TW200948855A - Method for producing polycarbonate - Google Patents

Abstract

Disclosed is a method for producing a high-purity polycarbonate which is not colored by a simple process without using a toxic compound such as phosgene. The method for producing a polycarbonate is characterized in that a polycarbonate is obtained by a transesterification reaction between a diol and at least one fluorine-containing carbonate selected from the group consisting of compounds represented by formula (1), compounds represented by formula (2) and compounds represented by formula (3), which reaction is carried out in the presence of a halogen salt serving as a catalyst.

Description

200948855 VI. Description of the Invention: TECHNICAL FIELD OF THE INVENTION The present invention relates to a method of producing a polycarbonate. [Prior Art "] The barrier acid ester is widely used in many fields as an engineering plastic excellent in heat resistance, impact resistance, and transparency. As a method for producing the aromatic polycarbonate, for example, the following method is known. (i) A method of interfacial polycondensation of bisphenol A and phosgene in the presence of a test catalyst (phosgene method). (ii) A method of melt-condensing bisphenol A and diphenyl carbonate (vinegar exchange method). In the method of (1), since the reaction is carried out at a low temperature, a colorless and transparent polycarbonate can be obtained. However, there are the following problems: use of toxic phosgene; inorganic salts such as vaporized sodium which is by-produced by the reaction must be used. Cleaning and removal; since a solvent such as di-methane is used, complicated steps such as polymer purification and solvent recovery must be provided after the reaction. In the method of (11), since it is not necessary to use a solvent, it is relatively easy to separate the polycarbonate from the reaction system. However, there are the following problems: the transesterification reaction of bisphenol A with diphenyl carbonate is slow, and it is necessary to carry out long-term polycondensation at a high temperature; the phenol having a higher separation point by the transesterification reaction is higher. In order to remove it, high temperature is required; due to high temperature, a side reaction or the like occurs in the polycondensation to color the polycarbonate. As a method for improving the problem of the method, the following method is known. 139493.doc 200948855 (iii) Prepolymer synthesized by reacting bisphenol A with diphenyl carbonate or other dialkyl carbonate A method in which diphenyl carbonate is reacted (see Patent Documents 1 and 2). However, the reaction form or the polycondensation reactivity in the method of (iii) is not different from the usual method (ii), and thus it is difficult to obtain properties equivalent to those of the polycarbonate produced by the method of (1). As the main raw material constituting the polyurethane, the aliphatic polycarbonate is widely used in a relatively low molecular weight. Therefore, an aliphatic polycarbonate diol having a molecular weight of about 1,000 to 10,000 is used in the industry. As a method for producing an aliphatic polycarbonate diol, the following method is known. (IV) A method of transesterifying a dimercaptocarbonate with an aliphatic diol (see Patent Document 3). However, in the method of (iv), the reaction rate is also slower than the method of (ii). Therefore, it is necessary to carry out a long-term reaction at a high temperature. Further, as a method for producing polycarbonate, the following method is known. (V) A method of reacting a bis(β-fluoroalkyl) carbonate with a divalent alcohol in the presence of a base (see Patent Document 4). However, at present, a catalyst represented by an alkali metal, an alkaline earth metal or the like is used as a catalyst, generally in the polymerization of polycarbonate.

In the case of If, there is no step of removing the catalyst after the polymerization, and therefore the quality of the polycarbonate obtained as a product is deteriorated. [Patent Document 1] Japanese Patent Laid-Open No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. [Problem to be Solved by the Invention] The present invention provides a process which can be manufactured in a simple step without using a toxic compound such as phosgene. A method of coloring, high purity polycarbonate. [Means for Solving the Problem] The method for producing a polycarbonate according to the present invention, in the presence of a tooth salt of a catalyst, is a compound selected from the following formula (1), a compound represented by the following formula (7), and the following formula. (3) A method in which at least one fluorine-containing carbonate in the group consisting of the compounds represented by the reaction is exchanged with an alcohol to obtain a polycarbonate. R1 ❹ R2^C~0~C-0-C-R2 (t) where R is a group represented by CXVRV jin, and two ^ may be the same or different 'R2 is a hydrogen atom or The group represented by CX2y2r5 may be the same or different, and each of the 卩3 gas R is a ruthenium atom or a group represented by CX3Y3R6 '2 R3 may be the same or may be different from j ^ and f I ' x to X3 are each a hydrogen atom, a source or a YY, respectively, a fluorine atom or Rf, and R4 to R6 are each a fluorine atom: Rf, 〇Rf or an alkyl group having 1 to 6 carbon atoms, and Rf is a carbon number of 1 to 4. A fluoroalkyl group (which may also contain ethereal oxygen). 139493.doc 200948855 [Chemical 2] R1 Η .I I —

Rz—·0—0—〇—0—C~CF2 (2) R3 O F2〇—rt7 wherein R1 is a group represented by Cffll4, R2 is a hydrogen atom or a group represented by CX2Y2R5, R3 a hydrogen atom or a group represented by c 3 6 Y R6, R is a perfluoroalkylene group having a carbon number of 1 to 5 (including ether oxygen), and X1 to X3 are each a hydrogen atom or a fluorine atom or Rf, γ]~% are each a fluorine atom or Rf, and R4 to R6 are each a fluorine atom, Rf, an alkyl group having 1 to 6 carbon atoms, and Rf is a carbon number! ~4 fluoroalkyl (which also contains ethereal oxygen). ‘, can [Chemical 3]

