Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
  • C08G64/20—General preparatory processes
  • C08G64/30—General preparatory processes using carbonates
  • C08G64/307—General preparatory processes using carbonates and phenols

Definitions

• the present invention relates to an industrial process for producing an aromatic polycarbonate. More specifically, the present invention industrially and stably produces a high-quality, high-performance aromatic polycarbonate that is free of coloring and has excellent mechanical properties from a cyclic carbonate and an aromatic dihydroxy compound in a large amount for a long period of time. Regarding the method.
• Aromatic polycarbonate is widely used in many fields as engineering plastics having excellent heat resistance, impact resistance and transparency.
• Various researches have been conducted on the production method of this aromatic polycarbonate, and among them, aromatic dihydroxy compounds such as 2,2-bis (4-hydroxyphenyl) propane (hereinafter referred to as bisphenol A) are included.
• bisphenol A 2,2-bis (4-hydroxyphenyl) propane
• Various polymerizers are known as a polymerizer for producing an aromatic polycarbonate by a melting method.
• a method using a vertical stirring tank type polymerizer equipped with a stirrer is generally well known.
• the vertical stirred tank type polymerizer has the advantage of high volumetric efficiency and small size on a small scale, and can proceed with polymerization efficiently, but on an industrial scale, as described above.
• As the polymerization proceeds it is difficult to efficiently extract phenol as a by-product out of the system, and the polymerization rate is extremely low.
• a large-scale vertical stirred tank type polymerization apparatus usually has a larger liquid volume ratio to the evaporation area than a small scale, and the so-called liquid depth is large.
• Aromatic dihydroxy compounds such as high-purity bisphenol A, are manufactured in large quantities industrially and are easy to obtain.To obtain high-purity diaryl carbonate in large quantities on an industrial scale, Impossible. It is therefore necessary to produce this.
• diaryl carbonate As a method for producing diaryl carbonate, an aromatic monohydroxy compound and phosgene are used. Reaction methods have been known for a long time, and various studies have been made recently. However, in this method, in addition to the problem of using phosgene, the diaryl carbonate produced by this method contains chlorine-based impurities that are difficult to separate, and cannot be used as a raw material for aromatic polycarbonate as it is. This is because this chlorine-based impurity significantly inhibits the polymerization reaction of the transesterification aromatic polycarbonate carried out in the presence of a very small amount of a basic catalyst. Can't progress.
• reaction systems are basically a batch system force and a switching system.
• the inventors of the present invention continuously supply dialkyl carbonate and aromatic hydroxy compound to a multistage distillation column, continuously react in the column in the presence of a catalyst, and contain a by-product alcohol.
• the boiling point component is continuously extracted by distillation, and the component containing the generated alkylaryl carbonate is extracted from the lower part of the column (see Patent Document 16).
• the alkylaryl carbonate is continuously supplied to the multistage distillation column.
• the reaction is continuously carried out in the column in the presence of a catalyst, and low-boiling components including dialkyl carbonate as a by-product are continuously extracted by distillation, and the generated components including diaryl carbonate are extracted from the bottom of the column.
• Reactive distillation (see Patent Document 17), these reactions are carried out using two continuous multistage distillation towers, and by-product dialkyl carbonate is effectively used.
• Reactive distillation method (see Patent Document 18), which continuously produces diaryl carbonate while being recycled, continuously supplies dialkyl carbonate and aromatic hydroxy compound to the multistage distillation column, and flows down in the column.
• the liquid to be discharged is extracted from a side outlet provided in the middle stage and / or the lowermost stage of the distillation tower, introduced into a reactor provided outside the distillation tower and reacted, and then from the stage having the outlet.
• These esters, such as reactive distillation (see Patent Document 19), in which the reaction is carried out in both the reactor and the distillation column by being introduced into the circulation inlet provided in the upper stage.
• the applicant of the present invention has disclosed a high boiling point substance containing a catalyst component as an active substance as a method for stably producing a high-purity aromatic carbonate for a long time without requiring a large amount of catalyst in a reactive distillation system.
• a catalyst component as an active substance
• the polyvalent aromatic hydroxy compound in the reaction system is kept at a mass ratio of 2.0 or less with respect to the catalyst metal.
• Patent Document 28 the present inventors use 70 to 99% by mass of phenol by-produced in the polymerization step as a raw material to produce diphenyl carbonate by a reactive distillation method and use this as a polymerization raw material for aromatic polycarbonate.
• Patent Document 29 See also proposed (see Patent Document 29).
• the production rate of the cart was only about 6.7 kg / hr, which was not strong on an industrial scale.
• the dialkyl carbonate used in the step (II) of the present invention needs to be produced on an industrial scale and further does not contain a halogen.
• the only method in which dialkyl carbonate is industrially produced in large quantities as a raw material for aromatic polycarbonate is the oxidative carbonylation method in which methanol is reacted with carbon monoxide and oxygen to produce dimethyl carbonate and water. Is due to.
• this oxidative carbonylation method (see Patent Document 30) requires a reaction in a slurry state using a large amount of CuCl-HCl as a catalyst, and the reaction system and separation / purification system are extremely corrosive. The problem is.
• carbon monoxide is easily oxidized to carbon dioxide by this method, the problem is that the selectivity based on carbon monoxide is as low as about 80%.
• the reaction cannot be completed completely and the reaction rate is low.
• the carbonate in order to increase the reaction rate of the cyclic carbonate, The carbonate must be distilled off using a very large amount of an aliphatic monohydric alcohol, requiring a long reaction time.
• the reaction can proceed at a higher reaction rate than in (1), (2), and (3).
• the method (4) that has been proposed so far is a method for producing a small amount of dialkyl carbonate and diol or a short-term production method, and is stable for a long time on an industrial scale. It was not about manufacturing.
• the object is to stably produce dialkyl carbonate in a large amount continuously (for example, 2 tons or more per hour) for a long period of time (for example, 1000 hours or more, preferably 3000 hours or more, more preferably 5000 hours or more). It was not something to achieve.
• Table 2 shows the maximum values for (cm), number of plates (n), dimethyl carbonate production P (kg / hr), and continuous production time T (hr).
• Patent Document 38 (paragraph 0060) states that "this embodiment is preferable as shown in FIG. 1 above".
• the process flow is the same as that of the embodiment, and the purpose is to operate a commercial scale apparatus for producing dimethyl carbonate and ethylene glycol by transesterification by a catalytic conversion reaction of ethylene carbonate and methanol.
• the numerical values described below in this embodiment are sufficiently applicable to the operation of an actual apparatus. As an example, it is described that 3 750 kg / hr of dimethyl carbonate was specifically produced. Since this scale described in the examples corresponds to an annual output of 30,000 tons or more, at the time of filing of Patent Document 38 (April 9, 2002), the world's largest large-scale commercial plant was operated by this method.
• Patent Document 1 Japanese Patent Publication No. 50-19600 (British Patent No. 1007302)
• Patent Document 2 Japanese Patent Publication No. 52-36159
• Patent Document 3 Japanese Patent Publication No. 53-5718 (US Pat. No. 3,888,826)
• Patent Document 4 Japanese Patent Laid-Open No. 2-153923
• Patent Document 5 JP-A-8-225641
• Patent Document 6 JP-A-8-225643
• Patent Document 7 JP-A-8-325373
• Patent Document 8 WO 97-22650
• Patent Document 9 Japanese Patent Laid-Open No. 10-81741
• Patent Document 10 JP-A-10-298279
• Patent Document l l WO 99/36457
• Patent Document 12 WO 99/64492
• Patent Document 13 JP-A-54-48732 (West German Patent Publication No. 736063, US Pat. No. 4,252,737)
• Patent Document 14 Japanese Patent Laid-Open No. 58-185536 (US Pat. No. 410464)
• Patent Document 15 Japanese Patent Laid-Open No. 56-123948 (US Pat. No. 4,182,726)
• Patent Document 16 Japanese Patent Laid-Open No. 3- No.291257
• Patent Document 17 Japanese Patent Laid-Open No. 4 9358
• Patent Document 18 Japanese Patent Application Laid-Open No. 4-211038 (WO 91/09832 Publication, European Patent 046 1274, US Patent 5210268)
• Patent Document 19 JP-A-4 235951
• Patent Document 20 Japanese Patent Laid-Open No. 6-157424 (European Patent 0582931 Specification, US Patent ⁇ 5334742 ⁇
• Patent Document 21 Japanese Patent Laid-Open No. 6-184058 (European Patent 0582930, US Patent 5344954)
• Patent Document 22 JP-A-9 40616
• Patent Document 23 JP-A-9 59225
• Patent Document 24 JP-A-9 176094
• Patent document 25 WO 00/18720 (US Pat. No. 6093842)
• Patent Document 26 JP 2001-64235 A
• Patent Document 27 WO 97/11049 (European Patent No. 0855384, US Patent No. 5 872275 Uzuki Itoda)
• Patent Document 28 Japanese Patent Laid-Open No. 11 92429 (European Patent No. 1016648, US Patent H6262210 ⁇ " spirit »)
• Patent Document 29 JP-A-9 255772 (European Patent 0892001 Specification, US Patent) ⁇ 5747609 ⁇
• Patent Document 30 WO 03/016257
• Patent Document 31 Japanese Patent Laid-Open No. 4 198141
• Patent Document 32 JP-A-9 194435
• Patent Document 33 WO99 / 64382 (European Patent No. 1086940, US Patent H6346638 ⁇ " course »)
• Patent Document 34 WO00 / 51954 (European Patent No. 1174406, US Patent H6479689 ⁇ " date »)
• Patent Document 35 Japanese Patent Laid-Open No. 5-213830 (European Patent No. 0530615, US Patent No. 5231212)
• Patent Document 36 Japanese Patent Laid-Open No. 6-9507 (European Patent No. 0569812, US Patent No. 5359118)
• Patent Document 37 Japanese Patent Laid-Open No. 2003-119168 (WO03 / 006418)
• Patent Document 38 Japanese Patent Laid-Open No. 2003-300936
• Patent Document 39 Japanese Patent Laid-Open No. 2003-342209
• the problem to be solved by the present invention is that a large amount of high-quality, high-performance aromatic polycarbonate having no mechanical coloring and excellent mechanical properties from a cyclic carbonate and an aromatic dihydroxy compound (for example, a large amount (for example, It is to provide a specific method capable of stable production over a long period (for example, 1000 hours or more, preferably 3000 hours or more, more preferably 5000 hours or more) over 1 ton per hour.
