4 to R6 are respectively u Ϊ are gas atoms or

R(10) or a carbon number of ruthenium, Rf is a gas group having a carbon number of 1 to 4 (which may include refractory oxygen). Base R 141334.doc 201006795 R7-CF2 h F2C-C-0-C-CK^ Cf2 (3) η 0 FaC^7 wherein r7 is a perfluoroalkylene group having 1 to 5 carbon atoms (which may include ethereal oxygen) 'two R7' may be the same or different. In the method for producing diphenyl carbonate of the present invention, it is preferred that the fluorocarbonic acid-containing vinegar and the above-mentioned vinegar exchange reaction are carried out in the presence of a metal salt catalyst. The above metal salt catalyst is preferably a metal fluoride or a metal alkoxide. Preferably, the transesterification reaction of the above fluorine-containing carbonate with the above phenol is carried out in the presence of a metal salt catalyst and a metal oxide. The above metal oxide is preferably selected from the group consisting of cerium oxide (Ce〇2/Ce2〇3), lanthanum aluminum oxide (Si〇2.Al2〇3), γ-alumina (ai2〇3), lanthanum magnesium oxide. At least one of the group consisting of (Si02.MgO), oxidized (Zr02), erbium oxide (si〇2.Zr〇2), Zn0.Zr02, and A1203.B203. The fluorine-containing carbonate is preferably a reaction product using at least one fluorine-containing alcohol selected from the group consisting of a compound represented by the following formula (4) and a compound represented by the following formula (5) as a starting material. And obtained: [Chemical 4] R1 R2-cold-OH (4) ft3 141334.doc 201006795 (δ) 斤Rl^cxlYlR4 is represented by a group, r2 is a hydrogen atom or a group represented by R, and R3 is a hydrogen atom or Expressed in ocW

Base, ^7 is a perfluoroalkylene group of carbon number 5 (which may include mysterious oxygen), xf~xf is a hydrogen atom, a fluorine atom or Rf' Y1~Y3 are respectively a fluorine atom or R 'R~ R6 is a fluorine atom, Rf, 〇Rf or an alkyl group of carbon number 6, respectively, and Rf is a fluoroalkyl group having a carbon number of 1 to 4 (wherein, an exhalatory oxygen may be included). The above fluorine-containing alcohol is preferably selected from the group consisting of 2,2,2-trifluoroethanol, 2,2,3,3,3·penta-propanol, 2,2,3,3·tetrapropanol, 1, 1,1,3,3,3_hexafluoroisopropanol,

The carbon number of the above fluorine-containing alcohol is preferably 2 to 1 Torr. R2 in the above formula (4) is preferably a group represented by cx2y2r5. The pKa of the above fluorine-containing alcohol is preferably less than 15. The boiling point of the above fluorine-containing alcohol is preferably less than 181. Hey. a group consisting of 2,2,3'4,4,4·hexafluorobutanol, 2,2,3,3,4,4,5,5-octane pentanol and perfluoro(t-butyl) alcohol At least one of them. [Effects of the Invention] According to the method for producing dicumyl carbonate of the present invention, diphenyl carbonate can be produced in a simple process and at a relatively low yield without using a toxic compound such as phosgene. [Embodiment] In the present specification, the compound represented by the formula (1) is labeled as the compound (1). Compounds represented by other formulas are also labeled in the same manner. 141334.doc 201006795 <Production Method of Diphenyl Carbonate> The method for producing diphenyl carbonate of the present invention is a method of obtaining a carbonic acid dimerization by a transesterification reaction of a specific fluorine-containing carbonated vinegar with benzene. (Fluorine carbonate) The fluorine-containing carbonate is at least one selected from the group consisting of the compound (1), the compound (2), and the compound (3): R1 R1 R2-C-〇-C~ 〇-(Jj-R2 (1) ^ 0 b where is the base represented by cxiyiR4, two R's may be the same or different, R is a hydrogen atom or a group represented by CX2Y2R5, and two R2 may be the same 3 It can be different 'R3 is a hydrogen atom or a group represented by cxW, two ^ can be the same as *, χ1~χ3 are respectively a hydrogen atom, a fluorine atom or Rf, and the Y knife is a fluorine atom or Rf, R4~ R6 is a fluorine atom, Rf, 〇Rf or an alkyl group having 1 to 6 carbon atoms, and Rf is a fluoroalkyl group having 1 to 4 carbon atoms (which may include ether oxygen);

f : 5' R1 is a group represented by cxiYiR4, R2 is a hydrogen atom or a group represented by CXYR, and r3 is a hydrogen atom or 141334 represented by CX3Y3R6. Doc 201006795 is:::~5 A calcination group (wherein, an oxygen group may be included), a money atom, a fluorine atom or Rf'Yl~~R is an alkyl group which is otherwise a fluorine atom, Rf, 〇Rf or a carbon number, and Rf is a carbon number of 1 to 4. Fluoroalkyl (which may include etheric oxygen); " [Chemical 7] f卞Η F2C~C-~〇-C-0-C-CF2 (3) Η 0 F2C-i7 where R7 is The perfluoroalkylene group having 1 to 5 carbon atoms (which may include ethereal oxygen) may be the same or different. Fluorinated carbonates are mostly low-viscosity liquids at normal temperatures, which is advantageous when reacting with benzene. Also, most of the boiling points range from 8 〇 to 250. (In the range of (:, the thermal stability is also high) Therefore, it is easy to obtain high-purity fluorine-containing carbonated vinegar by distillation and purification, and it is advantageous in producing a higher quality diphenyl carbonate. method)