P2〇—"0—Q—0—death_CFj (3} η o f2c-^7 where HZ is carbon number oxygen) '2 R may be the same or different from the above-mentioned fluorine-containing carbonated vinegar It is preferably obtained by using a reaction selected from the group consisting of a compound represented by the formula and a compound represented by the following formula: formula (5). In the group [Chemical 4] R1 j R^-c-OH hw r7-cf2 I (5) Η 139493.doc 200948855, formula: widely represented by CXVRV jin, R2 is hydrogen represented by CX Y2R5 a group, r3 π rolling mat or CX3Y3R6: base 圏, R7 is a carbon number of 1 to 5 of the total gas stretching base (which may also contain (tetra) oxygen), χΐ ~ χ 3 are chlorine atoms, gas atoms Or Rf, ~3 is a fluorine atom or Rf, r4~r% is a fluorine atom, Rf, a carbon number of the base 'Rf is a carbon number of 4 fluorononyl group (which may also contain anthraquinone oxygen) ).

The above-mentioned tooth salt is preferably selected from the group consisting of a halogen salt of an alkali metal lanthanum, a halogen salt of an alkaline earth metal, a halogen salt of ammonium, a tooth salt of a fourth grade, and an ion exchange resin having a halide salt structure of m^. At least one of the group consisting of. The above-mentioned tooth salt is preferably a fluoride of an alkali metal. The above sulfonium salt is preferably a brominated quaternary acid. Preferably, the ester exchange reaction is carried out in the presence of the above catalyst and a cocatalyst, and a solid acid catalyst is used as the above-mentioned promoter. The solid acid catalyst is preferably selected from the group consisting of a metal oxide having a strong acid point (Acid pomt), a heterogeneous polymeric acid (heter〇p〇iy aci (1), and a cation exchange resin. The metal oxide of a strong acid point is preferably selected from the group consisting of cerium oxide (Ce02/Ce203), cerium oxide _alumina (Si〇2 · erbium 2 〇 3), γ _ alumina (Al 2 〇 3), two Cerium oxide-magnesium oxide (SiO 2 · MgO), zirconium dioxide (ZrO 2 ), cerium oxide _ cerium oxide (si 〇 2 · Zr 〇 2 ), Zn 〇 · Zr 〇 2, and Ah 〇 3 · Β 2 〇 3 At least one of the groups of the above-mentioned fluorine-containing alcohols is preferably 2 to 1 Torr. R2 in the above formula (4) is preferably a group represented by cx2y2r5. 139493.doc 200948855 The pKa of the above fluorine-containing alcohol is preferably less than 15. The pKa of the above-mentioned fluorine-containing alcohol is preferably less than 1. The above-mentioned fluorine-containing alcohol is preferably selected from 1,1, U, 3, 3 - at least one of six gas-gas (third tau) alcohols, and 2,2,3,3,4,4,5,5,6,6-decafluorocyclohexanol斤, and the above diol is preferably an aliphatic diol or a aryl The above aromatic disaccharide is preferably a double A. The carbon number of the above aliphatic diol is preferably 2 to 丨〇. The above aliphatic diol is preferably selected from the group consisting of 3 fluorene. _1^ ▲, 戍-diol, hexanediol '1,3· propylene glycol, and M-butanediol are one group less. &amp; [Effects of the Invention] According to the present invention A method for producing a carbonate can be produced in a simple step without using a toxic compound such as phosgene, and a polycarbonate having no purity of *, 匕, or horse. Further, by using a specific catalyst, High-molecular weight body is obtained at a lower temperature, and the effect of the residual catalyst on the quality of the polycarbonate can be suppressed by using a neutral catalyst, so that high-quality polycarbon = ester oxime can be produced. [Embodiment] In the present specification, The compound represented by the formula (1) is referred to as the compound (1). The compound represented by the other formula is also described in the same manner. <Method for Producing Polycarbonate> Method for Producing Polycarbonate of the Present Invention To obtain a polycarbonate by transesterifying a specific fluorine-containing carbonated vinegar with a diol. 139493.doc -8 - 200948855 (Fluorocarbonate) The fluorine-containing carbonate is at least one selected from the group consisting of the compound (1), the compound (2), and the compound (3). 2 ff R ―中一CM2—(1) ft3 〇k where 2R is a group represented by CX γ R, and two R1 may be the same or different ' R 2 is a hydrogen atom or a group represented by CX2Y2R5 Group, 2 people 2 can be the same or different, R3 is a hydrogen atom or a group represented by CX3Y3R6 '2 R3 can be the same or different, χ1~χ3 are respectively a hydrogen atom, a gas atom or Rf, γ1~ Γ3 is a defeat atom or Rf, respectively, RW is a fluorine atom 'Rf, ORf or a carbon number of 6, and Rf is a carbon number of carbon number 4 (which may also contain etheric oxygen). 2 % j rCOCoC-CFa (2) wherein the formula is a group represented by CXVR4, R2 is an amino atom or a group represented by CXYU, and the r34 hydrogen atom or (3) is a group of the group 7^. R7 is a perfluoroalkylene group having a carbon number of 1 to 5 (wherein 'may also contain (tetra)oxy)' χ1 to χ3 are respectively a hydrogen atom, a fluorine atom or ν, and γ1 to γ3 are respectively fluorine atoms or Rf'R4 to R6, respectively. For the fluorine atom, Rf, the carbon number of 1~6, 1 attack