• An industrial production method for continuously producing high-quality aromatic polycarbonate from a cyclic carbonate and an aromatic dihydroxy compound (I) Cyclic carbonate and aliphatic monohydric alcohol are continuously fed into a continuous multistage distillation column T in which a catalyst exists, and reaction and distillation are simultaneously performed in the column to produce dialkyl power.
• Dialkyl carbonate and diols are obtained by a reactive distillation system in which a low-boiling reaction mixture containing bonates is continuously withdrawn in the form of gas from the top of the column and a high-boiling reaction mixture containing diols is continuously withdrawn in the form of liquid from the bottom of the column. Step (I) for continuously producing
• the dialkyl carbonate and the aromatic monohydroxy compound are used as raw materials, and this raw material is continuously fed into a first continuous multistage distillation column in which a catalyst exists, and the reaction and distillation are simultaneously performed in the first column.
• the first column low-boiling point reaction mixture containing the resulting alcohols is continuously withdrawn from the upper portion of the first column in the form of a gas, and the first column high-boiling point reaction mixture containing the generated alkylaryl carbonates is removed from the first column.
• the liquid is continuously withdrawn from the bottom of the first column, and the high-boiling point reaction mixture of the first column is continuously fed into the second continuous multi-stage distillation column in which the catalyst exists, and the reaction and distillation are simultaneously performed in the second column.
• the second tower low-boiling point reaction mixture containing dialkyl carbonates to be produced is continuously withdrawn in the form of a gas from the upper part of the second tower, and the second tower high-boiling point reaction mixture containing diaryl carbonates to be produced is removed from the second tower. Liquid and continuous from the bottom On the other hand, continuously supplying diaryl carbonate by continuously feeding the second column low boiling point reaction mixture containing dialkyl carbonates into the first continuous multi-stage distillation column, (II),
• the continuous multi-stage distillation column has a cylindrical body having a T force S, a length L (cm), and an inner diameter D (cm),
• the first continuous multi-stage distillation column has a cylindrical body having a length L (cm) and an inner diameter D (cm), and has an internal structure having an internal number n of stages.
• a gas outlet with an inner diameter d (cm), at the bottom of the tower or near the bottom of the tower.
• the second continuous multi-stage distillation column has a cylindrical body having a length L (cm) and an inner diameter D (cm).
• the tapered bottom casing constituting the bottom of the polymerization reaction zone is connected to the upper side casing at an angle C degree inside, and the angle C degree satisfies the formula (21).
• the continuous multistage distillation column ⁇ is a tray type distillation column having a tray as the internal
• the continuous multistage distillation column The perforated plate tray having a perforated plate portion and a downcomer portion
• the perforated plate tray of the continuous multi-stage distillation column is 100-1 per lm 2 of the perforated plate portion.
• D / ⁇ force S 2000 ⁇ L ⁇ 6000, 150 ⁇ D ⁇ 1000, 3 ⁇ L / ⁇ ⁇ 3 0, 30 ⁇ ⁇ 100, 8 ⁇ D / ⁇ ⁇ 25, 5 ⁇ D / ⁇ ⁇ 18 And
• L, D, L / D, n, D / d, D / d of the second continuous multistage distillation column are 2 respectively.
• D, L / ⁇ , n, D / d, D / d are 2500 ⁇ L ⁇ 5000, 200 ⁇ D, respectively
• the first continuous multistage distillation column is a tray-type distillation column having a tray as the internal
• the second continuous multistage distillation column is a distillation column having both a packing and a tray as the internal.
• Each of the trays of the first continuous multistage distillation column and the second continuous multistage distillation column is 17.
• the perforated plate tray has 100 to 1000 holes per area lm 2 of the multi-hole plate portion.
• the cross-sectional area per hole of the perforated plate tray of the first continuous multistage distillation column and the second continuous multistage distillation column is 0.5 to 5 cm 2 , Method,
• the ordered packing of the second continuous multi-stage distillation column is at least one selected from melapack, gempack, technopack, flexipack, sulza packing, good roll packing, and glitch grid force. 22. The method according to item 21 above,
• the side casing of the polymerization reaction zone is a cylindrical shape having an inner diameter D (cm) and a length L (cm), and is connected to the lower part thereof.
• the bottom casing has a tapered shape, and the lowermost discharge port of the tapered bottom casing has a cylindrical shape with an inner diameter d (cm), and D, L, and d are the formulas (27), (28) , (29) and (30) are satisfied,
• One of the guides is a cylindrical shape having an outer diameter r (cm) or a pipe shape in which a molten prepolymer is prevented from entering inside, and r satisfies the formula (32).
• step (IV) polymerization is carried out by connecting two or more guide contact flow type polymerization reactors.
• the two or more guide contact flow type polymerizers according to claim 27 are two polymerizers of a guide contact flow type first polymerizer and a guide contact flow type second polymerizer, the degree of polymerization in this order.
• the total external surface area SI (m 2 ) of the entire guide of the first polymerization vessel and the external total surface area S2 (m 2 ) of the entire guide of the second polymerization vessel satisfy the formula (33).
• a cyclic carbonate and an aromatic dihydroxy compound are combined. It has been found that high-quality, high-performance aromatic polycarbonates with no coloring and excellent mechanical properties can be produced on an industrial scale of 1 ton or more per hour at a high polymerization rate. It has also been found that high-quality aromatic polycarbonates can be stably produced over a long period of time with little variation in molecular weight, such as 2000 hours or more, preferably 3 000 hours or more, more preferably 5000 hours or more. Therefore, the present invention is an extremely effective method as an industrial production method for high-quality aromatic polycarbonate.
• step (I) for continuously producing dialkyl carbonate and diol on an industrial scale from cyclic carbonate and aliphatic monohydric alcohol is performed.
• the reaction in step (I) is a reversible transesterification reaction represented by the following formula.
• R 1 represents a divalent group — (CH 2) ⁇ (k is an integer of 2 to 6),
• the element may be substituted by an alkyl group having 1 to 10 carbon atoms or a carbaryl group.
• R 2 represents a monovalent aliphatic group having 1 to 12 carbon atoms, and one or more hydrogen atoms thereof may be substituted with an alkyl group having 1 to 10 carbon atoms or a aryl group.
• Examples of such cyclic carbonates include alkylene carbonates such as ethylene carbonate and propylene power carbonate, 1,3-dioxacyclohexan 2-one, 1,3-dioxacyclohepter 2- On and the like are preferably used, ethylene carbonate and propylene carbonate are more preferably used from the viewpoint of easy availability, and ethylene carbonate is particularly preferably used.
• aliphatic monohydric alcohols those having a boiling point lower than that of the generated diols are used. Therefore, although it may vary depending on the type of cyclic carbonate used, for example, methanol, ethanol, propanol (each isomer), aryl alcohol, butano (Each isomer), 3-butene 1 ol, amyl alcohol (each isomer), hexyl alcohol (each isomer), heptyl alcohol (each isomer), octyl alcohol (each isomer), nonyl Alcohol (each isomer), decyl alcohol (each isomer), undecyl alcohol (each isomer), dodecyl alcohol (each isomer), cyclopentanol, cyclohexanol, cycloheptanonore, cyclootanonore, methinore Cyclopentano monore (each isomer), e
• halogen lower alkoxy group, cyan group, alkoxycarbonyl group, It may be substituted with a substituent such as aryloxycarbonyl group, acyloxy group, nitro group.