The fluorine-containing carbonate can be obtained by a reaction using at least one fluorine-containing alcohol selected from the group consisting of the compound (4) and the compound (5) as a starting material: [Chem. 8] R1 (4) 141334.doc (5) 201006795

Where, R

The base 'f is a perfluoroalkylene group having 1 to 5 carbon atoms (which may include ethereal oxygen), and R is a hydrogen atom or X represented by cx3y3r6: a hydrogen atom, a fluorine atom or Rf, Y1 to Y3 Each is a fluorine atom or RR to R, respectively, a fluorine atom, Rf, 〇Rf or an alkyl group having 1 to 6 carbon atoms, and R is a fluoroalkyl group having 1 to 4 carbon atoms (where 'can include ether oxygen). Fluoroalcohol, from the viewpoint of increasing the transesterification reaction rate, it is preferred that the acid dissociation degree is higher. Therefore, it is preferred that the carbon atom of the α-position of the group (hereinafter, also referred to as 〇1 carbon) is directly bonded. A compound having a fluoroalkyl group is formed. However, an alcohol in which a fluorine atom is directly bonded to an α carbon is liable to cause a decomposition reaction of the dehalation reaction, and thus is not preferable. As a measure of the degree of acid dissociation, a fluorine-containing alcohol 2 pKa is used. The alcohol of the dialkyl carbonate used in the manufacture of the previous diphenyl carbonate is a hydrocarbon alcohol (methanol, ethanol, etc.), and the alcohol has a pKa of about 15 or more. Therefore, 'and the previous dialkyl carbonate In contrast, in order to obtain the target in a higher yield, it is preferred that the pKa of the fluorine-containing alcohol is less than 15. If the boiling point of the fluorine-containing alcohol Below the boiling point of the phenol used in the raw material, the fluorine-containing alcohol separated by the transesterification reaction is removed from the reaction system by distillation to the outside of the system, thereby increasing the yield of the target. The boiling point of the compound is preferably less than 181 ° C. As the compound (4) 'the more the fluoroalkyl group bonded to the α carbon, the higher the acid dissociation degree of the fluorine-containing alcohol becomes, so it is preferable that R 2 is The group represented by Cx2y2r5 (i.e., 'class 2 or 3 fluoroalcohol)' is more preferably r2 and R3 are a group represented by CX2Y2R5 and a group represented by CX3Y3R6 (ie, 3 grade 141334. Doc •10- 201006795 Fluorinated alcohol. The carbon number of the fluorine-containing alcohol is preferably 2 to 10. If the carbon number of the fluorine-containing alcohol is 2 or more 'the fluorine atom is not directly bonded to the α-position of the base group. A stable fluorine-containing alcohol. If the carbon number of the fluorine-containing alcohol is 10 or less, the fluorine-containing alcohol separated by the transesterification reaction can be removed from the reaction system by distillation at a relatively low temperature to the outside of the system. Therefore, the loss of phenol as a raw material can be suppressed, and diphenyl carbonate can be synthesized without using phenol in excess. Specific examples of the fluorine-containing alcohol include 2,2,2-trifluoroethanol, 2.2.3.3.3-pentafluoropropanol, 2,2,3,3-tetrafluoropropanol, and hexafluoroisopropanol. 2. Fluoropropanol, 2,2,3,4,4,4-hexafluorobutanol, 2,2,3,3,4,4,5,5-octafluoropentanol, perfluoro(third Alcohol, 2,2,3,3,4,4,5,5-octafluorocyclopentanol, 2,2,3,3,4,4,5,5,6,6-decafluorocyclohexane Alcohol, etc. As the fluorine-containing alcohol, from the viewpoints of acid dissociation and boiling point, it is particularly preferably selected from 2,2,2-trifluoroethanol (pKa: 12.4, boiling point: 73 yc), 2.2.3.3.3- Fluoropropanol (卩: ^: 12.7, boiling point: 80.7. (:), 2,2,3 3-tetrafluoropropanol (PKa: 12.7, boiling point: 1〇8t:). Yamagata hexafluoroisopropanol (pKa: 9.3, boiling point: 58.Vc), 2,2,3 4,4 4 hexafluorobutanol (PKa: 12.4, boiling point: 115. 〇, 2, 2, 3,3,4,4,5,5-octafluoropentanol (PKa: U.7, boiling point: and perfluoro(t-butyl) alcohol (pKa: 5.4, boiling point: 45 ° C) A specific method of obtaining a fluorine-containing carbonated vine by a reaction using a fluorine-containing alcohol as a starting material can be exemplified by the following methods (4) to (4), since it is not necessary to use a toxic compound such as phosgene and In view of higher yield, the method of (4) is preferred: 141334.doc 201006795 (a) a method of reacting phosgene with a fluorine-containing alcohol to obtain a fluorine-containing carbonate; (b) by a dialkyl carbonate a method of obtaining a fluorine-containing carbonate by transesterification of an ester with a fluorine-containing alcohol; (4) a method of reacting a compound (6) with a fluorine-containing alcohol in the presence of a catalyst to obtain a fluorine-containing carbonate: ] X11 X16 X12—?