It is a fluoroalkyl group having a number of 1 to 4 (which may also contain _ oxygen). j J 139493.doc 200948855 [7] r7-cf2 η F〇C_C—0—C—0~C—CFa (3) IH ( IH 0 F2C-R7 where R7 is a carbon number of 1 to 5 Perfluoroalkylene group (which may also contain etheric oxygen), and two R7 groups may be the same or different. Fluorinated carbonates are mostly low-viscosity liquids at normal temperature, which is advantageous for carrying out polycondensation reactions. The fluorine-containing carbonic acid S is usually a polymer having a boiling point of 80 to 25 (TC), and has high heat enthalpy. Therefore, it is easy to obtain a high-purity fluorine-containing carbonic acid by steaming and purifying, thereby producing a high-quality product. It is advantageous in terms of polycarbonate. (Manufacturing method of fluorine-containing carbonate) Fluorinated carbonate, which is obtained in the group consisting of the compound (4) and the compound (5) At least one fluorine-containing alcohol is used as a starting material to obtain R1 (4)

R2—C-0H

PzC-C-OH {S) R where R is a group represented by cxiy R4, a group represented by CXW*, a group represented by r3 h atomic center, and r7 atom is inverted by cx»% Number 1~5 of the whole Dunshen base (which can also be ^139493.doc 200948855 Υΐ \ γ·3, 〇Rf or 'may also have mysterious oxygen), χ1~χ3 respectively humiliate hydrogen atoms, say atoms or Rf, Each is a fluorine atom or Rf, R4 to R6 are each a fluorine atom, a carbon atom of Rf is 66, and Rf is a carbon number of 44 (which contains ether oxygen). As the fluorine-containing alcohol, in terms of increasing the transesterification reaction rate, the acid dissociation degree is higher than that of the diol. Therefore, a preferred base of the alkyl group and the alpha carbon atom of the radical (hereinafter referred to as alpha carbon) is directly bonded.

Compound. The alcohol of the towel and the direct-bonded alcohol are prone to decomposition reaction due to the de-HF reaction, and thus are not preferable. As a measure of acid dissociation, the pKa of a fluorine-containing alcohol is used. When the diol is an aromatic diol, the pKa of the dry alcohol contains about 10, so it is preferably less than 1 Torr. When the diol is an aliphatic diol, the pKa of the fluorine-containing alcohol is preferably less than 15 because the pKa of the aliphatic alcohol is about 15 to 16. As the compound (4), since the more the fluoroalkyl group bonded to the α carbon, the higher the degree of dissociation of the alcohol containing the alcohol, it is preferred that R2 is a group represented by cx2y2r5 (that is, 2' 2 two-level or The tertiary fluoroalcohol), and more preferably, the caliper 3 and the calilem 3 are a group represented by CXW and a group represented by cx3y3R6 (that is, a tertiary fluoroalcohol). — The carbon number of the fluorine-containing alcohol is preferably 2 to 1 Torr. If the carbon number of the fluorine-containing alcohol is 2 or more, it is possible to select a fluorine atom which is not directly bonded to the base of the base. When the carbon number of the fluorine-containing alcohol is 10 or less, the boiling point is a point at which the hourly b is easily removed under stable conditions when the |L-containing alcohol which is dissociated when the polycarb (4) is synthesized by polymerization, and is easily removed. When polymerizing, 139493.doc 200948855 must be set to a higher temperature to synthesize high quality polycarbonate. Specific examples of the fluorine-containing alcohol include 2,2,2-trifluoroethanol, 2,2,3,3,3·pentafluoropropanol, 2,2,3,3-tetrafluoropropanol, l,l,l,3,3,3-hexafluoroisopropanol, 2-fluoropropanol, 2,2,3,4,4,4-hexafluorobutanol, 2,2,3,3,4 , 4,5,5-octafluoropentanol, perfluoro(t-butyl) alcohol, 2,2,3,3,4,4,5,5-octafluorocyclopentanol, 2,2,3, 3,4,4,5,5,6,6-decafluorocyclohexanol, etc.; in terms of acid dissociation, especially 1,1,1,3,3,3-hexafluoroisopropyl Alcohol 'perfluoro(t-butyl) alcohol, 2,2,3,3,4,4,5,5,6,6-decafluorocyclohexanol. As a specific method for obtaining a fluorine-containing carbonic acid by a reaction using a fluorine-containing alcohol as a starting material, the following methods (4) to (4) can be used, in the case where a compound such as phosgene is not used. In terms of higher yield, the (c) method is preferred. (4) A method of obtaining a fluorine-containing carbonic acid by reacting phosgene with a fluorine-containing alcohol. (b) A method of obtaining a hydrocarbon-containing product by subjecting a dialkyl carbonate to a transesterification reaction with a fluorine-containing alcohol. () A method of reacting a compound (6) with a fluorine-containing alcohol in the presence of a catalyst to obtain a gas-containing carbonate.化 X12 一一 f χ1δ χ13ο χ14 χ13ο X14 where X&quot;~π is a hydrogen atom or a dentate atom χΐι~χ respectively, at least one of which is a prostaglandin χ14~X16 respectively a hydrogen atom or a sulphur At least one of the atoms, χ14 to χ16, is a dentate atom. 139493.doc 200948855 It is preferred that X11 to X16 are each a halogen atom, and more preferably a gas atom or a chlorine atom. In terms of obtaining a gas imitation as a by-product, the most preferred oxime is a chlorine atom. As for the compound (6), hexachloropropanoid, five-gas acetone, tetrachloroacetone, ι, ι, 2-trichloroacetone, hexafluoropropane, pentafluoroacetone, m-tetrafluoroacetone, U, 2 may be mentioned. - trifluoroacetone, u, 3, 3, h3_difluoropropane, trichloro-3,3, n-propyl m. , ..., gas-propylene net, ❹ ❹ 漠 嗣 嗣 五 五 五 五 五 五 ❹ ❹ ❹ ❹ ❹ ❹ ❹ ❹ ❹ ❹ ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; The chloropropanes in the compound (6) can be easily produced by a method in which acetone is vaporized as described in Japanese Patent Publication No. Sho 52741 and JP-A-61-16255. Further, a partially fluorinated compound can be easily produced by a method of fluorinating an aziridine with hydrogen fluoride as described in the specification of U.S. Patent No. 6,235,950. In terms of increasing the yield of the fluorine-containing carbonated vinegar, the ratio of the number of moles initially added to the fluorine-containing alcohol to the number of moles of the compound (6) initially added (the fluorine-containing alcohol/compound (6)) is preferably more than i. Further preferably, it is more than 2, and particularly preferably 2 or more. VIII As for the catalyst used in the method (c), the catalyst used in the following polycondensation reaction can be mentioned. ^ The amount of the catalyst is selected according to the catalyst, but it is preferably O.Oi to 30% by mass relative to the substrate, and further preferably 0.1 in consideration of the reactivity and the catalyst removal step after the reaction. ~1〇% by mass. In the method (4), a solvent may be used for the purpose of promoting the reaction. In 139493.doc -13- 200948855, the volumetric efficiency of the reactor is considered right, and the loss of the object at the solvent separation step is preferably carried out in a solvent-free condition, if possible. The reaction temperature in the method (C) is preferably 4 Å to 2 Torr. Hey. (c) The reaction pressure in the process is usually atmospheric pressure. (Glycol) As the diol, an aliphatic diol or an aromatic diol can be mentioned.

