TW201127875A - Method for production of polycarbonate - Google Patents

Abstract

Provided is a method by which a high-quality polycarbonate that is not discolored and has a high purity can be produced in a relatively short time by a simple process without using a toxic compound such as phosgene. Specifically provided is a method for the production of polycarbonate by transesterifying a fluorine-containing carbonate selected from among the compounds (1) to (3) with a diol in the presence of a Lewis acid catalyst. In general formulae (1) to (3), R1 is CX1Y1R4; R2 is H or CX2Y2R5; R3 is H or CX3Y3R6; R7 is C1-5 perfluoroalkylene; X1 to X3 are H, F or Rf; Y1 to Y3 are F or Rf; R4 to R6 are F, Rf, ORf, or the like; and Rf is C1-4 fluoroalkyl.

Description

201127875 VI. Description of the Invention: [Technical Field of the Invention] The present invention relates to a method for producing a polycarbonate. [Prior Art] Polycarbonate is widely used in various fields as a plastic which is excellent in heat resistance, impact resistance, transparency, and the like. As a method for producing an 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 base catalyst (phosgene method) (li) a method of melt-condensing bisphenol hydrazine with diphenyl carbonate (transesterification method) (1) The method is carried out at a low temperature, so that a colorless and transparent polycarbonate can be obtained. However, there are the following problems: use of toxic phosgene; cleaning and removal of inorganic substances such as vaporized sodium by the reaction Since a solvent such as di-methane is used, a complicated process such as purification of a polymer after the reaction and recovery of a solvent is required. The method of (Π) does not require the use of a solvent, and therefore it is easy to separate the polycarbonate from the reaction system. Problem: The reaction rate of transesterification of bisphenol A with diphenyl carbonate is slow. Polycondensation must be carried out at high temperature for a long time. The boiling point of phenol separated by transesterification is high, and high temperature is required for removal. Polycarbonate is colored due to a high temperature to cause side reactions or the like in the polycondensation. As a method for improving the problem of the method of (11), the following method is known. 150432.doc 201127875 (iii) Double-A and A method in which a prepolymer synthesized by reacting diphenyl ester or another dialkyl carbonate is reacted with diphenyl carbonate (refer to Patent Documents 1 and 2). However, the reaction form or polycondensation in the method of '(iii) The reactivity is not different from the usual method (ii), so that it is difficult to obtain the same characteristics as the polycarbonate produced by the method of (1). The aliphatic polycarbonate is widely used as a polyamine hydrazine. Therefore, an aliphatic polycarbonate diol having a molecular weight of about 1,000 to about 1 Å is industrially useful. As a method for producing an aliphatic polycarbonate diol, the following method is known. IV) A method of transesterifying an anti-deer with a dialkyl carbonate and an aliphatic diol (refer to 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) bis(β-fluoroalkyl)carbonate and two in the presence of a base Method of reaction of phenols According to Patent Document 4). In the manufacture of polycarbonate, "there is usually no removal of the catalyst after the reaction." This is used in the method of (ν) to use an alkali metal, an alkaline earth metal, or the like. When a catalyst such as an oxide is used as a catalyst, there is a problem that the quality of the obtained polycarbonate is deteriorated as a product, and when a base catalyst is used, it is easy to cause side reactions such as Fries rearrangement.有 432 432 432 432 432 432 432 432 432 432 432 432 432 432 432 432 432 432 432 432 432 432 432 432 432 432 432 432 432 432 432 432 432 432 432 432 432 432 432 432 432 432 432 432 432 432 432 432 432 432 432 432 432 432 432 Japanese Patent Laid-Open Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. 2, No. Hei. When a toxic compound such as phosgene is not used, a method of producing a colorless: high-purity and high-quality polycarbonate in a relatively short period of time and in a simple process can be produced. Means for Solving the Problem The method for producing a polycarbon (4) according to the present invention is characterized in that, in the presence of a channel acid catalyst, a compound selected from the following formula (1), a compound represented by the following formula (7), and At least one of the groups consisting of the compound represented by the formula (3) contains a carbonic acid exchange reaction with a diol to obtain a polycarbonate reaction; [Chemical Formula 1]

R1 (1) 〇 - c - c c - r2 Ο R3 2 R1 may be the same or not, R1 is CXW1; ^4 shows the same, 150432.doc 201127875 is a hydrogen atom or CX2Y2R5 Two R2s may be the same or different, R is a hydrogen atom or a group represented by CX3Y3R6, and two R3s may be the same or different, and X~X are each independently a hydrogen atom, a fluorine atom or Rf, and y1 to Y3 are respectively Independently a fluorine atom or Rf, Μ~R6 are independently a fluorine atom, Rf, 〇Rf or a carbon number of 6

Rf is a fluoroalkyl group of carbon number 4 (where ' can contain etheric oxygen), and in the case where a plurality of Rs are present, 'a plurality of Rfs may be the same or different from each other. [Chemical 2] 'R21"°ri Wherein R1 is a group represented by CXiY, R4, R2 is a hydrogen atom or a group represented by cx2y2r5, R3 is a hydrogen atom or a group represented by cx3y3r6, and V is a perfluoroextension group of carbon number 5 (wherein , may contain anthracene oxygen), X~X3 are each independently a hydrogen atom, a fluorine atom or Rf, and Υ and Υ3 are each independently a fluorine atom or Rf, R, OR or a carbon number of 1 to 6 and may have a facet property. Oxygen) may be the same or different from each other in the presence of a complex; R4 to R6 are each independently a fluorine atom, and Rf is a fluoroalkyl group having a carbon number of 1 to 4 (in the case of a plurality of Rfs, a plurality of Rfs are