一?- ΐ" II χ13ο ku In the formula, X1 1~X is one of the halogens. (6) —" Still scooping constant atoms, at least ~~x Is the atom of the atom. m is more than: It’s all about... It’s better to consider the gas atom or gas = the gas from the gas phase of the phase product. The best is to use the compound as a compound (6), which can be listed as a compound. Acetone, five-gas net, tetrachlorofluoropropene, U, 2_: preparation, fluoroacetone, five chaotic propyl ^ U'3'3- four' chloro 1 propyl I, 1 1 1 1 at i, 1, 1 ·Three gas-3,3,3-trifluoroacetone,: 'difluoroacetone, tetrabromopropanoid, five, ao, 3 · two gas ten ^ Hong tetrafluoroacetone, production industry comparison:: six desert C嗣 et al 'can be used together in higher yields. More useful gas imitation considerations 'better is six gas C 141334.doc •12· 201006795 ” compound (6), chloroacetone can be used in this patent special public Zhao The method of vaporizing propylene oxime described in Japanese Patent Publication No. Sho 61-16255, which is described in the specification of the Japanese Patent Publication No. SHO 61-16255, can be easily produced. Further, the gas acetone can be gasified by using hydrogen fluoride as described in the specification of US Pat. No. 623,595 G. The method 'to easily produce a partially fluorinated compound. · The initial addition of the fluorine-containing alcohol from the viewpoint of increasing the yield of the fluorine-containing carbonate The ratio of the number of ears to the number of moles initially added to the compound (6) (fluorinated alcohol/compound (6)) is preferably more than 丨', more preferably 5 or more, and particularly preferably 2 or more. Examples of the catalyst used in the method (c) include the catalysts used in the following transesterification reaction. The amount of the catalyst is variously selected depending on the catalyst, and is preferably 0.01 to the substrate. 30% by mass, if considering the reactivity and the catalyst removal step after the reaction, it is more preferably 11 to 1% by mass. In the method of (c), in order to promote the reaction, a solvent can be used. However, if the volumetric efficiency of the reactor and the loss of the target in the solvent separation step are taken into consideration, it is preferred to carry out the reaction in the absence of a solvent, if possible. The reaction temperature of the method (c) is preferably ~2 〇〇 art. The reaction pressure of the method of (C) is usually atmospheric pressure. ^ (Transesterification reaction) As a specific method for obtaining a diphenyl carbonate by transesterification of a fluorine-containing carbonate with phenol, a method of reacting a fluorine-containing carbonate and phenol in the presence of a catalyst can be used. The transesterification reaction is carried out at a temperature of about 50 to 100 ° C at the initial stage of the reaction at 141334.doc 13-201006795, but in order to complete the reaction and increase the yield of diphenyl carbonate, it is preferably at a temperature above 100C. The separation was carried out while distilling off the separated fluorine-containing alcohol. Further, if the temperature is too high, the yield due to decomposition of the product or the like is lowered, so that it is preferably carried out at a temperature of 2 ° C or less. The ratio of the number of moles initially added to the fluorine-containing carbonate and the number of moles initially added to the phenol (fluorinated carbonated vinegar/benzene) is as follows, in order to improve the yield of the diphenyl carbonate. It is as small as possible, if the amount of phenol becomes too much, it leads to the loss of phenol in the manufacturing process, or the loss of the target substance when the diphenyl carbonate is purified as a target in the distillation step, so the fluorine-containing carbonated vinegar/benzene The best hope is 〇.1~〇.5. The vinegar exchange reaction can be accelerated by the use of a catalyst. As the catalyst, at least one selected from the group consisting of the following materials; alkali metal hydride, alkaline earth metal hydrogenation