As the aliphatic diol, ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, 3-gas-1,2-propanediol, ingas-oxime, propylene glycol, cyclohexane Alcohol, 1,2-propanediol, dipropylene glycol, tripropylene glycol, hydrazine, 3-propanediol, 1,2-butanediol, U3_butanediol, M-butanediol, anthracene, 4-butenediol, 2·methyl -2,4-pentanediol (hexanediol), 3-methyl-10-pentanediol, -pentanediol 1,6-hexanol, fluorine-containing diol (3,3,3-trifluoro-i , 2-propanediol, etc.).

As the usefulness of the aliphatic polycarbonate diol used as a raw material of the polyamino carboxylic acid s, it is preferred that the aliphatic group has a carbon number of 2 to 10 The diol is particularly preferably % methyl -15-pentanediol, 1,6-hexanediol, hydrazine, 3-propylene glycol and M•butanediol. As for the aromatic; alcohol, it can be exemplified by: stupid, phthalate, benzene, and 2,2-(bis(4-p-phenyl)propane [alias: double age a], 2, 2_Bis(4_Phenylphenyl)hexafluoropropanil [alias: shuangfeng AF], bis(4_p-phenylene)di-diphenylbiphenyl, bis(4• 经基基基基_,二A condensate of a benzene, a benzene-like benzene, etc.; in terms of ease of obtaining a raw material or a poly-negative s, preferably bisphenol A. (Transesterification reaction) 139493.doc -14· 200948855 A specific method for obtaining a polycarbonate by transesterification of a fluorine-containing carbonate with a diol is exemplified by the following method (A) or (B), and in terms of production by a simple procedure. Preferably, the method is as follows: (A) A method of melt-condensing a fluorine-containing carbonate and a diol. (B) A method of performing a solution condensation condensation of a fluorine-containing carbonate and a diol. (A) A reaction in the method The temperature is preferably higher than the melting point of the diol in the initial stage of the reaction, and preferably higher than the melting point of the polycarbonate in the late stage of the reaction.

The reaction temperature in the method (A) is preferably 300 ° C or less in terms of suppressing the coloration of the polycarbonate. The ratio of the number of moles initially added to the fluorine-containing carbonate to the number of moles initially added to the second fermentation (fluorinated carbonate/diol) can be appropriately selected depending on the molecular weight of the polycarbonate. In the case of obtaining a fluorine-containing carbonate/diol ratio (mole ratio) in the case of obtaining an aliphatic polycarbonate diol, an aliphatic polycarbonate having a molecular weight of about 1 〜 to about 1 Å is obtained. In terms of the diol, it is preferably 〇8〇~〇·97. (Catalyst) The polycondensation reaction is carried out in the presence of a salt as a catalyst. In the present specification, the term "salt salt" refers to a metal cation or a salt formed by an organic cation and an i-ion ion. As the halogen salt, it is preferably selected from the group consisting of a tooth salt of a metal, a metal of a soil tester, an ammonium halide, a tooth salt of a fourth grade, and an ion parent resin having a salt structure of (4). At least one. As for the metal halide salt, the following are mentioned: LiF, Licl, UBr, NaF,