[化3J 150432.doc 201127875 F2C—C—〇~C—O—C-CF, (3) li & f2U7 where 'R7 is a total gas extension base with a carbon number of 1 to 5 (wherein, it may contain a bond) Oxygen) 'Two R7's may be the same or different. The Lewis acid catalyst is preferably at least one selected from the group consisting of compounds represented by the following formula (7) or selected from the compounds of the following formula (8) to h; Mi+(R8Xj-)m(Yk -)n . . . (7) ' where i=jxm+kxn, i and j are integers of 1 or more, k is an integer of 2 or more, m and η are integers of 〇~4, respectively, and Μ is a metal element Or a semimetal element, X' is a common test of an organic acid group, R8 is a hydrogen atom, a hydrocarbon group which may have a functional group, or a polyfluoroalkyl group having a functional group of 1 to 10 carbon atoms ,

Yk is an inorganic anion other than a halogen ion. The above formula (7) is preferably c〇〇·, s〇〆, 〇s〇3-, 〇ρ〇32· or 0;

Mp+s(R8X^)t(Y-)u (8) where 'pxs=qxt+r.xu, P and q are integers of 1 or more, r is an integer of 2 or more, and s is 2 or more The integer, 150432.doc 201127875 t, U is an integer of 〇 ~ 4 ' Μ is a metal element or a semi-metallic element,

Xq_ is a total of organic acid groups, R8 is a hydrogen atom, a hydrocarbon group having a functional group having a carbon number of 1 to 10, or a polyfluoroalkyl group having a functional group having a carbon number of 1 to 10, and γρ is a halogen-removing group. An inorganic anion other than ions. Xq_ in the above formula (8) is preferably c〇〇·, s〇3·, OSCV, 〇ρ〇32- or cr. The above Lewis acid catalyst is preferably a metal alkoxide, a metal trifluoromethane compound or a metal oxide. The above metal oxide oxide is preferably an alkoxide of a metal selected from the group consisting of Ti, Zr, 8 Å and Sn. The above metal difluoroantimony sulfonate compound is preferably selected from the group consisting of Ce, Hf,

A triflate compound of La, Nd, Sc, Tm, and a metal other than gamma. The above metal oxide is preferably selected from the group consisting of octa Zn and s oxide. The above-mentioned catalyzed carbonic acid rider is preferably obtained by using a compound selected from the group consisting of a compound represented by the following formula (4) and a compound represented by the following formula: ~_h^{J Π & 弋() At least one kind containing (iv) as a starting material for the reaction; in the middle of the species [4] R1

R2—C-OH 150432.doc (4) 201127875

Wherein R1 is a group represented by CX^Y1!^, R2 is a hydrogen atom or a group represented by cx2Y2R5, R3 is a hydrogen atom or a group represented by CX3Y3R6, and 1 is a perfluoroalkylene group having a carbon number of 1 to 5 ( Which may contain ethereal oxygen),

Xj~X3 are each independently a hydrogen atom, a fluorine atom or Rf, and γ1 ～ γ3 are each independently a fluorine atom or Rf, and Ά is independently a fluorine atom, Rf, 〇Rf or a carbon number of 6 alkyl groups, and Rf is a carbon number of 1 The fluorine material of ～4 (which may contain occupational oxygen) may be the same or different from each other in the case of a plurality of Rk. The carbon number of the above fluorine-containing alcohol is preferably from 2 to 10. R2 of the above formula (4) is preferably a group represented by CX2Y2R5. The PKa of the above-mentioned fluorine-containing alcohol is preferably less than 15, more preferably less than... The above fluorine-containing alcohol is preferably selected from the group consisting of (1) deca-hexafluoropropanol to all-third And 2, 2, 3, 3, at least one of the group of coffee. The above diol is preferably an aliphatic diol or an aromatic diol. The above aromatic diol is preferably bisphenol A. The above aliphatic diol is preferably an aliphatic diol having 2 to 1 carbon atoms. The above aliphatic diol is preferably selected from the group consisting of 3-pentanediol, hexanediol, 1,3-propanediol, hydrazine, and butylene glycol. At least 150432.doc 201127875 Effect of the Invention According to the method for producing a polycarbonate of the present invention, it is possible to manufacture in a relatively short period of time and in a process of singularity without using a toxic compound such as phosgene. No coloring, high purity and high quality polycarbonate. [Examples] In the present specification, the compound represented by the formula (1) is referred to as the compound (1). The compounds shown by other formulas are also described in the same manner. <Production Method of Polycarbonate> The method for producing a polycarbonate of the present invention is a polycarbonate obtained by transesterification of a specific fluorine-containing carbonate with a diol in the presence of a Lewis acid catalyst. method. (Fluorocarbonate) The fluorine-containing carbonic acid is selected from at least one selected from the group consisting of the compound (1), the compound (2), and the compound (3). ψ R1 R2+0 4 4 R 2 (1) a Ί R is a group represented by CX〗 YlR4, 2 Ri may be the same or not a hydrogen atom or a group represented by Cx2Y2R5, 2 R2 It may be the same or 5 R is a hydrogen atom or a group represented by CX3Y3R6, and two R3s may be the same or different, and the parent I