Or oxide, and vinegar exchange reaction catalyst. Species: alkali metal, alkaline earth metal; alkali metal hydroxide, alkali metal hydride, alkaline earth gold;

The metal salt catalyst of the salt (alkali metal toothing, _ ing, alkali metal alkoxide oxidatively better contains strong base and strong acid, alkaline earth metal halide, etc.) or 141334.doc -14- 201006795 A metal salt catalyst (alkali metal alkoxide, alkaline earth metal alkoxide, etc.) of an alcohol salt is particularly preferably a metal fluoride catalyst or a metal oxide. Examples of the metal tester include Li, Na, K, Rb, and Cs. Examples of the soil-checking metal include Be, Ca, and Sr. Examples of the alkali metal hydride include LiH, NaH, KH, RbH, and CsH.

Examples of the alkaline earth metal hydride include BeH2, CaH2, and SrH2. Examples of the alkali metal hydroxide include Li〇H, Na〇H, K〇H, RbOH, and CsOH. Examples of the alkaline earth metal hydroxide include Be (〇H) 2, Ca(〇H) 2, and Sr(OH); and 〇 as a phase transfer catalyst, and examples thereof include a quaternary salt and a quaternary rust salt. , four grades of Arsonium salt, nickel rust salt. As the quaternary ammonium salt, a compound (7) can be cited: [Chemical 10]

(7) wherein R to R14 each represent a hydrocarbon group, and γ- represents an anion. Examples of R to R include an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, a aryl group, an alkyl group, an aralkyl group, and the like, and an alkyl group, an aryl group or an aralkyl group is preferred. The total carbon number of R 1 to Rl 4 is preferably such that each molecule of RnR12R is 3R14N+ is 141334.doc -15-201006795 4 to 100 R"~ respectively may be the same group or different bases. The esters R11 to R14 may be subjected to a functional group by an inert functional group under the reaction conditions. Depending on the reaction conditions, cumene oxime may be an inert group, a nitrile group, a thiol group, a slow group or an oxime group. Further, 'R11 to R14' may be bonded to each other to form a hetero ring (a nitrogen-containing hetero ring or the like). R11 to R14 may be a part of a polymer compound. ❿ As RWR, there may be mentioned tetramethyl cation, tetraammonium ion, tetra-n-propylammonium ion, tetra-n-butylammonium ion, tri-n-octyl-based sulphide, hexadecanthyl-tri-f-group (tetra)-sub-H A nail base triethyl listener, ten city base? Dimethyl bond ion, hexadecane bite rust ion, positive ten n (tetra) sulfonium ion, stupid base triterpene fluorene: sub, stupid triple triion ion, Ν_¥ base f base „(四) 锵 ion, 1 A Record (pentamethonium) ions, hexamethylene ammonium, etc. Φ As Y. ' can be cited: gas ion, fluoride ion, _ sub, moth ion, sulfate ion, nuclear ion, meal ion, peroxy acid ion, sulfate nitrogen ion, hydrogen Oxygen ion, acetate ion, benzoic acid ion, stupid sulfonate ion, p-toluenesulfonic acid ion, etc., preferably chloride ion, bromide ion, iodide ion, hydrogen sulfate ion or hydroxide ion. General from compound (7) In view of properties and reactivity, the compound (7) is preferably a combination of the following and γ. R"RuRnRl4N+: tetramethylammonium ion, tetraethylammonium ion tetra-n-propylammonium ion, four N-butylammonium ion or tri-n-octylmethylammonium ion. Fluoride ion, gas ion or bromide ion 141334.doc • 16- 201006795 As a quaternary phosphonium salt, a compound (8) can be cited: [Chemical 11] R21 R22_ilR24 γ R23 wherein R21 to R24 represent a hydrocarbon group, respectively, and γ- represents an anion. R21~R24' can be listed. IA. Alkyl, cycloalkyl, alkenyl, sessile, aryl, alkylaryl, aralkyl, etc. aryl group, aryl or R21 The total carbon number of the R24 is preferably from 4 to 100. The good molecular weight of the aramid is R21 to R24, respectively, and the same group R21 can be used as a different base.

R to R may be an H-functional group under the reaction conditions, and I may be substituted according to the reaction conditions. Examples of the inert group, the guess base, the brewing group, the slow base, and the alkoxy group can be exemplified by a functional atom, vinegar as R2W3R24p+, a butyl sulfonium ion, a r-n-octyl group, and a tetraethyl scale rust ion. , tetra-negative sputum ion, hexadecane-based tri-n-butyl squama =: sixteen = ethyl tungsten ion, n-pentyl triphenyl scale _ sub-based squamous base triphenyl _ ion, tetraphenyl "two Phenyl cation, as Αν-based squamous ions. Examples of the hydrazine include: a gas ion sulfate ion, a nitrate ion, a _ sub, a (tetra), a cesium ion, a hydride ion, an acetate ion, a peroxy acid ion, a hydrogen sulfate, and a benzoic acid ion. It is gas = ion, benzoic acid ion, pair f, gas ion or desert ion. 141334.doc 201006795 As the quaternary arsenic salt, a compound (9) can be cited: R12 (9) R^-^-r34 y wherein W4 represents a nicotine group and γ_ represents an anion. Examples of R31 to R34 include a mercapto group, a cycloalkyl group, an alkenyl group, and a cycloolefin.

The base group, the aryl group, the alkyl group, the aryl group and the like are preferably an alkyl group. The total number of slaves of A R R is preferably r3ir32r33r34As+ 4 〜1 〇 〇 〇 * A R::~R34 respectively may be the same base or different bases. R~R34 can be substituted under the reaction conditions. Examples of the inert reaction conditions include a dentate atom, a hydroxy group, a nitrile group, a thiol group, a carboxyl group, and an alkoxy group. As compound (9), it can be listed as .g ^ listed · trisylmethyl arsenate fluorinated, fluorinated local sulphur rust, gasified triphenylmethylated tetra-lean A Snoring, brominated tetra-based arsenic bismuth, a polymer derivative of the hydrazine, and the like. As the onium salt, a compound (1〇) can be cited: [Chemical Formula 13] Μ, 43 〇 42^ r do) where R 4 and R 43 each represent a hydrocarbon group, and γ represents an anion 141334. doc 4 201006795 Listed: a group, a cycloalkyl group, a dilute group, an aryl group, a aryl group, an aryl group, etc., preferably an alkyl group or an aryl group: an aralkyl group. Privately, the carbon number of R is preferably 4 to 100 per molecule of R41R42R43S+ rabbit. ^ R=~R43 may be the same base or different bases.