NaCl, NaBr, KF KC1, KBr, RbF, RbCl, RbBr, 139493.doc -15- 200948855

CsF, CsCn, CsBr, etc. As the south salt of the alkaline earth metal, BeF2, BeCl2, BeBr2, CaF2, CaCl2, CaBr2, SrF2, SrCl2, SrBf2, etc. are mentioned. As the ammonium i salt, NH4F, NH4c, NH4Br and the like can be mentioned. As the quaternary ammonium halide salt, the following compound (?) can be mentioned. [Chem. 10] R1,

Rl2-N-Rt4 r m R13 wherein R11 to R14 each represent a hydrocarbon group, and γ_ represents a halogen ion. The R11 to Rl4' may, for example, be an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, an aryl 'alkylaryl group or an aralkyl group; and more preferably an alkyl group, an aryl group or an aryl group. The total carbon number of R11 to R14 is preferably from 4 to 100 per molecule of rI, r12r] and 丨4N + . R11 to R14 may each be the same group or may be different groups. R&quot;~R&quot; can also be replaced by inert functional groups under the reaction conditions. The inert functional group varies depending on the reaction conditions, and examples thereof include a dentine atom, an ester group, a nitrile group, a decyl group, a carboxyl group, and an alkoxy group. 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 also be a part of a polymer compound. As for R11R] 2R13R14N+', it can be exemplified by • tetramethylammonium ion, tetraethylammonium ion, tetra-n-propylammonium ion, tetra-n-butylammonium ion, tri-n-n-nyl ion, and hexadecyl-trimethyl chloride Section III (4) from ^ 139493.doc -16- 200948855 stilbene diethyl ammonium ion, cetylbenzyl dimethyl ammonium ion, hexadecanoyl pyridinium ion, n-dodecyl pyridinium ion The phenyl triterpene-based ion-based diethyl group is determined by ion, N-block basis ratio, pentamethonium ion, hexamethonium ion, and the like. As for γ, chlorine ions, fluorine ions, bromide ions, and iodide ions are exemplified; • Chloride ions, fluorine ions, and bromide ions are preferred. As the compound (7)', in terms of versatility and reactivity of the compound (7), a combination of the following R&quot;R12R13R14N+ and the following Y· is preferred. p 11 ώ 1 2τ^ 1 3 τ&gt; 14χΤ + . . tetramethylammonium ion, tetraethylammonium ion, tetra-n-propylammonium ion, tetra-n-butylammonium ion or tri-n-octylmethylammonium ion. Y·Deng ion, gas ion or bromide ion. As the ion exchange resin having a halide salt structure, an anion type ion exchange resin having a halogen ion as an anion can be mentioned. As for the commercial products, DIAION (registered trademark) series (Mitsubishi Chemical Co., Ltd., AMBERLITE (δ main volume trademark) series (made by R〇hm and Haas), ❹ AMBERLYST (6 main volume trademark) series (R) 〇hm an (j Haas company), etc. As the _salt, in terms of reactivity and utilization on an industrial scale, it is better to use alkali metal protons (NaF, KF, etc.) or desert. 4. The tooth salt may be carried on a metal oxide or a composite oxide, and the compound may be exemplified by soda lime or the like. (Assisting catalyst) Polycarbon (4) in the present invention In the method for producing a compound, it is preferred to carry out the above transesterification reaction in the presence of a catalyst and a co-catalyst in the presence of a catalyst and a cocatalyst. The catalyst activity can be improved by using a cocatalyst. A solid acid catalyst is used. As the solid acid catalyst, at least one selected from the group consisting of a metal oxide having a strong acid point, an anisotropic polymer acid, and a cation exchange resin is preferred. Oxides, exemplified by: Si〇 2 .