~Χ is independently a hydrogen atom, a fluorine atom or Rf, Υ1~Υ3 are independently g M atoms or R, R~R6 are each independently a fluorine atom, Rf, 〇Rf J50432.doc 201127875 or a slave number 1~6 The alkyl group, Rf is a fluoroalkyl group having 1 to 4 carbon atoms (which may contain ether oxygen). When a plurality of "in the case of a plurality of", a plurality of "may be the same or different from each other." R2~C~〇-C-〇-6-cp (2) R3 〇 wherein R is a group represented by Οχΐγ1!^4, R2 is a hydrogen atom or a group represented by cx2y2R5, and R3 is a hydrogen atom. Or a group represented by CX3Y3R6, R7 is a total alkyl group of carbon number 5 (which may contain etheric oxygen), and χ1~χ3 are each independently a hydrogen atom, a fluorine atom or Rf, and Υ1~Υ3 are independently fluorine. The atom or Rf, R4 to R6 are each independently a fluorine atom, Rf, 0Rf or an alkyl group having 1 to 6 carbon atoms, and Rf is a fluoroalkyl group having 1 to 4 carbon atoms (which may contain ether oxygen), in the presence of plural In the case of Rf, a plurality of Rfs may be the same or different from each other. F-〒 f2 η F2C—9—0~C—〇~C—CF2 (3> ή ϋ where ' R7 is a perfluoroalkylene group having a carbon number of 1 to 5 (which may contain ether oxygen) The two R7s may be the same or different. The fluorine-containing carbonate is a liquid having a low viscosity at normal temperature, and is advantageous in carrying out a polycondensation reaction. Further, the boiling point is 8 Å to 25 Å. : The range is larger, the thermal stability is also higher, so it is easy to obtain high-purity 150432.doc 201127875 fluorocarbonate by distillation purification. It is more suitable for manufacturing high quality polycarbonate ( Method for Producing Fluorinated Carbonate The fluorine-containing carbonate can be obtained by using at least one fluorine-containing one of the selected groups. [Chemical Formula 8] The alcohol of the compound (4) and the compound (5) is used as a starting material. Reacted to obtain R1 R2—C-OH (4) ft3

Wherein the base 'r2 represented by 'RUcxW' is a hydrogen atom or a group represented by cx2y2R5, a group represented by a nitrogen atom or cxW, r7 is a carbon number w, a base group (wherein (4) oxygen may be contained), and χ1 to χ3 Independently for the wind 4 original 6, fluorine atom or Rf, Υ, ~ γ3 are each independently a fluorine atom or: ~ R are independently a gas atom, Rf, 0Rf or carbon number 烷基 alkyl, Rf = several plants (4) (Where, it may contain, oxygen generation), in the case of a plural number, the plurality of * may be the same or different from each other. As the fluorine-containing alcohol, in terms of improving the exchange rate of s, it is preferred that the acid dissociation degree is higher than the acid dissociation degree of the diol. It is preferred that the fluorine: group is directly bonded to the carbon atom of the alpha position of the radical (hereinafter also referred to as the charcoal), since the atom is directly bonded to the alcohol of (iv) and is easily desorbed by the HF. I50432.doc 12 201127875 It is preferred to cause a decomposition reaction. As a measure of the degree of acid dissociation, the pKa of the fluorine-containing alcohol can be used. Since the ubiquitous PKa is about 10, the pKa of the fluoroalcohol when the diol is an aromatic diol is preferably less than 10. Since the pKa of the aliphatic alcohol is about 15 to 16, the pKa of the fluorine-containing alcohol in the case where the diol is a fatty phthalic diol is preferably less than 15. As the compound (4), the more the fluoroalkyl group bonded to the α carbon, the higher the dissociation degree of the alcohol-containing alcohol, and therefore it is preferable that the rule 2 is a group represented by CX2Y2R5, that is, a fluorine of a grade or a third grade. The alcohol is more preferably a base of CX2W and a base of CX3Y3R6, that is, a three-stage fluorine-containing alcohol. : 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, a stable fluorine-containing yeast in which the fluorine atom is not directly bonded to the α position of the hydroxyl group can be selected. When the carbon number of the fluorine-containing alcohol is 10 or less, the boiling point of the fluorine-containing alcohol is: Steaming: When the alcohol-containing alcohol which is dissociated during the transesterification reaction is removed, the boiling point of the alcohol-containing alcohol can be easily removed, so It is not necessary to apply a relatively high temperature during the reaction, and it is possible to produce a polycarbonate of high quality. As a specific example of the fluorine-containing alcohol, .9 . , 0 ^ J magical 2,2,2-difluoroethanol, 2,3,3-tetramethylpropanol, 1,1,1,3,3,3 - hexafluoro-2-propanol, 2-fluoropropanol, 2,2,3 4 gas 'fluorobutanol, 223 3 44 ς< octafluoropentanol, perfluoro (third butyl 2, 2, 3, 3 ,4,4,5,5_ ^ Earth alcohol 2,2,3,3,4,4,5,5-octafluorocyclohexane, 2,2,3,3,4,4,5,5,6 , 6- decafluoroquinone? Expanded from pentacene, Μ α λ π 3 hexyl hexanol. In terms of acid dissociation, particularly good is selected from u Hui Erding, ▲ ' ' 'rat - 2-propanol 'perfluoro(first butyl) alcohol, 2,2,3,3,4,4,5,5 king (different ^ ^ ^ ± ^ ,, decafluorocyclohexanol乍 乍 由 由 由 150 432 432 432 432 432 432 432 432 432 432 432 432 432 432 432 432 432 432 432 432 432 432 432 432 432 432 432 432 432 432 432 432 432 432 432 432 432 432 432 432 432 432 432 432 432 432 432 The method of (c) is preferred in terms of a higher yield of the toxic compound. (a) A method of reacting phosgene with a fluorine-containing alcohol to obtain a milk-containing carbonate. (b) by carbonic acid Method for obtaining a carbonated vinegar by transesterification of an alkyl ester with a fluorine-containing alcohol (c) A method of reacting a compound (6) with a fluorine-containing alcohol in the presence of a catalyst to obtain a fluorine-containing carbonate.