• alcohols having 1 to 6 carbon atoms are preferably used, and more preferably methanol, ethanol, propanol (each heterogeneous substance), butanol ( Each isomer) is an alcohol having 1 to 4 carbon atoms.
• methanol and ethanol are preferable, and methanol is particularly preferable.
• any method may be used for allowing the catalyst to be present in the reactive distillation column.
• the catalyst can be present in the liquid phase in the reactive distillation column by continuously supplying the catalyst into the reactive distillation column, or it does not dissolve in the reaction solution under the reaction conditions.
• a catalyst can be present in the reaction system by disposing a solid catalyst in the reactive distillation column, or a method using these in combination.
• the homogeneous catalyst When the homogeneous catalyst is continuously supplied into the reactive distillation column, it may be supplied simultaneously with the cyclic carbonate and / or the aliphatic monohydric alcohol, or supplied at a position different from the raw material. May be. Since the reaction actually proceeds in the distillation column is a region under the catalyst supply position force, it is preferable to supply the catalyst to a region between the top of the column and the raw material supply position.
• the stage where the catalyst exists must be at least 5 stages, preferably 7 More than 10 stages, more preferably more than 10 stages.
• the number of stages in which the catalyst exists needs to be 5 or more, preferably 7 or more, and more preferably 10 or more.
• a solid catalyst that also has an effect as a packing for a distillation column can be used.
• Examples of the catalyst used in the step (I) include:
• Alkali metals and alkaline earth metals such as lithium, sodium, potassium, norevidium, cesium, magnesium, canoleum, strontium, barium;
• Basic compounds such as alkali metal and alkaline earth metal hydrides, hydroxides, alkoxides, aryl-oxides, amidates, etc .;
• Basic compounds such as alkali metal and alkaline earth metal carbonates, bicarbonates, organic acid salts;
• Tertiary amines such as trichinoleamine, tribubutenoleamine, trihexenoleamine, benzyljetylamine;
• Cyclic amidines such as diazabicycloundecene (DBU) and diazabicyclononene (DBN);
• Thallium compounds such as thallium oxide, thallium halide, thallium hydroxide, thallium carbonate, thallium nitrate, thallium sulfate, organic acid salts of thallium;
• tributyl methoxytin tributyl ethoxy tin
• dibutyl dimethoxy tin jetyl methoxy tin
• dibutyl methoxy tin dibutyl phenoxy tin
• diphenyl methoxy tin dibutyl tin acetate
• tributyl tin chloride tin 2-ethylhexanoate, etc.
• dumbbell compounds Dimethoxy nitro diethoxy nitro ethylene bismuth, dibutoxy dumbbell, etc. dumbbell compounds; Aluminum compounds such as aluminum trimethoxide, aluminum triisopropoxide, aluminum tributoxide;
• Phosphorus compounds such as trimethylphosphine, triethylphosphine, tributylphosphine, triphenylphosphine, tributylmethylphosphonium halide, trioctylbutylphosphonium halide, triphenylmethylphosphonium halide;
• Zirconium compounds such as zirconium halide, zirconium acetyl cetate, zirconium alkoxide, zirconium acetate;
• Lead and compounds containing lead for example, lead oxides such as PbO, PbO, PbO; PbS
• Lead salts such as PbO and CaPbO
• Mouth carbonates such as PbC ⁇ , 2PbCO -Pb (OH)
• lead minerals such as howenite and senyanite, and hydrates of these lead compounds.
• These compounds can be used as homogeneous catalysts when they are dissolved in reaction raw materials, reaction mixtures, reaction byproducts, etc., and can be used as solid catalysts when they are not dissolved. Furthermore, it is also preferable to use a mixture obtained by dissolving these compounds in advance with reaction raw materials, reaction mixtures, reaction by-products or the like, or using a mixture obtained by reaction as a homogeneous catalyst. Is the method.
• an anion exchange resin having a tertiary amino group an ion exchange resin having an amide group, an ion exchange resin having at least one exchange group of a sulfonic acid group, a carboxylic acid group, and a phosphoric acid group
• Ion exchangers such as solid strongly basic anion exchangers with quaternary ammonium groups as exchange groups; silica, silica-alumina, silica-magnesia, aluminosilicates, gallium silicates, various zeolites, various metal-exchanged zeolites, Solid inorganic compounds such as ammonium exchanged zeolites are used as catalysts.
• a solid strong basic anion exchanger having a quaternary ammonium group as an exchange group is particularly preferably used.
• a solid catalyst include a quaternary ammonium group as an exchange group.
• Strong basic anion exchange resin, cellulose strong basic anion exchanger having a quaternary ammonium group as an exchange group, inorganic carrier-supported strong basic anion exchange having a quaternary ammonium group as an exchange group, etc. are listed.
• the strongly basic anion exchange resin having a quaternary ammonium group as an exchange group for example, a styrenic strongly basic anion exchange resin is preferably used.
• a styrene-based strong base anion exchange resin is a strong base anion exchange resin having a quaternary ammonium (type I or type II) as an exchange group based on a copolymer of styrene and dibutenebenzene. For example, it is schematically shown by the following formula.
• X represents an anion, and usually X is F_, Cl_, Br_, ⁇ , HCO_, CO
• anion is used.
• gel type gel type
• macroreticular type (MR type) V the ability to use misalignment, high resistance to organic solvents, and MR type are particularly preferred from the viewpoint.
• Examples of the strong cellulose basic anion exchanger having a quaternary ammonium group as an exchange group include, for example, OCH CH NR obtained by trialkylaminoethylation of a part or all of —OH groups of cellulose. Examples thereof include cellulose having an exchange group of X.
• R represents an alkyl group, and methyl, ethyl, propyl, butyl, etc. are usually used, and methyl and ethyl are preferably used.
• X represents an anion as described above.
• An inorganic carrier-supported strong basic cation exchange having a quaternary ammonium group as an exchange group is a quaternary ammonium group by modifying part or all of the surface hydroxyl group OH of the inorganic carrier.
• ⁇ (CH) This means that NR X is introduced. However, R and X are
• silica, alumina, silica alumina, titania, zeolite, and the like can be used, preferably silica, alumina, silica alumina, and particularly preferably silica.
• any method for modifying the surface hydroxyl group of the inorganic carrier any method can be used.
• solid strongly basic ayuone exchangers having a quaternary ammonium group as an exchange group can also be used. In that case, it can be used as a transesterification catalyst after ion exchange with a desired anion species in advance as a pretreatment.
• the solid catalyst is preferably used as a transesterification catalyst. Furthermore, solid catalysts in which some or all of these nitrogen-containing heterocyclic groups are quaternized are also used. In addition, solid catalysts such as ion exchangers function as packing materials. Achieving power S
• the amount of the catalyst used in step (I) varies depending on the type of catalyst used, but when a homogeneous catalyst that is dissolved in the reaction solution under the reaction conditions is continuously supplied, a percentage of the total mass of the cyclic carbonate and an aliphatic monohydric alcohol as a raw material to Table Wa, usually 0.000;! ⁇ 50 weight 0/0, preferably from 0.005 to 20 mass 0/0, more preferably 0 01 ⁇ ; Used at 10% by mass.
• a solid catalyst is used in the distillation column, it is 0.0;! To 75% by volume, preferably 0.05 to 60% by volume with respect to the empty volume of the distillation column. More preferably, 0.;! ⁇ 60% by volume of catalyst is preferably used.
• step (I) the continuous multistage distillation column T, which is a reactive distillation column, is added to the cyclic carbon as a raw material.
• the nate and the aliphatic monohydric alcohol there is no particular limitation that they are catalysts in the region of at least 5 or more, preferably 7 or more, more preferably 10 or more of the distillation column. Any supply method can be used as long as it can be brought into contact with the substrate.
• the cyclic carbonate and the aliphatic monohydric alcohol can be continuously supplied from the necessary number of inlets to the stage satisfying the above conditions of the continuous multistage distillation column. Further, the cyclic carbonate and the aliphatic monohydric alcohol may be introduced into the same stage of the distillation column, or may be introduced into different stages.
• the cyclic carbonate and aliphatic monohydric alcohol as raw materials are continuously supplied to the continuous multistage distillation column T as a liquid, a gas, or a mixture of a liquid and a gas. In this way
• a gaseous raw material from the lower portion of the distillation column intermittently or continuously.
• cyclic carbonate is continuously supplied to the distillation column in a liquid or gas-liquid mixed state to the upper stage from the stage where the catalyst exists, and the aliphatic monohydric alcohol is gaseous and / or lower to the lower part of the distillation tower.
• a continuous supply method in a liquid state is also a preferable method. In this case, it goes without saying that an aliphatic monohydric alcohol is contained in the cyclic carbonate.
• the feedstock may contain dialkyl carbonate and / or diol as the product.
• the content of the dialkyl carbonate is usually 0 to 40% by mass, preferably 0 to 30% by mass, and more preferably represented by the mass% of dialkyl carbonate in the aliphatic monohydric alcohol / dialkyl carbonate mixture.