Al2〇3, Si〇2 · MgO, Si〇2 · Zr02, A1203 · B2〇3, Al2〇3, ZK)2, ZnO · Zr02, Ce02, Ce2〇3, various zeolites, etc.; In terms of properties, it is preferably selected from the group consisting of cerium oxide (Ce02/Ce203), cerium oxide-alumina (Si〇2 · Αΐ2〇3), γ alumina (ΑΙ2Ο3), and oxidized granule-emulsified town ( Groups consisting of Si〇2 · MgO), dioxins (Zr02), cerium oxide-cerium oxide (Si〇2 · Zr〇2), Zn〇. Zr〇2, and Al2〇3 · B2〇3 At least one of them. In the method for producing a polycarbonate of 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 transesterified with the second fermentation, the phosgene can be used without using phosgene. In the case of a toxic compound, a coloring, high-purity vinegar is produced in a simple and early step. That is, the fluorine-containing carbonate compound of the present invention has a high degree of dissociation of an ester moiety due to an electron-withdrawing effect of a fluorine atom, so that a transesterification reaction with an aromatic diol or an aliphatic diol is easy, and therefore, The production method of the present invention can solve the problem that the conventional polycarbonate production method using the transesterification method is excellent in the problem of coloring due to long-term reaction at a high temperature. 139493.doc • 18- 200948855 [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 (GC) Analysis) GC analysis was carried out using a 6890 series manufactured by Agilent. (Infrared Absorption Spectrum (IR) Analysis) Using Avatar/Nicolet FT-IR360 manufactured by ThermoFisher Scientific Co., Ltd., the occurrence of carbonate bonds and the disappearance of absorption by hydroxyl groups were confirmed by total reflection. (Gel gel permeation chromatography (GPC) analysis) The analysis was carried out under the following conditions using HLC-8220GPC manufactured by Tosoh Corporation, and the molecular weight was determined by standard polystyrene conversion. Column: TSK GUARDCOLUMN SUPERHZ series column (HZ-L protection column 4000, 3000, 2500 and 2000), mobile phase: tetrahydrofuran, flow rate: 0.3 5 mL/min, detection method: RI detection (refractive index detection ), column temperature: 40 ° C. (NMR analysis) The sample was dissolved in a solvent of deuterated chloroform (CDC13), using JMTC-3 00/54/SS manufactured by JEOL Ltd., using tetramethyl decane as a standard sample, and accumulating at room temperature. The proton nucleus was measured 126 times. [Production Example] 139493.doc • 19- 200948855 Production of bis(2,2,3,3-tetrafluoropropyl)carbonate (compound (11)): reflux condenser and distillation with a stirrer at 20 ° C Adding hexachloroacetone 201 g (〇.76 mol), 2,2,3,3-tetrafluoropropanol 358 g (2.71 mol) and KF 10 g to the 500 mL glass reactor of the outlet, stirring The temperature was slowly raised, and the reaction was carried out at an internal temperature of 1001 for 20 hours. After the completion of the reaction, 560 g of the crude reaction liquid present in the reactor was recovered. GC analysis of the recovered liquid confirmed that the compound (11) was formed. [化11]

0 吼f人八广(10) [Example 1] Add compound (11) 68 5 g (〇3〇m〇) to a 2〇〇mL glass reactor equipped with a stirring device, heating jacket, rectification column and pressure reducing device. 1), bisphenol A (compound (12)) 93.1 g (0_32 m〇1), KF 174 mg (3 〇mm〇1), after nitrogen substitution, heating and melting.

[化 12]

(12) After stirring for 30 minutes, the temperature was raised to 180 ° C. The surface was slowly depressurized, and the resulting 2,2,3,3-tetrapropanol was removed while the surface was removed for 1 hour. After @ 'heating to 2 〇〇. 〇, then slowly decompressing, ^ 1 〇〇 mmHg reaction for 30 minutes. Further heating, depressurization and continue the reaction in the same way as above to reach 250 ° C /1 mmHg was reacted at 139493.doc •20·200948855 and finally reacted at 250 ° C / 1 mmHg for 2 hours. The obtained polymer was subjected to IR analysis, and the absorption by the carboxyl group was observed at the position 1746 cnT1. The position of the cnT1 at 1228 was observed by the absorption of the ether bond, and it was confirmed that it had a carbonate bond. Further, the absorption by the radical was hardly observed at the position of 3650 to 3200 cm·1. Therefore, it was confirmed that the polymer was of the following formula ( 1 3) Polycarbonate represented. [Chem. 13]

(13) The mass average molecular weight (Mw) of the polycarbonate obtained by GPC analysis was 905, the number average molecular weight (?n) was 530, and the degree of dispersion (Mw/Mn) was 1.79. A mixture of molecules of n=2 to 10 centered at n=3. The polycarbonate was not colored, and it was confirmed that it was high in purity. [Example 2]

The polymer was obtained in the same manner as in Example 1 except that CsF 455 mg (3.0 mmol) was used instead of KF as a catalyst. It was confirmed by IR analysis that the polymer was a polycarbonate represented by the formula (13). The mass average molecular weight (Mw) of the polycarbonate obtained by GPC analysis was 1 047, the number average molecular weight (?n) was 667, and the degree of dispersion (Mw/Mn) was 1.58. The polycarbonate was n=4. A mixture of molecules of n=2~10 centered. The polycarbonate was not colored, and it was confirmed that it was high in purity. [Example 3] A polymer was obtained in the same manner as in Example 1 except that CsF 4.6 mg (0.03 mmol) was used in place of KF as a catalyst, 139493.doc • 21 - 200948855. It was confirmed by IR analysis that the polymer was a polycarbonate represented by the formula (13). The mass average molecular weight (Mw) of the polycarbonate obtained by GPC analysis was 820, the number average molecular weight (?n) was 500, and the degree of dispersion (Mw/Mn) was 1.64. The polycarbonate was centered at n=3. A mixture of molecules of n = 2 to 7. The polycarbonate was not colored, and it was confirmed that it was high in purity. [Example 4] In addition to using 2,2-bis(4-hydroxyphenyl)hexafluoropropane (compound (14)) 50.4 g (0.15 mol) in place of bisphenol A as a diol component, and using CsF 227 mg (l .5 mmol) was used in the same manner as in Example 1 except that KF was used as a catalyst. [Chem. 14]

IR analysis of the obtained polymer revealed that the absorption by a few groups was observed at the position of 1740 cnT1, and the absorption by the ether bond was observed at the position of 1210 cm_1, thereby confirming the presence of a carbonate bond. Further, the absorption by the hydroxyl group was hardly observed at the position of 3650 to 3200 cnT1. Therefore, it was confirmed that the polymer is a polycarbonate represented by the following formula (15). [化15]