Atom, just as

Among them, Xn -1, at least one of the atomic atoms, is preferably: more preferably, in terms of a fluorine atom or a gas, it is preferably a disordered atom.

For example, fluoroacetone, 1,11-dioxatetraacetone, U, ruthenium trichloride can be cited as hexachloroacetone, :chloropurine 1,1,3-three

Tetrabromopropionate

, pentabromopropyl, hexabromopropyl 150432.doc 201127875 ketone and so on. It is produced in a high yield at the same time as ^> in an industrially useful aspect of the gas, and a' is preferably a six-gas acetone. In the compound (6), the method of chlorinating acetone is described in the Japanese Patent Publication No. Sho 60-52741, and the method of chlorinating acetone described in the Japanese Patent Publication No. SHO 61-16255. It is made in the valley. Further, a partially fluorinated compound can be easily produced by a method in which chloroacetic acid is fluorinated by using a sulfonium halide 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 initial molar amount of the fluorine-containing alcohol to the initial molar amount of the compound (6) (the alcohol-containing alcohol/compound (6)) is preferably more than 2 , more pregnancy, the f 疋 2.5 or more, particularly good is 3 or more 0 as the catalyst used in the method of (4), can be listed: metal test; soil test metal; metal hydride test; soil metal hydride; Metal oxides; soil metal hydroxide; phase transfer catalyst; alkali metal #; soil metal halide; ammonia halide; ion exchange for fat;

a compound or oxide of at least a metal in a group consisting of Ti, A, W, Mo, and Zmn; a transesterification reaction catalyst or the like. The amount of the catalyst used in the method (c) is variously selected depending on the catalyst, and is preferably 0.01 to 30% by mass based on the substrate, and it is more preferable to consider the reactivity and the catalyst removal step after the reaction. It is 〇 mass%. In the method of (C), a solvent may also be used for the purpose of promoting the reaction. Among them, in consideration of the volumetric efficiency of the reactor and the loss of the target in the solvent separation step, it is preferred to carry out the reaction as much as possible without a solvent. The reaction temperature in the method (c) is preferably 4 〇 to 2 〇〇 °c. 150432.doc The reaction pressure in the method of 201127875 (C) is usually atmospheric pressure. (Glycol) Examples of the diol include an aliphatic diol and an aromatic diol. Specific examples of the aliphatic diol include ethylene glycol, diethylene glycol, t ethylene glycol, tetraethylene glycol, gas-oxime, propylene glycol, propylene glycol, M·cyclohexanediol, i, 2_. Propylene glycol, dipropylene glycol, tripropylene glycol, 1,3-propanediol, butanediol, butanediol, hydrazine, 4-butanediol, hydrazine, 4-butenol, 2-mercapto-2,4-pentanediol (hexanediol), 3-methyl-oxime, 5-pentanediol, 1'5-pentanediol, hydrazine, 6-hexanediol, fluorochemical diol (3,3,3-trifluoro-propanediol) and many more. The aliphatic diol is an aliphatic diol having a carbon number of 2 to 10, more preferably an aliphatic diol having a carbon number of 2 to 10, in terms of usefulness as an aliphatic polycarbonate diol used as a raw material of a polyurethane or the like. Particularly preferred are aliphatic diols selected from the group consisting of 曱 丨 丨, _ _ 户, hexanol, 1,3-propanol and 1,4-butanediol. Specific examples of the aromatic private glycol include resorcin, catechol, hydroquinone, and 2,2-bis(4-hydroxyphenyl)propane [alias: bisphenol A], 2, 2 _ bishydroxyphenyl) hexafluoropropane [alias: bisphenol AF], bis(4-hydroxyphenyl)decane, 4,4'-dihydroxybiphenyl, bis(4-hydroxyphenyl)ether, dihydroxy A condensate of naphthalene, m-trisphenol, phenol, etc., is preferably bisphenol A in terms of easiness of obtaining a raw material or usefulness of polycarbonate. (Lewis acid catalyst) The term "Lewis acid catalyst" refers to a substance which enhances reactivity by accepting an electron pair of a raw material of a reaction system.

If For Lewis & Catalyst' is more effective in promoting the exchange of reactivity, 150432.doc -16·201127875 and in terms of inhibiting the coloration of the synthesized polymer, it is preferably selected from the compound (7). At least one or at least one compound selected from the group consisting of the following formula (8) 0 (7)

Mi+(R8xj-)m(Yk-)n where i=jxm+kxn, i and j are integers of i or more, respectively, and are integers of 2 or more, and m and η are integers of 〇4, respectively.