• it is 0 to 20% by mass
• the diol is represented by mass% in the cyclic carbonate / diol mixture, and is usually 0 to; 10% by mass, preferably 0 to 7% by mass, and more preferably 0 to 5%. % By mass.
• step (I) When the reaction of step (I) is carried out industrially, in addition to the cyclic carbonate and / or aliphatic monohydric alcohol newly introduced into the reaction system, it is recovered in this step or / and other processes. It is preferable that the material mainly composed of cyclic carbonate and / or aliphatic monohydric alcohol can be used as these raw materials.
• the present invention makes this possible and is an excellent feature of the present invention.
• the other process includes, for example, a process (II) for producing diaryl carbonate from a dialkyl carbonate and an aromatic monohydroxy compound. In this process (II), an aliphatic monohydric alcohol is by-produced. Is collected.
• This recovered by-product aliphatic monohydric alcohol usually contains dialkyl carbonates, aromatic monohydroxy compounds, alkylaryl ethers, etc., and even small amounts of alkylaryl carbonates, diaryl carbonates, etc. May occur.
• the by-product aliphatic monohydric alcohol can be used as it is as the raw material for step (I), or after the content of substances having a boiling point higher than that of the aliphatic monohydric alcohol is reduced by distillation or the like (I ).
• preferable cyclic carbonates used in the step (I) are those produced by reaction of alkylene oxide such as ethylene oxide, propylene oxide and styrene oxide with carbon dioxide, One round carbon dioxide containing a small amount of the above compound can be used as a raw material for the step (I).
• step (I) the amount ratio between the cyclic carbonate and the aliphatic monohydric alcohol supplied to the reactive distillation column varies depending on the type and amount of the transesterification catalyst and the reaction conditions, but is usually supplied.
• the aliphatic monohydric alcohols can be supplied in a molar ratio of 0.01 to 1000 times with respect to the cyclic carbonate.
• the molar ratio of the aliphatic monohydric alcohol to the cyclic carbonate is preferably 2 to 20, more preferably 3 to 15, and even more preferably 5 to 12; Unreacted annular carbon If a large amount of acid remains, it reacts with the product diols to produce by-products such as dimers and trimers. Is preferably reduced as much as possible.
• the reaction rate of the cyclic carbonate can be 97% or more, preferably 98% or more, and more preferably 99% or more. This is also one of the features of the present invention.
• step (I) preferably a force that continuously produces about 0.4 tons or more of dialkyl carbonate per hour.
• the amount is usually 0.44 tons / hr, preferably 0.42 tons / hr, more preferably 0.4 tons / hr, relative to the amount of aromatic polycarbonate to be produced (P tons / hr). is there . In a more preferred case, it can be less than 0 ⁇ 39 P ton / hr.
• the continuous multistage distillation column T used in step (I) is a length (cm) and an inner diameter D (cm).
• a gas outlet with an inner diameter d (cm), the bottom of the tower or
• L, D, L / D, n, D / d, D / d forces satisfy the formulas (;!) To (6) respectively.
• top of the tower or near the top of the tower used in the present invention means a portion of about 0.25 L downward from the top of the tower, and the term “bottom of the tower or near the bottom of the tower”
• distillation column it is 0 ⁇ 25L and 0 ⁇ 25L respectively.
• a continuous multi-stage distillation column T that simultaneously satisfies the formulas (1), (2), (3), (4), (5) and (6) is used.
• the dialkyl strength-bonate is preferably 0.4 ton or more and / or the diol is preferably 0.26 ton or more per hour. Since it was found that it can be stably produced for a long period of time, such as 1000 hours or more, preferably 3000 hours or more, and more preferably 5000 hours or more, on an industrial scale, with a high reaction rate and high selectivity. is there. The reason why it is possible to produce dialkyl carbonates and diols on an industrial scale having such excellent effects by carrying out the step (I) is not clear! ) To (6) are presumed to be due to the combined effect. The preferred range of each factor is shown below.
• L must be 8000 or less in order to reduce equipment costs while ensuring a reaction rate that can achieve the target production volume.
• the more preferable range of L (cm) is 2300 ⁇ L ⁇
• the preferred range of D (cm) is 200 ⁇ D ⁇ 1000, more preferably 210 ⁇ D
• n is less than 10, the reaction rate decreases and the target production volume cannot be achieved.
• n is not less than 120.
• n is 30 ⁇ n ⁇ 100, more preferably 40 ⁇ n ⁇ 90.
• the more preferred range of D / d is 4 ⁇ D / d ⁇ 15, and more preferably 5 ⁇ D / d
• the range of 0 02 is 7 ⁇ D / d ⁇ 25, more preferably 9 ⁇ D / d ⁇ 20.
• the d and d of the continuous multistage distillation column T used in the step (I) satisfy the formula (24).
• the long-term stable operation in the process (I) is based on operating conditions where there is no flooding, piping clogging or erosion for 1000 hours or more, preferably 3000 hours or more, more preferably 5000 hours or more! This means that a certain amount of dialkyl carbonate and diol can be produced while maintaining a high reaction rate, high selectivity, and high productivity.
• the selectivity of the dialkyl carbonate and the diol is relative to the reacted cyclic carbonate, and in the present invention, the selectivity is usually 95% or more, preferably 97%. As described above, a high selectivity of 99% or more can be achieved.
• the reaction rate in the step (I) usually represents the reaction rate of the cyclic carbonate. In the present invention, the reaction rate of the cyclic carbonate is 95% or more, preferably 97% or more, more preferably 99% or more, and further It is preferably 99.5 or more, and even more preferably 99.9% or more.
• One of the excellent features of step (I) is that a high reaction rate can be achieved while maintaining a high selectivity.
• the continuous multi-stage distillation column T used in step (I) is used as an internal tray and / or Is preferably a distillation column with packing.
• the term “internal” as used in the present invention means a portion where the gas-liquid contact is actually performed in the distillation column.
• a tray for example, a foam tray, a perforated plate tray, a valve tray, a counter-flow tray, a super flack tray, a max flack tray, etc. are preferred fillings such as Raschig rings, less rings, pole rings, Berle saddles.
• Irregular packing such as Interlocks saddle, Dixon packing, McMahon packing, Helipac, etc.
• n internal plate number in the present invention means the number of trays in the case of trays, and the theoretical plate number in the case of packing.
• the number of stages n is the sum of the number of trays and the number of theoretical stages.
• the continuous continuous multi-stage distillation column and / or the packing comprising a tray and / or a packing having a predetermined number of internal plates High reaction rate using any of the tower-type continuous multistage distillation columns
• the internal distillation column-type distillation column was found to be more preferable. Furthermore, it has been found that a perforated plate tray having a perforated plate portion and a downcomer portion is particularly excellent in terms of function and equipment cost. It was also found that the perforated plate tray preferably has 100 to 1000 holes per area lm 2 of the perforated plate portion. More preferably, the number of holes is 120 to 900 per lm 2 , and more preferably 150 to 800. It has also been found that the cross-sectional area per hole of the perforated plate tray is preferably 0.5 to 5 cm 2 .
• the cross-sectional area per hole is more preferably 0.7 to 4 cm 2 , and further preferably 0.9 to 3 cm 2 .
• the perforated plate tray has 100 to 1000 holes per lm 2 area of the perforated plate portion, and has a cross-sectional area of 0.5 to 5 cm 2 per hole. In particular, it has been found to be particularly preferred.
• the aperture ratio of the perforated plate tray is preferably 1.5 to 15%. It was. More preferably, the aperture ratio is 1.7 to 13%, and more preferably 1.9 to 11%.
• the aperture ratio of the perforated plate tray represents the ratio of the cross-sectional area of all the holes existing in the perforated plate to the area of the perforated plate portion (total hole cross-sectional area).
• the force S may be different in the area of the perforated plate portion and / or the total hole cross-sectional area, and in this case also, the aperture ratio of each multi-holed plate tray is preferably in the above range.
• the number of holes in the perforated plate portion may be the same in all perforated plates, or may be different.
• the cyclic carbonate as a raw material and the aliphatic monohydric alcohol are continuously fed into a continuous multistage distillation column in which a catalyst exists, and the reaction and distillation are carried out in the column.
• the low-boiling reaction mixture containing dialkyl carbonate to be produced is continuously withdrawn in the form of gas from the top of the tower, and the high boiling point reaction mixture containing diols is continuously withdrawn in the form of liquid from the bottom of the tower. Diols are produced continuously.
• step (I) in order to continuously supply the raw material cyclic carbonate and aliphatic monohydric alcohol into the continuous multistage distillation column T, the gas outlet at the top of the distillation column is more than
• It may be supplied in liquid and / or gaseous form as a raw material mixture or separately from one or several inlets installed in the lower part but at the upper part or the middle part of the tower.
• the raw material containing a large amount thereof is supplied in the form of an introduction loca in the upper part or middle part of the distillation column, and the aliphatic monohydric alcohol or the raw material containing a large amount of the raw material is provided above the liquid outlet at the lower part of the distillation column. It is also preferable to supply it in the form of gas from the inlet installed in the middle or lower part.