The polycarbonate had a mass average molecular weight (Mw) of 139493.doc -22-200948855 of 541, a number average molecular weight (?n) of 422, and a degree of dispersion (Mw/Mn) of 1.28. It is a mixture of molecules of n=2 to 4 centered on n=3. The polycarbonate was not colored, and it was confirmed that it was high in purity. [Example 5] • Add hexanediol (HO-(CH2)6-OH) 4.55 g (38.5 mmol) to a 30 mL glass-to-glass reactor equipped with a stirring device, oil bath, cooling trap, and pressure reducing device. The oil bath was kept at 1 liter and dehydrated under reduced pressure of 5 mmHg for 2 hours. After nitrogen substitution, cooling, in a nitrogen glove operating box, add compound (11) 1 〇 5 to 35 mmol), CsF 150 mg (0.9 mmol) ' and then raise it to i2 〇 &lt; t While slowly depressurizing, the formed 2,2,3,3-tetrafluoropropanol was distilled off and reacted at 400 mmHg for 1 hour. Then, the temperature was raised to 15 (rc, and then the pressure was gradually reduced, and the reaction was carried out for 5 hours at ^mmHg. The NMR analysis of the obtained polymer confirmed that the product was produced by the viscous acid ester at a position of 4. 〇 to 4.1 ppm. The peak of the adjacent methylene group was confirmed. Therefore, it was confirmed that the polymer was a polycarbonate represented by the following formula (丨6). [Is 16] 'I 〇\ ^ in the polycarbonate obtained by GPC analysis The mass average molecular weight (Mw) was 5773, the number average molecular weight (?η) was 1933, and the degree of dispersion (Mw/Mn) was 2.99. The polycarbonate was not colored, and it was confirmed to be high in purity. 139493.doc -23- 200948855 [Example 6] A polymer was obtained in the same manner as in Example 5 except that instead of 1,6-hexanediol, 3-mercapto-1,5-pentanediol 4.55 g (38.5 mmol) was used. The NMR analysis of the product confirmed the modification of the adjacent fluorenylene group at the position of 4.0 to 4.1 ppm produced by the polycarbonate. Therefore, it was confirmed that the polymer was a polycarbonate represented by the following formula (17). 17]

m η The mass average molecular weight (Mw) obtained by GPC analysis of the polycarbonate was 3048, the number average molecular weight (?n) was 1521, and the degree of dispersion (Mw/Mn) was 2.01. The polycarbonate was not colored, and it was confirmed that it was high in purity. [Example 7] A polymer was obtained in the same manner as in Example 5 except that 2.33 g (3 8.5 mmol) of 1,3-propanediol was used instead of 1,6-hexanediol. The obtained polymer was subjected to NMR analysis to confirm the peak of the adjacent methylene group which was produced from the polycarbonate at a position of 4.0 to 4.1 ppm. Therefore, it was confirmed that the polymer is a polycarbonate represented by the following formula (18). [Chem. 18]

(18) The mass average molecular weight (Mw) of the polycarbonate obtained by GPC analysis was 139493.doc -24- 200948855, which was 1268 ′, the number average molecular weight (Mn) was 735, and the degree of dispersion (Mw/Mn) was 1.73. The polycarbonate was not colored, and it was confirmed that it was high in purity. [Example 8] A polymer was obtained in the same manner as in Example 5 except that 3.47 g (3 8.5 mmol) of 1,4-butanediol was used instead of 1,6-hexanediol. The NMR analysis of the obtained polymer confirmed the peak of the adjacent methylene group which was produced from the polycarbonate at a position of 4 〇 to 41 ppm. Therefore, it was confirmed that the polymer is a polycarbonate represented by the following formula (19). [Chem. 19]

The polycarbonate had a mass average molecular weight (Mw) of 2060, a number average molecular weight (Mn) of 125 Å, and a degree of dispersion (Mw/Mn) of 1.65. The polycarbonate was not colored, and it was confirmed that it was high in purity. The present invention has been described in detail above with reference to the specific embodiments thereof, and it is obvious to those skilled in the art that various changes or modifications can be made without departing from the spirit of the invention. The present application is based on Japanese Patent Application No. 2008-090433, filed on March 31, 2008, the content of [Industrial Applicability] The aromatic polycarb meaning obtained by the production method of the present invention can be used as an engineering plastic. The aliphatic polycarbonate obtained by the production method of the present invention can be used as a raw material for polyamine phthalic acid vinegar, polyhydric alcohol, polycool, and the like. 139493.doc -25-

Claims (1)