Mp+s(R8xq-)t(Yr-)u ... (where ' pxs=qxt+rxu, p and q are integers of 1 or more, r is an integer of 2 or more, s is an integer of 2 or more, t, u In the compound (7) and the compound (8), M is a metal element or a semimetal element. Examples of the metal element include Li, Be, Na, Mg, and ab.

Ca Sc, Τι, V, Cr, Μη, Fe, Co, Ni, Cu, Zn, Ga,

Rb Sr, Y, Zr, Nb, Mo, RU, Rh, Pd, Ag, Cd, In, Sn Cs, Ba, La, Ce, pr, Nd, Sm, Eu, Gd, Tb, Dy 'H〇, Er , Tm, Yb, Lu, Hf, Ta, w, Re, 〇s, ir, pt,

Au Hg, T1, Pb, Bi, and the like. Examples of the semimetal element include B, Si, Ge, As, Sb, Te, and p〇. X () in the compound (7) and hydrazine in the compound (8) (ϊ_ is a conjugate base of an organic acid group as a co-basic base of an organic acid group, and may be exemplified by (〇〇., §〇3-, 〇8〇3-〇Ρ〇3, Ο, CO, SCO·, ONOCT, CONH·, CHNO., SO, NHCOO-, S-, NO-, etc., in terms of thermal stability and reactivity, 5 Preferably, it is c〇〇_, s〇3-, 〇s〇3-, 〇p〇32- or. In the compound (7) and the compound (8), r8 is a hydrogen atom and may have a functional group. a group of 1 to 10, or a group of carbons having a functional group of 1 (), 150432.doc • 17·201127875. Compound (7) is made in # and compound (8) is a dentate ion The inorganic anion. Examples of yk• and yr. include 〇2, S2·, ^·, etc. As the Lewis acid catalyst, the reaction activity and the chromaticity of the synthetic polymer are preferred, and the metal alkoxide is preferred. , metal tri-methanesulfonate compound, or metal oxide. Appearance oxide, in terms of reactivity, low toxicity, better 疋 selected from the heart of the heart, coffee metal oxide. :: Metal oxide oxide Specific examples include titanium tetramethoxide, tetraethyl butyl dipropoxy phthalate, titanium tetraisopropoxide, titanium tetra-n-butoxide, tetra-: butoxide-based titanium, and tetra-butoxy group. Titanium, tetrapentyloxy, tetrahexyloxytetraheptyloxytitanium, tetraoctyloxy, tetradecyloxytitanium, tetradecyloxytitanium, tetrakis(undecyloxy)titanium, tetra (twelve