R~R can be substituted with an inert functional group under the reaction conditions. The inert functional group may, depending on the reaction conditions, be a dentin atom, a acetoxy group, a nitrile group, a brewing group, a slow group or an alkoxy group. R R may be bonded to each other to form a hetero ring (a nitrogen-containing hetero ring or the like). R to R 3 may be a part of the polymer compound. As Y-, various anions may be mentioned, preferably a south ion, more preferably a fluoride ion, a chloride ion or a bromide ion. Examples of the compound (10) include: moth di-n-butylmethyl sulfonium tri-n-butyl tetrafluoroborate ruthenium, dihexylmethyl ruthenium iodide, dicyclohexylmethyl sulfonium iodide, and chlorinated 12 Alkylmethylethyl hydrazine, tris(diethylamino)difluorotrimethyl decanoate rust, and the like. Examples of the halide of an alkali metal include LiF, LiCl, and LiBr.

NaF, NaCl, NaBr, KF, KC1, KBr, RbF, RbCl, RbBr, CsF, CsC, CsBr and the like. Examples of the halide of the alkaline earth metal include BeF2, BeCl2, BeBr2, CaF2, CaCl2, CaBr2, SrF2, SrCl2, and SrBr2. As the alkoxy compound of the alkali metal, LiOCH3, LiOCH2CH3, LiOPh, LiOCH2CF2CHF2, NaOCH3, 141334.doc -19-201006795 *

NaOCH2CH3, NaOPh, NaOCH2CF2CHF2, KOCH3, KOCH2CH3, KOPh, KOCH2CF2CHF2, RbOCH3, RbOCH2CH3, RbOPh, RbOCH2CF2CHF2, CsOCH3, CsOCH2CH3, CsOPh, CsOCH2CF2CHF2, and the like. Examples of the alkoxy compound of the alkaline earth metal include Be(OCH3)2, Be(OCH2CH3)2, Be(OPh)2, Be(OCH2CF2CHF2)2, Ca(OCH3)2, Ca(OCH2CH3)2, Ca(OPh). )2 ,