• the reaction time of the transesterification performed in the step (I) is the reaction time in the continuous multistage distillation column T.
• the reaction temperature in the step (I) varies depending on the type of raw material compound used and the type and amount of the catalyst, and is usually 30 to 300 ° C. Increasing the reaction temperature to increase the reaction rate However, when the reaction temperature is high, side reactions are liable to occur.
• Preferred reaction temperatures range from 40 to 250 ° C, more preferably from 50 to 200 ° C, even more preferably from 60 to;
• the reaction distillation can be carried out at a column bottom temperature of 150 ° C. or lower, preferably 130 ° C. or lower, more preferably 110 ° C. or lower, and even more preferably 100 ° C. or lower. .
• the reaction pressure may vary depending on the type and composition of the raw material compound used, the reaction temperature, etc., and may be any of reduced pressure, normal pressure, and increased pressure, usually 1 Pa to 2 X 10 7 Pa, preferably 10 3 Pa. To 10 7 Pa, more preferably 10 4 to 5 ⁇ 10 6 .
• the reflux ratio of the continuous multistage distillation column T in step (I) is usually from 0 to 10;
• the material constituting the continuous multistage distillation column T used in step (I) is mainly carbon steel, stainless steel.
• Stainless steel is preferred from the viewpoint of the quality of the metal material such as stainless steel and the quality of the dialkyl carbonate to be produced.
• step (II) for continuously producing diaryl carbonate on an industrial scale from the dialkyl carbonate produced in step (I) and the aromatic monohydroxy compound is performed.
• the dialkyl carbonate used in the step (II) is represented by the following formula described in the following formula.
• R 2 is as described above.
• dialkyl carbonates having R 2 examples include dimethyl carbonate, jetyl carbonate, dipropyl carbonate (each isomer), diaryl carbonate, dibutyr carbonate (each isomer), dibutyl carbonate (each Isomer), dipentyl carbonate (each isomer), dihexyl carbonate (each isomer), diheptyl carbonate (each isomer), dioctyl carbonate (each isomer), dinonyl carbonate (each Isomers), didecyl carbonate (each isomer), dicyclopentyl carbonate, dicyclohexenole carbonate, dicycloheptinole carbonate, dibenzino carbonate, diphenetino carbonate (each different organism), di (Fuenore propinore) carbonate (each Isomers), di (phenylbutyl) carbonate (each isomer) di (black benzyl) carbonate (each iso
• R 2 is preferably a dialkyl carbonate composed of an alkyl group containing 4 or less carbon atoms that does not contain halogen, and dimethyl carbonate is particularly preferred.
• dialkyl carbonates more preferred are dialkyl carbonates prepared in a substantially halogen-free state, for example, alkylene carbonate and halogen substantially free of halogen. Alcohol power not included in the product.
• the aromatic monohydroxy compound used in the step (II) is represented by the following general formula, and any compound may be used as long as the hydroxyl group is directly bonded to the aromatic group. It may be.
• Ar 3 represents an aromatic group having 5 to 30 carbon atoms.
• aromatic monohydroxy compounds having Ar 3 include phenol, talesol (each isomer), xylenol (each isomer), trimethylphenol (each isomer), tetramethylphenol (each isomer), Ethylphenol (each isomer), propylphenol (each isomer), butylphenol (each isomer), jetylphenol (each isomer), methylethylphenol (each isomer), methylpropylphenol (each) Isomers), dipropylphenol (each isomer), methylbutinophenol (each isomer), pentylphenol (each isomer), hexylphenol (each isomer), cyclohexylphenol (each isomer), etc.
• Alkylphenols methoxyphenol (each isomer), ethoxyphenol (each isomer), etc.
• Various alkoxyphenols arylpropylphenols such as phenylpropylphenol (each isomer); naphthol (each isomer) and various substituted naphthols; hydroxypyridine (each isomer), hydroxycoumarin (each isomer) ), And heteroaromatic monohydroxy compounds such as hydroxyquinoline (each isomer).
• aromatic monohydroxy compounds are used as a mixture of one or more. That power S.
• aromatic monohydroxy compounds those preferably used in the present invention are aromatic monohydroxy compounds in which Ar 3 is an aromatic group having 6 to 10 carbon atoms, particularly preferably phenol. is there.
• Ar 3 is an aromatic group having 6 to 10 carbon atoms, particularly preferably phenol. is there.
• those that are preferably used in the present invention are those that do not substantially contain halogen.
• diaryl carbonate as used in the present invention is generally represented by the following formula.
• Ar 3 and Ar 4 each represent a monovalent aromatic group.
• Ar 3 and Ar 4 each represent a monovalent carbocyclic or heterocyclic aromatic group.
• one or more hydrogen atoms are other groups that do not adversely affect the reaction.
• Substituents such as halogen atoms, alkyl groups having 1 to 10 carbon atoms, alkoxy groups having 1 to 10 carbon atoms, phenyl groups, phenoxy groups, bur groups, cyan groups, ester groups, amide groups, nitro groups, etc. It may be what was done.
• Ar 3 and Ar 4 may be the same or different.
• Representative examples of the monovalent aromatic groups Ar 3 and Ar 4 include a phenyl group, a naphthyl group, a biphenyl group, and a pyridyl group. These may be substituted with one or more substituents as described above.
• Ar 3 and Ar 4 include those represented by the following formulas, respectively.
• a particularly preferred diaryl carbonate is a substituted or unsubstituted diphenyl carbonate represented by the following formula.
• R 9 and R 1 () are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an alkoxy group having 10 to 10 carbon atoms, or a ring having 5 to 5 carbon atoms.
• 10 represents a cycloalkyl group or a phenyl group
• p and q are integers of 1 to 5, and when p is 2 or more, each R 9 may be different, or q is 2 In the above case, each R 1 () may be different.
• diaryl carbonates symmetrical diaryl carbonates such as unsubstituted diphenyl carbonate and lower alkyl-substituted diphenyl carbonates such as ditolyl carbonate and di-butyl phenyl carbonate are preferable. Particularly preferred is diphenyl carbonate having the simplest structure.
• diallyl carbonates may be used alone or in combination of two or more! /, With respect to an aromatic monohydroxy compound of dialkyl carbonate used as a raw material in step (II).
• the amount ratio is preferably a molar ratio of 0.
• the molar ratio is preferably 0.5 to 5 forces, more preferably 0.8 to 3, and still more preferably!
• Step (II) a force that continuously produces 1 ton or more of aromatic polycarbonate per hour.
• a high-purity diaryl force of about 0.85 ton or more per hour is continuously applied. It needs to be manufactured. Therefore, in Step (II), the minimum amount of aromatic monohydroxy compound continuously supplied is usually 15 P ton / hr with respect to the amount of aromatic polycarbonate to be produced (P ton / hr). And preferably 13 P ton / hr, more preferably 10 P ton / hr. If more preferable, it can be less than 8P ton / hr
• the dialkyl carbonate and aromatic monohydroxy compound used as raw materials in the step (II) each have high purity! /, Even if it is! /, And le, which contains other compounds.
• it may contain a compound or reaction byproduct produced in the first continuous multistage distillation column or / and the second continuous multistage distillation column.
• these raw materials were recovered from the first continuous multistage distillation column and / or the second continuous multistage distillation column in addition to the dialkyl carbonate and aromatic monohydroxy compound newly introduced into the reaction system. It is preferable to use also.
• the top component which is a low boiling point reaction mixture in the second continuous multistage distillation column
• the second column low boiling point reaction mixture may be supplied as it is to the first continuous multistage distillation column! /, Or after a part of the components are separated! / ,.
• the raw materials supplied to the first continuous multistage distillation column include alcohols, alkylaryl carbonate, dialyl carbonate, alkylaryl ether, and the like.
• the product is preferably used even if it contains a small amount of high-boiling by-products such as a fleece transfer product of alkylaryl carbonate or diallyl carbonate and its derivatives.
• dimethyl carbonate as a dialkyl carbonate and phenol as an aromatic monohydroxy compound are used as raw materials.
• diphenyl carbonate it is preferable that the raw material contains methyl alcohol as a reaction product, methyl phenyl carbonate and diphenyl carbonate.
• anisole is salicylic acid as a reaction byproduct. It may contain a small amount of phenyl, methyl salicylate and high-boiling by-products derived from these.
• step (II) most of the aromatic monohydroxy compound used in step (II) is composed of the aromatic monohydroxy compound by-produced in step (IV) of the present invention. This by-product aromatic monohydroxy compound needs to be recycled to step (II) by step (V).
• the diaryl carbonate produced in the step (II) is produced by the transesterification reaction between the dialkyl carbonate and the aromatic monohydroxy compound.
• This transesterification reaction involves one or two alkoxy compounds of the dialkyl carbonate. A group is exchanged with the aryloxy group of an aromatic monohydroxy compound to remove alcohols, and a disproportionation reaction that is a transesterification reaction between two molecules of the generated alkylaryl carbonate.
• the reaction to be converted is included.