Au, , 丄1 - alkoxy) titanium, tetrakis (tetradecyloxy) titanium, tetrakis (hexadecyloxy) titanium, tetra-eighteen milk « Λ, paste-based titanium, tetra-cyclopropene _,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,, Titanium, tetracyclic decyloxy (tetra), decyl, titanium, 1 ring, tetradecyl, tetraethoxy, tetrapropoxy, 'tetratetramethoxy, rhododendron, "propyl acrylate, tetra-n-butylene , four third butoxy ruthenium, four second j rolled tetrahexanthene; milk base fault, tetrapentyloxy oxime, tetradecyloxy hammer, tetraheptyloxy fluorene, tetradecyloxy group, tetra (octaoxide) Base product, tetradecyloxy, tetraalkoxy) zirconium, tetrakis (tuprahylene oxy), tetrakis (hexadecyloxyoxy), tetrakis (decacyclic, tetracyclobutoxy) Wrong, tetracyclic, octadecyloxy, tetrahydroxyl, tetracyclohexyloxy, sulphate, sulphate, sulphate, sulphate, sulphate, sulphate, sulphate, sulphate, sulphate Oxylate, tetracyclohexaoxy ισ, four percent ten-formation, fluorenyl, tetracyclododecyloxy, tetramethyl Oxy decane, tetraethoxy sulphate, tetrapropoxy decane, tetraisopropoxy decane, tetra-n-butoxy decane, di-butoxy oxan, tetra-butoxy decane, tetrapentyloxy Decane, _tetrazed decane, tetraheptyloxydecane, tetraoctyloxy cleavage; tetradecyl decyl decane, tetradecyloxydecane, tetrakis(undecyloxy) calcined, four ( Twelve virgins, (butty oxy) decane, tetrakis (tetradecyloxy) decane, tetrakis (hexadecyloxy) (four), four. ten decyloxy money, four ring propylene gas base stone 4% butoxylate, tetracyclopentyloxycarbazide, tetracyclohexyloxycarbazide, tetracycloheptyloxycarbazide, tetracyclooctyloxyxetane, tetracyclic alkoxy oxacyclohexane, tetracyclic癸oxydecane, tetracycloundecyloxydecane, tetracyclododecyloxydecane, tetramethoxytin, tetraethoxytin, tetrapropoxytin, tetraisopropoxy tin, tetra-negative Butoxytin, tetra-tertiary butoxide, tetra-butoxide, tetrapentyltin-tetradecyloxytin, tetraheptyloxytin, tetraoctyloxytin, tetradecyloxy tin Tetramethoxy group , tetrakis(undecyloxy)tin, tetrakis(dodecyloxy)tin, tetrakis(tetradecyloxy)tin, tetrakis(hexadecyl)tin, tetra-octadecyloxy tin, Sihuan No_Shame ^ Tin, tetracyclobutoxytin, tetracyclopentyloxy tin, tetracyclohexyloxy tin, tetracycloheptyloxy tin, tetracyclooctyloxy tin tetracyclononanoxide, four Cyclodecyl tin oxide, tetracycloundecyl tin oxide, tetracyclododecyloxy tin, etc. As the metal triflate compound, from the viewpoint of reactivity, it is preferably selected from Ce a trifluorosulfonium sulfonate compound of a metal of Hf, La, Nd, Sc, Tm, Yb and γ. Specific examples of the metal trifluorite compound are exemplified by three I 曱 150432.doc -19- 201127875 Rhubarb acid decoration (III), three gas bismuth acid copper (I) benzene, tri-I bismuth copper phthalate (ιι), trifluorosulfonium sulfonate (IV), bismuth triflate (III) , lithium bis(trifluoromethanesulfonyl) phthalimide, lithium trisulfonate, magnesium triflate, titanium tris (III), potassium trifluoroantimonate, trifluoroantimony Vanadium sulfonate (111), silver tris-sulfonate, trifluoroantimonate Trifluoromethyl citrate (III), trifluoromethyl tin (II), trifluoromethanesulfonate mirror (III), trifluorosulfonium sulfonate (111), tri-a zinc citrate (Π), etc. . As the metal oxide, an oxide of a metal selected from the group consisting of Al, Zn, Sn, and Pb is preferred in terms of reactivity. (Transesterification reaction) As a specific method for obtaining a polycarbonate reaction by subjecting a fluorine-containing carbonate to a hydrazine exchange reaction in the presence of a Lewis acid catalyst, the following method (A) or (B) can be mentioned. In terms of being able to be manufactured in a simple process, the method of (A) is preferred. (A) A method of melt-condensing a fluorine-containing carbonate and a diol in the presence of a Lewis acid catalyst. (B) A method of performing solution polycondensation of a fluorine-containing carbonate and a diol in the presence of a Lewis acid catalyst. The reaction temperature in the method (A) is preferably at least the melting point of the diol at the initial stage of the reaction. The melting point of the polycarbonate is preferably at least in the late stage of the reaction. Further, in terms of suppressing the coloration of the polycarbonate, the reaction temperature in the method (A) is preferably 3001: or less. The ratio of the initial mole number of the fluorine-containing carbonate to the initial mole added amount of the diol (fluorinated carbonate/diol) is appropriately selected according to the target molecular weight of the polycarbonate 150432.doc • 20-201127875. A fluorine-containing carbonate/diol obtained when an aliphatic or aromatic polycarbonate diol is obtained in terms of obtaining an aliphatic or aromatic polycarbonate diol having a molecular weight of about 1,000 to about 1 Å. The ratio (mole ratio) is preferably 0_90 to 1,30. In the method for producing a polycarbonate according to the present invention described above, a specific fluorine-containing carbonic acid derived from a fluorine-containing alcohol having a relatively high acid dissociation degree is subjected to a transesterification reaction with a diol, so that light can be used without using light. In the case of a toxic compound such as gas, the polymerization reaction speed is faster, and a colorless, high-purity polycarbonate is produced in a simple process. In other words, the fluorine-containing carbonate compound of the present invention has a high degree of dissociation at an ester site due to an effect of electron attraction of a fluorine atom, and is easily exchange-reacted with an aromatic diol or an aliphatic diol. The method for producing a polycarbonate of the present invention of a fluorocarbonate compound is an excellent production method capable of solving the following problems: a method of producing a polycarbonate by a conventional transesterification method, that is, a reaction at a high temperature for a long period of time And cause coloring. Further, in the above-described method for producing a polycarbonate of the present invention, a specific Lewis acid catalyst is used, so that the knives can be obtained at a faster reaction rate. Therefore, it is difficult to cause a side reaction such as Fries rearrangement which occurs when the prior alkali catalyst is used, and the effect of coloring or branching on the quality of the polycarbonate can be suppressed, and a high-quality polycarbonate can be produced. EXAMPLES Hereinafter, the present invention will be described in more detail by way of examples, but the present invention is not limited to the examples. 150432.doc -21· 201127875 (Gas Chromatography (GC) Analysis) GC analysis was carried out using a 6890 series manufactured by Agilent. (Gel Permeation Chromatography (GPC) Analysis) Using HLC-8220GPC manufactured by Tosoh Corporation, the analysis was carried out under the following conditions, and the molecular weight was determined by standard polystyrene conversion. Column: TSK GUARDCOLUMN SUPERHZ System | J column (HZ-L guard column, 4000, 3000 ' 2500 and 2000), mobile phase: tetrahydrofuran, flow rate: 0.35 mL / min, detection method. RI detection, column temperature: 40 ° C. (Synthesis Example 1) Synthesis of bis(2,2,3,3-tetrafluoropropyl)carbonate (compound (11)): 500 mL with a stirrer, a reflow cooler at 20 ° C, and a distillation line 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 to the glass reactor, the temperature was slowly increased by stirring. The reaction was carried out for 20 hours at an internal temperature of 1 °C. After the reaction was completed, 560 g of the crude reaction liquid remaining in the reactor was recovered. GC analysis of the recovered liquid confirmed the formation of the compound (11). Compound (11) was purified by distillation and used for the synthesis of the following polycarbonate. 15011.doc -22- (11) (11)201127875 hf2cx (Example 1) Synthesis of polycarbonate 1 (tetra-n-butoxytitanium catalyst): reaction in a 300 mL melt polymerization apparatus 87.3 g (〇.30 mol) of bisphenol A (compound (12)), 75_4 g (0.33 mol) of compound (11) '1.02 g (3.0 mmol) of tetra-n-butoxytitanium were added. The following deoxygenation steps were repeated three times. Deoxidation step: Exhaust at o ° c until the pressure in the reactor becomes about 1 Torr, whereby oxygen is discharged and the reactor is filled with nitrogen again. [化11]