Ca(OCH2CF2CHF2)2, Sr(OCH3)2, Sr(OCH2CH3)2, Sr(OPh)2, Sr(OCH2CF2CHF2)2, and the like. ❹ Examples of the halide of ammonia include NH4F, NH4C1, and NH4Br. As the halogenated substance, NaF, KF, NaCl, KC1, and CsF are preferable in terms of reactivity and utilization on an industrial scale. The halide can be supported on a metal oxide or a composite oxide. As the compound, soda lime or the like can be mentioned. Examples of the ion exchange resin include a cationic ion exchange resin and an anionic ion exchange resin. As a commercial item, Diaion (registered trademark) series (manufactured by Mitsubishi Chemical Corporation), Amberlite (registered trademark) series® (manufactured by Rohm and Haas Co., Ltd.), and Amberlyst (registered trademark) series (manufactured by Rohm and Haas Co., Ltd.) Wait. From the viewpoint of the reaction rate, an ion exchange resin is preferably an anion type ion exchange resin in which a halogen ion is an anion. The compound or oxide of at least one metal selected from the group consisting of various rare earth metals typified by tin, chin, ming, zhen, 19, yttrium, zinc, iron, copper, yttrium, and ytterbium is exemplified. : Titanium compound (tetrabutyl titanate 141334.doc -20- 201006795 ester, tetrapropyl titanate, tetraethyl titanate, tetradecyl titanate, etc.), titanium oxide (Ti〇2), organotin compound (octanoic acid) Tin, monobutyltin oxide, monobutyltris(2-ethylhexanoate)tin, dibutyltin oxide, dibutyltin laurate, dibutyltin diacetate, monobutylhydroxytin oxide, etc.) , stannous oxide (Sn〇), tin halide (stannized stannous oxide (SnCh), stannous bromide (snBr2), stannous iodide (Snl2), etc.), aluminum chloride, aluminum oxide (AGO3), gasification Zirconium (zrCl4), zirconium oxide (Zr02), vaporized copper (CuCl, CuCl2), copper oxide (Cu20, CuO), iron oxide (FeCl2, FeCl3), iron oxide (Fe〇, Fe203), oxide Φ ( CeO, Ce203), cerium oxide (Si〇2), and the like. The transesterification reaction catalyst 'is exemplified by a base or an acid catalyst (alkali metal alkoxide, butyl group, p-benzoic acid, sulfuric acid, peroxy acid, Bf3, etc.). In the present invention, it is particularly preferable that the vinegar exchange reaction of the above-mentioned agricultural carbonate-containing ester with the above phenol is carried out in the presence of a metal salt catalyst and a metal oxide. The metal salt catalyst further enhances the catalytic activity by combining with a metal oxide. The above metal oxide is preferably selected from the group consisting of cerium oxide (Ce〇2/Ce2〇3), lanthanum aluminum oxide (SiOrAl203), γ-alumina (Al2〇3), lanthanum magnesium oxide _ (Si〇2. At least one of a group consisting of Mg〇), zirconia (ZrO 2 ), cerium zirconium oxide (Si〇2.Zr〇2), ZnO.Zr〇2, and Α12〇3_Β2〇3. As a metal oxide, it is better to use Miao Ming oxide, antimony oxide, antimony oxide, and the best. In the method for producing dicumyl carbonate according to the present invention described above, since the specific fluorine-containing carbonated vinegar derived from a fluorine-containing alcohol having a relatively high acid dissociation degree is subjected to a vinegar exchange reaction with benzene, it can be simply used. The process and higher yields produce diphenyl carbonate without the use of toxic compounds such as phosgene. 141334.doc -21· 201006795 In other words, the fluorine-containing carbonate compound used in the present invention has a high degree of dissociation of an ester moiety due to an electron-withdrawing effect of a fluorine atom, and a transesterification reaction with phenol is relatively easy. The method solves the problem of lower yield in the subject of the manufacturing method for producing diphenyl carbonate by the previous transesterification method, and does not require a multi-stage complicated reaction process, and can produce diphenyl carbonate in a simple process and a high yield. An excellent manufacturing method for esters. [Examples] Hereinafter, the present invention will be described in more detail by way of examples, but the invention is not limited to the examples. (Gas Chromatography Analysis) GC analysis was carried out using a 6890 series manufactured by Agilent. [Production Example 1] Production of bis(2,2,3,3-tetrafluoropropyl carbonate) (compound (11)): 500 mL glass equipped with a stirrer, a 20 ° C reflux cooler, and a distillation line In the reactor, after adding 201 g (0.76 mol) of hexa-gas acetone, 358 g (2.71 mol) of 2,2,3,3-tetrafluoropropanol, and 10 g of KF, the temperature was slowly increased while stirring. The reaction was carried out at an internal temperature of 100 ° C for 20 hours. After the reaction was completed, 560 g of the crude reaction liquid present in the reactor was recovered. GC analysis of the recovered liquid confirmed the formation of the compound (11). 214 g of the compound (11) was isolated by distillation of the crude reaction. The yield of the compound (11) based on hexa-gas acetone was 97%: [Chem. 14] F2 141334.doc • 22-201006795 [Production Example 2] bis (2,2,2-difluoroethyl ester) (Production of compound (丨2)): To a pressure-resistant reactor made of 500 mL of Hastel®, add 201 g (〇.76 mol) of six-gas acetone and 271 g (2 71 m). 〇1) 2 2,2 Trifluoroethanol, 1 〇g of CsF, while stirring, the temperature was gradually increased, and the reaction was carried out at an internal temperature of 100 ° C for 20 hours. After the reaction was completed, 480 g of the crude reaction liquid present in the reactor was recovered. The recovered liquid was analyzed, and it was confirmed that the compound (12) was formed. The 163 g compound (12) was isolated by distillation of the crude reaction. The yield of the compound (12) based on hexa-gas acetone was 95%: [Chem. 15] γ γ 3 (12) 〇 [Production Example 3] Carbonic acid bis(1,1,1,3,3,3-hexafluorocarbon) Manufacture of isopropyl ester (compound (π)): To a pressure reactor of 1,000 mL of Herstrom C, 2 〇 1 g (0.76 mol) of six-gas acetone and 455 g (2.71 111 〇) were added. 1) After 1,1,1,3,3,3-hexafluoroisopropanol and 10 g of CsF, the temperature is slowly increased while stirring at an internal temperature of 1 ° C for 20 hours. After the end, 480 g of the crude reaction liquid present in the reactor was recovered. The recovered liquid was subjected to gc analysis, and as a result, it was confirmed that the compound (13) was formed. 41 g of the compound (13) was isolated by distillation of the crude reaction. The yield of the compound (13) based on hexa-acetone was 15%: 141334.doc -23- 201006795 [Chem. 16] 5.丫〇丫 O^CFa "13) CFS 0 CF3 [Example 1] 500 mL glass with a blender, 2 (TC reflux cooler and distillation line)

In the reactor, 174 g (〇.60 mol) of compound (11), 14i g〇5 mol) of phenol, and 3 g of KF were added, and the mixture was slowly heated while facing the reactor. The transesterification reaction was carried out at a temperature of 110 °C. The 2,2,3,3-tetrafluoropropanol produced by the transesterification reaction was distilled off from the distillation line while reacting for 11 hours. After completion of the reaction, the mixture was heated to n L, and the volatile components were distilled off under reduced pressure (3 Torr) to a total recovery capacity. Thereby, the reaction crude liquid is recovered. For the GC analysis of the recovered organic granules, the composition shown in Table 确认 was confirmed. Knife proceeding [Table 1]

Hf2c,

(14) Compound yield (m〇n compound (11) 0.18 2, 2^3) 3 tetra-propanol 0.80 diphenyl hydrazine-- -0.38 compound (14) 0.04 phenol 0.70 [Chem. 17] 141334.doc •24 - 201006795 It is understood from the results of Table 1 that the conversion ratio of the starting material (compound (11)) is 70%, and the selectivity of the diphenyl carbonate as the target is 90% (yield 63%). [Example 2] The reaction crude liquid was recovered in the same manner as in Example 1 except that the same reactor as in Example 1 was used, using 3 g of CsF as a catalyst. GC analysis of the recovered organic components confirmed the composition shown in Table 2. [Table 2] Compound Yield (mol) Compound (11) 0.06 2,2,3,3-Tetrafluoropropanol 0.99 Diphenyl carbonate 0.45 Compound (14) 0.09 Phenol 0.51