• mainly alkylaryl carbonate is obtained
• this alkylaryl power is mainly obtained by the disproportionation reaction of the carbonate.
• dialkyl carbonate dialkyl carbonate.
• the diaryl carbonate obtained in the step (II) does not contain any halogen, it is important as a raw material for industrially producing the aromatic polycarbonate of the present invention. This is because if the amount of halogen present in the polymerization raw material is less than, for example, 1 ppm, the polymerization reaction is inhibited, the stable production of aromatic polycarbonate is inhibited, and the strength is also generated. This is because the physical properties of the aromatic polycarbonate are deteriorated and coloring is caused.
• the catalyst used in the first continuous multistage distillation column and / or the second continuous multistage distillation column in step (II) is selected from the following compounds, for example.
• Lead salts such as Ca PbO and CaPbO; Lead carbonates such as PbCO and 2PbCO 2 -Pb (OH) And its basic salts; Pb (OCOCH), Pb (OCOCH), Pb (OCOCH) -PbO-3H
• Ph represents a phenyl group.
• Alkoxyleads such as Pb—Na, Pb—Ca, Pb—Ba, Pb—Sn, Pb—Sb, etc .
• Lead minerals such as howenite, senyanite, and these Hydrates of lead compounds
• ⁇ Copper group metal compounds > CuCl, CuCl, CuBr, CuBr, Cul, Cul, Cu (OAc), Cu (acac), copper oleate, Bu Cu, (CH 2 O) Cu, AgNO, AgBr, silver picrate, A
• Alkali metal complexes such as Li (acac) and LiN (C H);
• Zinc complex such as Zn (acac);
• ⁇ Zirconium complex Zr complexes such as Zr (acac) and zirconocene;
• ⁇ Lewis acid compounds > A1X, TiX, TiX, VOX, VX, ZnX, FeX, SnX (here
• X is halogen, acetoxy group, an alkoxy group or an aryloxy group.
• Organotin compounds such as SnO (OH);
• a metal-containing compound such as is used as a catalyst such as is used as a catalyst.
• These catalysts may be solid catalysts fixed in a multistage distillation column! /, Or may be soluble catalysts that dissolve in the reaction system! /.
• organic compounds in which these catalyst components are present in the reaction system for example, aliphatic alcohols, aromatic monohydroxy compounds, alkylaryl carbonates, diaryl carbonates, dialkyl carbonates, etc. It may have been reacted, or may have been heat-treated with raw materials or products prior to the reaction.
• step (II) When the step (II) is carried out with a soluble catalyst that dissolves in the reaction system, these catalysts must be under the reaction conditions! / And have high solubility in the reaction solution! /. I like it! Preferred catalysts in this sense include, for example, PbO, Pb (OH), Pb (OPh); TiCl, Ti (OMe), (M
• the catalyst used in the first continuous multistage distillation column and the catalyst used in the second continuous multistage distillation column may be the same or different.
• the first continuous multi-stage distillation column used in step (II) is a cylindrical body having a length L (cm) and an inner diameter D cm), and an internal having n stages inside.
• the second continuous multistage distillation column used in step (II) is a length (cm), an inner diameter D
• dialkyl carbonate and aromatic monohydroxy compound can be used.
• the reason why it is possible to produce an aromatic carbonate on an industrial scale having such excellent effects by carrying out the method of the present invention is not clear, but the formulas (7) to (; It is presumed that this is due to the combined effect brought about when the conditions in 18) are combined.
• the preferred range of each factor constituting the continuous multistage distillation column used in step (II) is shown below.
• L and L In order to reduce the equipment cost while securing the reaction rate that can achieve the target production volume, L and L must be 8000 or less respectively.
• More preferred L (cm) and L (cm) ranges are 2000 ⁇ L ⁇ 6000 and
• D (cm) and D (cm) are 150 ⁇ D ⁇ 1000 and
• the inner diameter may be the same from the upper part to the lower part of the tower, or the inner diameters may be partially different.
• the inner diameter of the upper part of the column may be smaller or larger than the inner diameter of the lower part of the tower.
• the pressure difference between the top and bottom of the column becomes too large, and long-term stable operation becomes difficult. This leads to a decrease in selectivity.
• the more preferred L / ⁇ and L / ⁇ ranges are 3 ⁇ L / D ⁇ 30 and 3 ⁇ L / D ⁇ 30, respectively.
• 5 ⁇ L / ⁇ 15 and 5 ⁇ L / ⁇ 15 Preferably, 5 ⁇ L / ⁇ 15 and 5 ⁇ L / ⁇ 15.
• n force is less than 3 ⁇ 40, the reaction rate decreases, so the target production amount in the first continuous multistage distillation column cannot be achieved, and the equipment cost is reduced while ensuring the reaction rate that can achieve the target production amount.
• n In order to lower it, n must be 120 or less.
• the n force is greater than 20, the pressure difference between the top and bottom of the column becomes too large, and the long-term stable operation of the first continuous multistage distillation column becomes difficult, and the temperature at the bottom of the column must be increased. Side reactions are likely to occur, leading to a decrease in selectivity.
• a more preferable range of n is 30 ⁇ n ⁇ 100, and more preferably 40 ⁇ n ⁇ 90.
• n In order to reduce equipment costs while securing a reaction rate that can achieve the desired production volume, n must be 80 or less. If n is greater than 80
• n 15 ⁇ n ⁇ 6
• a more preferable range of D / ⁇ is 5 ⁇ D / ⁇ 18, and
• the range of 2 is 7 ⁇ D / d ⁇ 25, more preferably 9 ⁇ D / d ⁇ 20
• step (II) the d and the d satisfy the formula (25), and the d and the d satisfy the formula (26).
• the long-term stable operation in the step (II) means 1000 hours or more, preferably 3000 hours or more, more preferably 5000 hours or more, such as flooding, piping clogging or erosion. This means that the operation can be continued in a steady state based on the driving conditions, and a predetermined amount of diaryl carbonate is produced while maintaining a high selectivity.
• the step (II) is characterized by stably producing a gear reel carbonate at a high selectivity for a long period of time with a high productivity of preferably 1 ton or more per hour. Is to produce a gear reel of 2 tons or more per hour, more preferably 3 tons or more per hour.
• L, D, L / D, n, D / d, D / d force S of the first continuous multistage distillation column are 2000 ⁇ L ⁇ 6000, 150 ⁇ D ⁇ 1000,
• It is characterized by producing a dial reel carbonate of 2.5 tons or more, more preferably 3 tons or more per hour.
• step (II) L, D, L / D, n, D / d, D / ⁇ S of the first continuous multistage distillation column, 2500 ⁇ L ⁇ 5000, 200 ⁇ D ⁇ 800, respectively. , 5 ⁇ L / D ⁇ 15,
• L, D, L / ⁇ , n, D / d, D / d of the tower are 2500 ⁇ L ⁇ 5000
• diallyl carbonate of 4 tons or more per hour.
• the selectivity of diaryl carbonate in step (II) refers to the reacted aromatic monohydroxy compound, and in step (II), the selectivity is usually 95% or higher, which is favorable. A high selectivity of preferably 97% or more, more preferably 98% or more can be achieved.
• the first continuous multistage distillation column and the second continuous multistage distillation column used in step (II) are distillation columns having trays and / or packings as internal.
• the term “rear internal” refers to a portion where the distillation column is actually brought into contact with gas and liquid. As such a tray, those described in the section of step (I) are preferable.
• the number of internal stages n is as described above.
• step (II) a reaction for mainly producing an alkylaryl carbonate from a dialkyl carbonate and an aromatic monohydroxy compound is carried out, but this reaction has an extremely small equilibrium constant. Since the reaction force is slow, it has been found that the first continuous multistage distillation column used for the reaction distillation is preferably an internal column type distillation column. Further, in the second continuous multi-stage distillation column, the reaction force S, in which the reaction for disproportionating the alkylaryl carbonate is mainly performed, and this reaction also has a small equilibrium constant, and the reaction rate is slow.
• the second continuous multistage distillation column used for reactive distillation, it has been found that an internal distillation column having both a packing and a tray is more preferable. It was also found that the second continuous multistage distillation column is preferably one with a packing at the top and a tray at the bottom. It has also been found that the packing of the second continuous multistage distillation column is particularly preferred among the ordered packings that are preferred for ordered packings.
• the tray installed in each of the first continuous multistage distillation column and the second continuous multistage distillation column has a perforated plate tray having a perforated plate portion and a downcomer portion. It was found to be excellent. It was also found that the perforated plate tray had 100 to 1000 holes per area lm 2 of the perforated plate part! /, A force S preferred! /. More preferred! / The number of pores is 120-900 per lm 2 of the area, more preferably 150-800
• the cross-sectional area per hole of the perforated plate tray is preferably 0.5 to 5 cm2.
• the cross-sectional area per hole is more preferably 0.7 to 4 cm 2 , and even more preferably 0.9 to 3 cm 2 .