150432.doc -23· 201127875 The pressure in the reactor was reduced to 500 Torr and maintained for 30 minutes. The 2,2,3,3-tetrafluoropropanol was continuously distilled off into the receiving flask. After the temperature in the reactor was raised to 250 ° C to reduce the pressure in the reactor to 100 Torr, the condition was maintained for 30 minutes. Thereafter, when the temperature in the reactor is raised to 290 ° C and the pressure in the reactor is lowered to 1 Torr, the viscosity of the molten material starts to rise. After maintaining for 30 minutes, the polycarbonate represented by the following formula (13) was obtained by terminating polymerization by cooling at room temperature. [化 12]

〇 \ II \ θ-c inch (13)

The mass average molecular weight (Mw) obtained by GPC analysis of the polycarbonate obtained from In was 25, the 数量 'number average molecular weight (^!!) was UJOO, and the degree of dispersion (Mw/Mn) was 1.89. It was confirmed that the polycarbonate was not colored or high in purity. (Example 2) Synthesis of polycarbonate 2 (indium triflate): In addition to using 1.48 g (3.0 mmol) of vanadium triflate (111) instead of tetra-n-butoxytitanium In addition to the catalyst, with the embodiment! Polycarbonate was obtained in the same manner. The mass average molecular weight (Mw) obtained by GPC analysis of the obtained polycarbonate was 14,900, the number average molecular weight (Mn) was 7,487, and the degree of dispersion (Mw/Mn) was 1.99. It was confirmed that the polycarbonate was not colored or high in purity. The present invention has been described in detail with reference to the specific embodiments thereof, and various changes or modifications may be made without departing from the spirit and scope of the invention. The present application is based on Japanese Patent Application No. 2009-198478, filed on Jan. 28, 2009. Industrial Applicability The aromatic polycarbonate obtained from the manufacturing method of this month is useful as a work. The aliphatic/^ obtained by the production method of the present invention is used as a raw material for polyurethane, polyol, polyg, etc. 150432.doc •25·

Claims (1)