As is clear from the results of Table 2, the conversion ratio of the starting material (compound (11)) was 90%, and the selectivity of the target diphenyl carbonate was 83% (yield was 75%). [Example 3] The same reaction as in Example 1 was carried out except that the same reactor as in Example 1 was used, and 3 g of KF and 3 g of cerium oxide (Ce203/Ce02) were used as a catalyst, and the reaction crude liquid was added. Recycling. GC analysis of the recovered organic components confirmed the composition shown in Table 3. 141334.doc -25- 201006795 [Table 3] Compound yield (mol) Compound (11) 0.08 2,2,3,3-tetrafluoropropanol 0.97 Diphenyl carbonate 0.45 Compound (14) 0.07 Phenol 0.53 From Table 3 As a result, it was found that the conversion ratio of the starting material (compound (11)) was 87%, and the selectivity of the target diphenyl carbonate was 87% (yield 76%). [Example 4] The same reaction as in Example 1 was carried out except that the same reactor as in Example 1 was used, using 3 g of CsF and 3 g of cerium oxide (Ce203/Ce02) as a catalyst, and the reaction crude liquid was added. Recycling. GC analysis of the recovered organic components confirmed the composition shown in Table 4. [Table 4] Compound yield (mol) Compound (11) 0.00 2,2,3,3-tetrafluoropropanol 1.19 Diphenyl carbonate 0.59 Compound (14) 0.01 Phenol 0.31 From the results of Table 4, the starting material (compound ( The conversion ratio of 11)) was 100%, and the selectivity of diphenyl carbonate as a target was 98% (yield 98%). [Example 5] 14I334.doc -26-201006795 In the same manner as in Example 1, except that the same reactor as in Example 1 was used, and the reaction solution was recovered, the reaction crude liquid was recovered. . GC analysis of the recovered organic components confirmed the composition shown in Table 5. [Table 5] Compound yield (mol) Compound (11) 0.12 2,2,3,3-tetrafluoropropanyl acid 0.84 Diphenyl carbonate 0.36 Compound (14) 0.12 Phenol 0.66 From the results of Table 5, the starting material (compound ( The conversion rate of 丨丨)) is 8〇%, and the selectivity of diphenyl carbonate as the target is 75% (yield is 6〇%). [Example 6] To a mixer having a stirrer, 20 ° C, and Adding 136 g (0.60 mol) of compound (12), 141 g (1.5 mol) of this compound, and 3 g of KF to the 500 mL glass reactor of the distillation line, one side is slowly mixed in the reactor. The temperature rise was carried out at an internal temperature of 11 ° C. The 2,2,2-trifluoroethanol produced by the vinegar exchange reaction was distilled off from the distillation line, and further reacted for 11 hours. The conversion ratio of the raw material (compound (12)) was 70%, and the selectivity of diphenyl carbonate was 9% to obtain the target. [Example 7] To a scrambler, a 20 ° C reflux cooler, and a museum outlet In a 500 mL glass-breaking reactor, 217 g (0.60 mol) of compound (13), 141 gQ 5 141334.doc -27- 201006795 mol of phenol, 3 g of KF were added, and the reactor was placed in the reactor. OK stirring, slowly warmed side, a transesterification reaction at an inner temperature of 80 ° C. The 1,1,1,3,3,3-hexafluoroisopropanol produced by the transesterification reaction was distilled off from the distillation line, and further reacted for 3 hours to thereby use the starting material (compound (13)). The conversion rate was 100%, and the selectivity of diphenyl carbonate was 98% to obtain a target. [Example 8] The same reaction as in Example 1 was carried out except that the same reactor as in Example 1 was used, and 3 g of NaOPh was used as a catalyst, and the reaction crude liquid was recovered. The organic component recovered was subjected to GC analysis to confirm the composition shown in Table 6. [Table 6] Compound yield (mo) Compound (11) 0.00 2,23,3-tetrafluoropropanol 1.18 Diphenyl carbonate 0.58 Compound (14) 0.02 Phenol 0.67 From the results of Table 6, the starting material (compound (11) The conversion rate of 100%) was 98% (the yield was 98%) of the target diphenyl carbonate. The present invention has been described with reference to the specific embodiments thereof, and it is understood that various modifications and changes can be made without departing from the spirit and scope of the invention. The present application is based on the patent application filed on June 30, 2008. The contents of 2008-170793 are hereby incorporated by reference. 141334.doc -28- 201006795 [Industrial Applicability] The diphenyl carbonate obtained by the production method of the present invention is effectively used as a raw material of polycarbonate which is widely used as an engineering plastic in many fields.