• the perforated plate tray has 100 to 1000 holes per area lm 2 of the perforated plate portion, and the cross-sectional area per hole is 0.5 to 5 cm 2.
• the raw material dialkyl carbonate and the aromatic monohydroxy compound are continuously fed into the first continuous multistage distillation column in which the catalyst is present, and the reaction is carried out in the first column.
• 1st column low boiling point reaction mixture containing alcohols The product is continuously withdrawn in the form of gas from the upper part of the first column, and the first tower high-boiling point reaction mixture containing the generated alkylaryl carbonates is continuously withdrawn in liquid form from the lower part of the first column,
• the first column high boiling point reaction mixture is continuously fed into the second continuous multistage distillation column in which the catalyst is present, and the reaction and distillation are simultaneously performed in the second column.
• a low boiling point reaction mixture is continuously withdrawn in the form of gas from the upper part of the second tower, and a second tower high boiling point reaction mixture containing the generated diaryl carbonate is continuously withdrawn in liquid form from the lower part of the second tower,
• diaryl carbonate is continuously produced by continuously feeding the second column low boiling point reaction mixture containing dialkyl carbonates into the first continuous multistage distillation column.
• This raw material contains reaction by-products such as alcohols, alkylaryl carbonates, diaryl carbonates, alkylaryl ethers, and high-boiling compounds as reaction products! /, Even! /, Les, as described above. Considering the equipment and cost for separation and purification in other steps, in the case of the present invention which is actually carried out industrially, it is preferable to contain a small amount of these compounds.
• step (II) in order to continuously supply the raw material dialkyl carbonate and aromatic monohydroxy compound into the first continuous multi-stage distillation column, from the gas outlet at the top of the first distillation column
• it may be supplied in liquid and / or gaseous form from one or several inlets installed in the upper or middle part of the tower, or a raw material rich in aromatic monohydroxy compounds.
• step (II) the first high-boiling point reaction mixture containing alkylaryl carbonates continuously extracted from the lower part of the first continuous multistage distillation column is continuously supplied to the second continuous multistage distillation column.
• the supply position is lower than the gas outlet at the top of the second distillation column, it is liquid and / or from one or several inlets installed at the top or middle of the column. It is preferable to supply in gaseous form.
• at least one of the inlets is installed between the packed portion and the tray portion. Is preferred.
• the packing is composed of two or more regular packings, it is also a preferable method to install introduction ports at intervals that constitute these multiple packings.
• step (II) after condensing the gas components extracted from the top of the first continuous multistage distillation column and the second continuous multistage distillation column, respectively, a part of them is returned to the upper part of each distillation column.
• the reflux ratio of the first continuous multistage distillation column is from 0 to 10; the reflux ratio of the second continuous multistage distillation column is from 0.01 to 10; preferably from 0.08 to 5, Preferably, it is in the range of 0.1 to 2.
• a reflux operation is not performed, and a reflux ratio of 0 is also preferred! /.
• step (II) any method may be used in which the catalyst is present in the first continuous multistage distillation column.
• the catalyst when the catalyst is in a solid state insoluble in the reaction solution, It is preferable to fix in the tower by a method of installing in a stage in a single continuous multi-stage distillation column or a method of installing in a packed form.
• the catalyst solution dissolved in the raw material or the reaction solution may be introduced together with the raw material, or the catalyst solution may be introduced from an inlet different from the raw material.
• the amount of catalyst used in the first continuous multi-stage distillation column of the present invention varies depending on the type of catalyst used, the type of raw material and its ratio, reaction temperature, reaction pressure, and other reaction conditions. expressed as a percentage of the total mass, usually 0.000;! ⁇ 30 mass 0/0, preferably ⁇ is 0. 0005 ⁇ ; 10 mass 0/0, more preferably ⁇ is 0. 0 0;! ⁇ 1 mass Used in%.
• any method may be used for allowing the catalyst to be present in the second continuous multistage distillation column.
• the second continuous multi-stage distillation column is preferably fixed in the column by a method of being installed in a stage or a method of being installed in a packed form.
• the catalyst solution dissolved in the raw material or the reaction liquid may be introduced together with the raw material, or the catalyst liquid may be introduced from an inlet different from the raw material.
• the amount of catalyst used in the second continuous multi-stage distillation column of the present invention varies depending on the type of catalyst used, the type of raw material and its ratio, the reaction temperature and the reaction pressure, but the total amount of raw materials. Ratio to mass Expressed in normal 0.000;! ⁇ 30 mass 0/0, preferably ⁇ is 0. 0005 ⁇ ; 10 mass 0/0, more preferably ⁇ is 0. 00; as used to 1 mass%! .
• the catalyst used in the first continuous multistage distillation column and the catalyst used in the second continuous multistage distillation column may be the same type or different types. Preferably, it is preferable to use the same type of catalyst. Further preferred are catalysts of the same type that can be dissolved in both reaction solutions. In this case, the catalyst is usually dissolved in the high boiling point reaction mixture of the first continuous multi-stage distillation column, and is extracted from the lower part of the first distillation column together with the alkylaryl carbonate, etc., and is directly used in the second continuous multi-stage distillation column. This is a preferred embodiment. If necessary, a new catalyst can be added to the second continuous multi-stage distillation column.
• the reaction time of the transesterification reaction performed in step (II) is considered to correspond to the average residence time of the respective reaction liquids in the first continuous multistage distillation column and the second continuous multistage distillation column. This differs depending on the internal shape and number of stages of each distillation column, the amount of raw material supply, the type and amount of the catalyst, the reaction conditions, etc., but in each of the first continuous multistage distillation column and the second continuous multistage distillation column. Is usually from 0.01 to 10 hours, preferably from 0.05 to 5 hours, more preferably from 0.;! To 3 hours.
• the reaction temperature of the first continuous multistage distillation column varies depending on the type of raw material compound and the type and amount of the catalyst used, but is usually in the range of 100 to 350 ° C. In order to increase the reaction rate, it is preferable to increase the reaction temperature. However, if the reaction temperature is high, side reactions are liable to occur. For example, by-products such as alkylaryl ethers are increased. In this sense, the preferable reaction temperature in the first continuous multistage distillation column is in the range of 130 to 280 ° C, more preferably 150 to 260 ° C, and still more preferably 180 to 250 ° C.
• the reaction temperature of the second continuous multistage distillation column varies depending on the type of raw material compound and the type and amount of the catalyst used, but is usually in the range of 100 to 350 ° C. In order to increase the reaction rate, it is preferable to increase the reaction temperature. However, if the reaction temperature is high, side reactions are likely to occur. For example, alkyl aryl ethers and alkyl aryl carbonates that are raw materials and products are used. This is not preferable because by-products such as the product of fries rearrangement of diols and carbonates and their derivatives increase. In this sense, the preferred reaction in the second continuous multistage distillation column. Response temperature is 130-280. C, more preferably 150-260. C, more preferably in the range of 180-250 ° C.
• the reaction pressure of the first continuous multistage distillation column varies depending on the type and composition of the raw material compound used, the reaction temperature, and the like.
• the reaction pressure is any of reduced pressure, normal pressure, and increased pressure.
• the column top pressure is 0.;! ⁇ 2 X 10 7 Pa, preferably 10 5 ⁇ ; 10 7 Pa, more preferably 2 X 10 5 to 5 X 10 6 .
• the reaction pressure of the second continuous multi-stage distillation column is different from the force S, the reduced pressure, the normal pressure, and the increased pressure depending on the type and composition of the raw material compound used, the reaction temperature, etc. It is carried out in the range of 0.1 to 2 ⁇ 10 7 Pa, preferably 10 3 to; 10 6 Pa, more preferably 5 ⁇ 10 3 to 10 5 .
• Two or more distillation towers may be used as the first continuous multi-stage distillation tower in the step (II). In this case, two or more distillation columns can be connected in series, connected in parallel, or combined in series and parallel. In addition, two or more distillation towers can be used as the second continuous multistage distillation tower in the step (II). In this case, it is possible to connect two or more distillation columns in series, connect them in parallel, or connect a combination of series and parallel.
• the materials constituting the first continuous multistage distillation column and the second continuous multistage distillation column used in step (II) are mainly metallic materials such as carbon steel, stainless steel, etc. Quality of aromatic carbonate produced From the above aspect, stainless steel is preferred.
• the high boiling point reaction mixture in the second column extracted continuously in liquid form from the bottom of the second continuous multistage distillation column in step (II) is a force mainly composed of diaryl carbonate. It contains alkyl reel carbonate, a small amount of unreacted raw material, a small amount of high-boiling by-products, etc., and when a homogeneous catalyst is used, this catalyst component is also included. Therefore, it is necessary to carry out a purification step (III) for obtaining high-purity diaryl carbonate from the second tower high boiling point reaction mixture.
• Step (III) may be any method as long as it can obtain high-purity diaryl carbonate from the second tower high boiling point reaction mixture.
• step (III) is performed using two distillation towers (a high-boiling substance separation tower, a diaryl carbonate purification tower having a side cut outlet), and the high-boiling substance separation tower.