201127875 VII. Application for a patent garden 1. A method for producing a polycarbonate, which is selected from the group consisting of a compound represented by the following formula (1) and a formula (2) in the presence of a Lewis acid catalyst. a transesterification reaction of at least one of the fluorine-containing carbonates in the group consisting of the compound and the compound represented by the following formula (3) with a diol to obtain a polycarbonate; [Chemical Formula 1] R1 OCOc-〇i3 (1) wherein R1 is a group of CtY», and R is an argon atom or a group represented by CX2Y2r5, and R3 is a hydrogen atom or a group represented by CX3Y3r6, and two R1 may be used. The same or not, the two R2 may be the same or two, the two R3 may be the same or the X X knife may be independently a hydrogen atom, a fluorine atom or Rf, and Y1 to Y3 are each independently a fluorine atom or Rf, R~R respectively Independently a fluorine atom, Rf, 〇Rf or a chaotic alkyl group having a carbon number of 1 to 6 (wherein, a plurality of ether oxygens may be contained, and ten batches of yf pores may be present). It can also be phased [2J & + 1J ' J50432.doc 201127875 R1 R2—C 〇一q δ —o~c~ (2) Based on 2, R is the base shown by °^^4, R2 is a hydrogen atom or a CX2Y2R5, R3 is a hydrogen atom or a group represented by CX3Y3R6, and R: is a perfluoroalkyl group of several 丨~5 (its; x: 〜x: each independently is a gas atom or a gas atom) Or R: (4) Oxygen)' γ~γ are each independently a fluorine atom or Rf, and R4 to R6 are each independently a fluorine atom, OR or an alkane having a carbon number of 1 to 6 is a fluoroalkyl group having a carbon number of 1 to 4 (wherein , when multiple Rf cases A plurality of Rfs may contain ether oxygen in the presence or absence of each other; r7~cf2 η F2C-C-0-C-0-C-CF2 (3) Η O F2C-R7 ' R7 is a perfluoroalkylene group (in which oxygen) of the number 1 to 5, and two R7s may be the same or different. The ether may be contained. 2. The method for producing a polyacetate of claim 1 And a compound selected from the following formula (7), wherein Mi+(R8Xj-)m(Yk')n (7)' is at least one of the above-mentioned Lewis acids; wherein i=jxm+kxn, i, j are respectively An integer of 1 or more '150432.doc -2- 201127875 k is an integer of 2 or more, m and η are integers of 〇~4, respectively, Μ is a metal element or a semimetal element, and _ is a conjugate base of an organic acid group, R8 is a hydrogen atom, a hydrocarbon group having a carbon number of a functional group, or a polyfluoroalkyl group having a carbon number of 1 to 10 which may have a functional group, and Yk' is an inorganic anion other than a dentate ion. The method for producing a polycarbonate according to claim 2, wherein Xj- in the above formula (7) is coo., s〇3·, os〇3_, op〇32- or 〇.. 4_ Method for producing carbonated vinegar, wherein The Lewis acid catalyst is selected from at least one of the compounds represented by the following formula (8); Mp+s(R8X^)t(Yr-)u (8) wherein, pxs=qxt+r><u, P and q are each an integer of 1 or more, r is an integer of 2 or more, s is an integer of 2 or more, t and u are each an integer of 0 to 4, M is a metal element or a semimetal element, and xq is an organic acid group. A light base, R8 is a hydrogen atom, a hydrocarbon group having a carbon number of 1 to 10 which may have a functional group, or a polyfluoroalkyl group having a carbon number of 10 which may have a functional group, and Y is an inorganic anion other than a dentate ion. A method for producing a polysulfate vinegar according to the fourth aspect of the present invention, wherein xq_ in the above formula (8) is c〇〇-, so3-, 〇so3·, ΟΡ〇32· or 〇. The method for producing a polycarbonate according to any one of claims 1 to 5, wherein the Lewis acid catalyst is a metal alkoxide compound. 7. The method of producing a polycarbonate according to claim 6, wherein the metal alkoxide compound is an alkoxide compound of a metal selected from the group consisting of Ti, Zr, Si and Sn. 8. The process for producing a polycarbonate according to any one of claims 1 to 5, wherein the Lewis acid catalyst is a metal triflate compound. 9. The method for producing a polycarbonate according to claim 8, wherein the metal trifluoroantimonite compound is a metal trifluorosulfonate selected from the group consisting of Ce, Hf, La, Nd, Sc, Tm, Yb and Y. Salt compound. The method for producing a polycarbonate according to any one of claims 1 to 5, wherein the Lewis acid catalyst is a metal oxide. The method for producing a polysulfate vinegar of the Moonman 10, wherein the metal oxide is selected from the group consisting of oxides of metals such as Ab, Sn, and Pb. 1 2. If you ask for it! The method for producing a polycarbonate according to any one of the preceding claims, wherein the fluorocarbonate is a group consisting of a compound selected from the group consisting of the compound represented by the following formula (4) and a compound represented by the following formula (5) Obtaining at least a fluorinated alcohol in the reaction as a starting material; [Chemical 4] R2 (4) 150432.doc -4 - 201127875 wherein R1 is a group represented by CXW4, R2 is a hydrogen atom or a group represented by CX2y2r5, R3 is a hydrogen atom or a group represented by cx3y3r6, and R7 is a carbon number of 1 to 5. a perfluoroalkylene group (which may contain an etheric oxygen), X1 to X3 are each independently a hydrogen atom, a fluorine atom or Rf, and y1 to Y3 are each independently a fluorine atom or Rf, and R to R are each independently a fluorine atom, Rf 〇Rf or a carbon number i~6, R is a fluoroalkyl group having a carbon number of 1 to 4 (which may contain etheric oxygen), and in the case of a plurality of R/, a plurality of Rfs may be the same They can also be different from each other. 13. The process for producing a polycarbonate according to claim 12, wherein the fluorine-containing alcohol has a carbon number of from 2 to 10. 14_ The method for producing a polycarbonate according to claim 12 or 13, wherein R2 in the above formula (4) is a group represented by CX2Y2R5. Wherein the polycarbonate of any one of claims 12 to 14 is subjected to a pKa of less than 15 for the above-mentioned fluorine-containing alcohol. The method for producing a polycarbonate according to any one of claims 12 to 15, wherein the pKa of the above-mentioned fluorine-containing alcohol is less than 10. 17. The polycarbonate according to any one of claims 12 to 16, wherein the fluorine-containing alcohol is selected from the group consisting of 1,1,1,3,3,3-hexafluoride. Tripropanol, all ir-butyl butyl alcohol, and 2,2,3,3,4,4,5,5,6,6-decafluorocyclohexane, diterpene, sterol, 150432.doc 201127875 At least one. The method for producing a polycarbonate according to any one of claims 1 to 17, wherein the diol is an aliphatic diol or an aromatic diol. The method for producing a polycarbonate according to any one of items 1 to 18, wherein the diol is bisphenol A. The method for producing a polycarbonate according to any one of claims 1 to 18, wherein the diol is an aliphatic diol having 2 to 1 carbon atoms. The method for producing a polycarbonate according to any one of claims 1 to 1 and 2, wherein at least one of an alcohol and a .1,6-hexane is used. Wherein the above diol is selected from the group consisting of 3-methyl-1,5-pentanediol 'propylene glycol and iota, 4-butanediol 150432.doc 201127875 IV. Designated representative figure: (1) Representative of the case The picture shows: (none) (2) The symbol of the symbol of this representative figure is simple: 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—»c—o—C—0—c An AS b (1) R2- •C—O—C_0—ά—CF2—C—0—C_0_C· CF2 R3 O F2c-i7 H 0 Fac-i7 (2) (3) 150432.doc