141334.doc -29-

Claims (1)

201006795 VII. Patent application range: A method for producing diphenyl carbonate, which is characterized by being selected from a compound represented by the following formula (1), a compound represented by the following formula (2), and the following formula (3) In the group consisting of the compounds represented by the group, the gas is carbonated vinegar, and the benzene is exchanged with benzene to obtain carbonic acid > epiform: [Chemical 1] Wherein R1 is a group represented by CX1Y1R4, and two of them may be the same or different, and R2 is a hydrogen atom or a group represented by CX2Y2R5, and two R2玎 may be the same or different. R3 is a hydrogen atom or a group represented by CX3Y3R6, and two R3s may be the same or different, and X1 to X3 are each a hydrogen atom, a fluorine atom or Rf, and γ1 to Y3 are respectively a fluorine atom or Rf, and R4 to R6 are respectively fluorine. Atom, Rf, 0Rf or a condensed group having a carbon number of 1 to 6, R is a fluoroalkyl group having a carbon number of 1 to 4 (which may include an etheric oxygen); [Chemical 2] R1 H R2 - a broad-based f p(7) R 〇f2c-r7 141334.doc 201006795 wherein R丨 is a group represented by CX丨Y丨R4, R2 is a hydrogen atom or a group represented by cx2y2r5, and R is a hydrogen atom or a group represented by CX3Y3R6, V It is a perfluoroalkylene group having a carbon number of 1 to 5 (wherein 'may include etheric oxygen), and X1 to X3 are each a hydrogen atom, a fluorine atom or Rf, and γ1 to Y3 are each a fluorine atom or Rf, and R4 to R6 are respectively a fluorine atom, Rf, ORf or an alkyl group having a carbon number of i to 6, R is a fluoroalkyl group having 1 to 4 carbon atoms (which may include ether oxygen); [Chemical 3] r7-cf3 : 2C~i Η C—Ο—C—CFj 0 F2C − ie (3) where R 7 is a perfluoroalkylene group having 1 to 5 carbon atoms (which may include ethereal oxygen) 'two R 7 ' may be the same or different. 2. The method for producing diphenyl carbonate according to claim 1, wherein the transesterification reaction of the gas-containing carbonate with the phenol is carried out in the presence of a metal salt catalyst. 3. The diphenyl carbonate according to claim 2 A manufacturing method, wherein the metal salt catalyst is a metal fluoride or a metal alkoxide. 4. The method for producing diphenyl carbonate according to claim 2, wherein the transesterification reaction of the gas-containing carbonate with the phenol is carried out in the presence of a metal salt catalyst and a metal oxide. 5. The method for producing diphenyl carbonate according to claim 4, wherein the metal oxide 141334.doc • 2 - 201006795 is selected from the group consisting of oxides (Ce〇2/Ce2〇3) and Miaoshao oxide (Si02.Al203). ), γ-alumina (Al2〇3), lanthanum magnesium oxide (SiO 2 Mg0), yttrium oxide (Zr02), lanthanum oxide (Si〇2.zr〇2), ΖηΟ·Ζι·〇2, and Α12 At least one of the groups consisting of 〇3·Β2〇3. 6. The method for producing diphenyl carbonate according to any one of claims 1 to 5, wherein the fluorocarbonate is obtained by using a compound selected from the following formula (4) and the following formula (5) The reaction of at least one fluorine-containing alcohol in the group consisting of the compounds represented as a starting material is obtained: • R1 (4) R2-? - 0Η i"?F2 F2C-C-0H (5 Where R1 is the base represented by cx^4, 7. If r2 is a hydrogen atom or a group represented by CX2Y2R5, R3 is a hydrogen atom or a group represented by & CX3Y3R6, and 7 is a perfluoroalkylene group having a carbon number of 1 to 5 (wherein ether oxygen may be included) ), X1 to X3 are each a hydrogen atom, a fluorine atom or Rf, and γ1 to Y3 are each a fluorine atom or a fluorine atom, a fluorine atom, a Rf, a fluorene Rf or a carbon number 6 alkyl group, and are fluorine having a carbon number of 1 to 4, respectively. An alkyl group (which may include ether oxygen). The method for producing a diphenyl carbonate according to claim 6, wherein the carbon number of the above-mentioned fluorine-containing alcohol 141334.doc 201006795 is 2 to 10. 8. The method for producing diphenyl carbonate according to claim 6 or 7, wherein R2 in the above formula (4) is a group represented by CX2Y2R5. The method for producing diphenyl carbonate according to any one of claims 6 to 8, wherein the fluorine-containing alcohol has a pKa of less than 15. 10. The process for producing diphenyl carbonate according to any one of claims 6 to 9, wherein the above-mentioned fluorine-containing alcohol has a boiling point of less than 181. The method for producing diphenyl carbonate according to any one of claims 6 to 1, wherein the fluorine-containing alcohol is selected from the group consisting of 2,2,2-trifluoroacetonitrile, 2, 2, 3, 3,3-pentafluoropropanol, 2,2,3,3·tetrafluoropropanol, 1,1,1,3,3,3-hexafluoroisopropanol, ,, 4'4-hexabutanol At least one of the group consisting of 2,2 3 3 3,4,4,5,5-octane pentanol and total gas (tert-butyl) alcohol. 141334.doc 201006795 IV. Designated representative map ( a) The representative representative of the case is: (none) (2) A brief description of the symbol of the representative figure: 5. If there is a chemical formula in this case, please disclose the chemical formula that best shows the characteristics of the invention: R1 R1 R2—occupy one-C —0~C—(1} i3 o /i3 141334.doc -2-