200948855 VII. Patent Application Range: 1. A method for producing a polycarbonate, characterized in that, in the presence of a halogen salt as a catalyst, a compound selected from the following formula (1), and a formula U) At least one fluorine-containing carbonate in the group consisting of the compound represented by the following formula (3) and the diol is subjected to a transesterification reaction, thereby obtaining a polycarbonate; [Chemical Formula 1] ❿ 2 F R1 R2-C~〇~C-〇-C_r2 {1) R3 S R R is a group represented by CfY1!^4, and two R1's may be the same or different, _ is a hydrogen atom or represented by Cx2Y2R5 The two R2 groups may be the same or different, and are a hydrogen atom or a group represented by CX3Y3r6. The two R3 groups may be the same or different, and ^~X3 are respectively a hydrogen atom, a fluorine atom or Rf, Y~Y respectively. It is a fluorine atom or Rf, and R is a fluorine atom; Rf, 〇Rf or a carbon number of ϊ~6 is the /IV-alkane IL in the carbon number 1 [Chemical 2], and may also contain ethericity. Oxygen); CUO I ο 1 '- 3 RICIR I 2 (2) 2 F 7 CIR HIc-li I39493.doc 200948855 where R is represented by CX^Y1!^ a group wherein Rj is a hydrogen atom or a group represented by CX2Y2R5, and is a hydrogen atom or a group represented by CX3Y3R6, and R7 is a perfluoroalkylene group having a carbon number of 5 (which may also contain an ether) X to X are each a hydrogen atom, a fluorine atom or Rf, and Y1 to Y3 are each a fluorine atom or Rf, and R to R6 are each a fluorine atom, Rf, 〇Rf or an alkyl group having a carbon number of 66, and Rf is a carbon number of 1 a fluoroalkyl group of ~4 (which may also contain etheric oxygen); [Chemical 3] In the formula, R is a perfluoroalkylene group having 1 to 5 carbon atoms (which may also contain a bond oxygen). Two R7's may be the same or different. 2. The method for producing a polycarbonate according to claim 1, wherein the salt is selected from the group consisting of an alkali metal halide salt, an alkaline earth metal tooth salt, an ammonium south salt, a quaternary ammonium halide salt, and a salt structure. At least one of the group consisting of ion exchange resins. 3. The method of producing a polycarbonate according to claim 1 or 2, wherein the salt is a fluoride of the metal. 4. The method of producing a polycarbonate according to claim 1 or 2, wherein the gingiva is a brominated quaternary salt. The method for producing a polycarbonate according to claim 1 or 2, wherein the transesterification reaction is carried out in the presence of the catalyst and the cocatalyst, and the cocatalyst is a solid acid catalyst. 6. The method for producing a polycarbonate according to the fifth aspect of the invention, wherein the solid acid catalyst is a group selected from the group consisting of a metal oxide having a strong acid site, an asymmetrical polymeric acid, and a cation exchange resin. At least one of them. 7. The method for producing a polycarbonate according to claim 6, wherein the metal oxide having a strong acid D point is selected from the group consisting of cerium oxide (Ce〇2/ce2〇3), cerium oxide-alumina (Si〇2). Al2〇3), γ-alumina (Al2〇3), cerium oxide _ magnesium oxide (SiO 2 · MgO), dioxin (Zr02), cerium dioxide-cerium dioxide (Si02 · ZrO 2 ), ZnO · At least one of Zr02 and Al2〇3 · B2〇3. 8. The method for producing a polycarbonate according to claim 1 or 2, wherein the fluorocarbonate is composed of a compound selected from the group consisting of a compound represented by the following formula (4) and a compound represented by the following formula (5); At least one fluorine-containing alcohol in the group is obtained as a reaction of a starting material; [Chemical 4] R1 R2-C-0H (4) R3 f-?F2 F2C-0-OH (5) Η wherein R1 is a group represented by CXiyiR4, 139493.doc 200948855 R2 is a hydrogen atom or a group represented by CX2Y2r5, R3 is a hydrogen atom or a group represented by cx3y3r6, and 7 and R are perfluorocarbons having a carbon number of 1 to 5.仲拉甘 | gas 1 methyl group (which may also contain ethereal oxygen), X1 Y1 R4 group, x is a hydrogen atom, a fluorine atom or Rf, respectively, Y is a fluorine atom or Rf, respectively, R is a fluorine atom, Rf, 4, UK or a carbon number of 1 to 6 is burned 9. 10 11. 12. 13. 14. 15. Rf is a fluoroalkyl group having a carbon number of 1 to 4 (wherein the manufacture of the polycarbonate of claim 8 The number is 2~1 〇. 'Can also contain ethereal oxygen). The method wherein the above-mentioned fluorine-containing alcohol is produced by the polycarbonate of claim 8 is a group represented by CXW5. The method for producing polycarbonate according to claim 8 has a pKa of less than 15. The method for producing a polycarbonate according to claim 8 which has a pKa of less than one of the above formula (4) wherein the above-mentioned fluorine-containing alcohol of the above-mentioned fluorine-containing alcohol is a method of producing the polycarbonate of claim 8 The above 3 fluoroalcohol A in white ± 111 is selected from U, l, 3, 3, 3 hexafluoroisopropanol, 4 Wangqi (dibutyl butyl) alcohol, and is 2, 2, 3, 3, 4, The species consisting of 4,5,5,6,6-decafluorocyclohexane &amp; Λ and Dingfu L. Ττ &lt; 芏 Less The manufacturing method of the polycarbonate of claim 1 or 2, wherein the above diol 139493.doc 200948855 is bisphenol A. A method for producing a polycarbonate according to claim 1 or 2, which is an aliphatic diol having 2 to 10 carbon atoms. 1 7. The method for producing a polycarbonate according to claim 1 or 2, which is selected from the group consisting of 3-methyl-1,5-pentanediol and 1,6-hexanediol 1,4-butanediol At least one of them. Wherein the above diol is wherein the diol is 1,3-propanediol and 139493.doc 200948855 IV. Designated representative map: (1) The representative representative of the case is: (none) (2) The symbol of the symbol of the representative figure is simple: 5. If there is a chemical formula in this case, please reveal the best indication of the characteristics of the invention. Chemical formula: (none) 139493.doc -2-