• a column top component mainly composed of unreacted alkylaryl carbonate, a small amount of unreacted raw material and diaryl carbonate
• a column bottom component mainly composed of a small amount of high-boiling by-products and / or a catalyst component.
• the top component of the high-boiling-point material separation tower is continuously supplied to the dialyl carbonate purification tower.
• the dial reel carbonate purification tower It has been found that a distillation separation method in which a high-purity diaryl carbonate is obtained as a side-cut component, which is continuously separated into three components, ie, a component and a bottom component, is more preferable.
• the whole or part of the bottom component of the high-boiling-point material separation tower is recycled to the first continuous multistage distillation tower and / or the second continuous multistage distillation tower as the catalyst component in step (II). It is preferable to use it.
• this tower top component is left as it is or a low boiling point component contained in the tower top component is separated.
• all or part of the bottom component of the distillation column is returned to the high boiling point separation column and / or the diaryl carbonate purification column to be recovered as high purity diaryl carbonate. Both are preferable methods.
• high-purity diaryl carbonate of usually 99.9% or more, preferably 99.99% or more is obtained.
• the content of high-boiling by-products is usually 10 ppm or less, preferably 50 ppm or less, and more preferably 10 ppm or less.
• the halogen content of the obtained high-purity diaryl carbonate is 0.1 ppm or less, preferably 10 ppm or less, and more preferably Is less than lppb.
• step (IV) is performed. That is, an aromatic dihydroxy compound is reacted with the high-purity diaryl carbonate to produce a molten prepolymer of an aromatic polycarbonate, and the molten prepolymer is allowed to flow along the surface of the guide, and the molten prepolymer is melted during the flow.
• This is a process for producing an aromatic polycarbonate using a guide contact flow type polymerization apparatus for polymerizing a prepolymer.
• the aromatic dihydroxy compound used is a compound represented by the following general formula.
• Ar represents a divalent aromatic group
• the divalent aromatic group Ar is preferably represented by the following general formula, for example.
• Ar 1 and Ar 2 each independently represent a divalent carbocyclic or heterocyclic aromatic group having 5 to 70 carbon atoms, and Y represents a divalent carbocyclic or heterocyclic aromatic group having 1 to 30 carbon atoms. O represents an alkane group
• one or more hydrogen atoms are not substituted with other substituents that do not adversely influence the reaction, for example, a halogen atom, an alkyl group having 1 to 10 carbon atoms, It may be substituted by an aralkoxy group, phenyl group, phenoxy group, vinylol group, cyanol group, ester group, amide group, nitro group or the like having 10 to 10 carbon atoms.
• substituents for example, a halogen atom, an alkyl group having 1 to 10 carbon atoms, It may be substituted by an aralkoxy group, phenyl group, phenoxy group, vinylol group, cyanol group, ester group, amide group, nitro group or the like having 10 to 10 carbon atoms.
• the heterocyclic aromatic group include aromatic groups having one or more ring-forming nitrogen atoms, oxygen atoms or sulfur atoms.
• Ar 2 represents, for example, a group such as substituted or unsubstituted phenylene, substituted or unsubstituted biphenylene, substituted or unsubstituted pyridylene.
• the substituents here are as described above.
• the divalent alkane group Y is, for example, an organic group represented by the following formula.
• R 4 each independently represents hydrogen, an alkyl group having 1 to 10 carbon atoms, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 10 carbon atoms, a 5- to 10-carbon ring structure; a cycloalkyl group having 10 to 10-carbon atoms.
• R 4 In R 5 and R 6 , other substituents such as a halogen atom, an alkyl group having 1 to 10 carbon atoms, an alkyl group having 1 to 10 carbon atoms and an alkyl group having 10 to 10 carbon atoms as long as one or more hydrogen atoms do not adversely influence the reaction. It may be substituted with a silyl group, a phenyl group, a phenoxy group, a bur group, a cyan group, an ester group, an amide group, a nitro group, or the like. )
• Such a divalent aromatic group Ar includes, for example, those represented by the following formulae:
• R 7 and R 8 are each independently a hydrogen atom, a halogen atom, an alkyl having 1 to 10 carbon atoms; A group having 1 to 10 carbon atoms, an alkoxy group having 10 to 10 carbon atoms, a cycloalkyl group or a phenyl group having 5 to 10 carbon atoms, and m and n are integers of !! to 4 and m is 24
• Each R 7 may be the same or different! /, And when n is 24, R 8 may be the same or different.
• divalent aromatic group Ar may be represented by the following formula.
• Ar 1 and Ar 2 are as described above, and Z represents a single bond or a divalent group such as —O— —CO— —S— —SO 2 SO COO CON (R 1 ) —, where R 1 is before
• Examples of such a divalent aromatic group Ar include those represented by the following formulae:
• divalent aromatic group Ar examples include substituted or unsubstituted phenylene, substituted or unsubstituted naphthylene, substituted or unsubstituted pyridylene, and the like.
• the aromatic dihydroxy compound used in the present invention may be a single type or two or more types.
• a typical example of the aromatic dihydroxy compound is bisphenol A.
• a trivalent aromatic trihydroxy compound for introducing a branched structure may be used in combination as long as the object of the present invention is not impaired.
• the aromatic dihydroxy compound and high-purity diaryl carbonate in step (IV) The usage ratio (preparation ratio) varies depending on the type of aromatic dihydroxy compound and diaryl carbonate used, the polymerization temperature, and other polymerization conditions, but diaryl carbonate is usually used for 1 mol of aromatic dihydroxy compound. It is used in an amount of 0.9 to 2.5 mol, preferably 0.95 to 2.0 monole, more preferably 0.98 to 1.5 monole.
• a molten state prepolymer (hereinafter referred to as a molten prepolymer) produced from an aromatic dihydroxy compound and diaryl carbonate is produced from an aromatic dihydroxy compound and diaryl carbonate. It means a melt in the middle of polymerization having a degree of polymerization lower than that of an aromatic polycarbonate having a desired degree of polymerization, and may of course be an oligomer.
• a melted prepolymer used in step (IV) may be obtained by any known method.
• a molten mixture of a predetermined amount of an aromatic dihydroxy compound and diaryl carbonate is usually used in a temperature range of about 120 ° C. to about 280 ° C.
• a method of continuously producing a melted polymer having a required degree of polymerization by sequentially increasing the degree of polymerization using two or more vertical stirring tanks connected in series is particularly preferable.
• this molten prepolymer is continuously supplied to a guide contact flow type polymerization apparatus to continuously produce an aromatic polycarbonate having a desired degree of polymerization.
• This guide contact flow type polymerizer is a polymerizer in which a polymer is melted and flowed along a guide, and can produce an aromatic polycarbonate of 1 ton or more per hour.
• the guide contact flow type polymerization reactor is
• the tapered bottom case of the polymerization reaction zone is connected to the upper side casing at an angle C degree inside the upper side casing, and the angle C degree satisfies the formula (21).
• A is less than 0.7 m 2 , the target production volume cannot be achieved, and in order to achieve this production volume while reducing the equipment cost, A must be 300 m 2 or less. It is. [0160] In addition, the ratio of the between A (m 2), the internal cross-sectional area in the horizontal plane of the aromatic polycarbonate discharge port 7 (b-b 'surface) B (m 2) is, satisfies equation (20) Is also necessary.
• a / B is expressed by the formula (20) Must be satisfied.
• a tapered bottom casing 11 constituting the bottom of the polymerization reaction zone 5 is provided at an angle C degrees with respect to the upper side casing 10 at an angle C degrees. It is also necessary to satisfy (21).
• the length h (cm) of the guide satisfies the formula (22).
• the degree of polymerization of the melted polymer can be increased, but the degree is not sufficient, and the variation in the degree of polymerization becomes about 200 or more in number average molecular weight, which is not preferable.
• the h force is longer than S5000cm, the difference in the melt viscosity of the melted prepolymer between the upper and lower parts of the guide becomes too large, so the variation in the degree of polymerization is about 300 or more (in some cases, about 500 or more). This is not preferable because the physical properties of the resulting aromatic polycarbonate vary with increasing size.
• the large variation in the degree of polymerization means, for example, a variation in which there is a difference of about 200 or more, expressed in terms of number average molecular weight.
• the total external surface area S (m 2 ) of the guide 4 needs to satisfy the formula (23).
• S is less than 2m 2 , the target production volume cannot be achieved, and in order to achieve this production volume while reducing equipment costs and to eliminate variations in physical properties, S should be 50000m 2 or less. is required.
• Step (IV) it is not clear why it is possible to produce an aromatic polycarbonate having such excellent effects on an industrial scale, but in addition to the above reasons, This is presumed to be due to the combined effects that appear when conditions are combined.
• the molten prepolymer can be polymerized at a relatively low temperature, and a large amount of high-quality aromatic polycarbonate having the desired molecular weight can be produced.
• the taper-shaped bottom casing that satisfies formula (21) can reduce the time it takes for this large quantity of high quality product aromatic polycarbonate falling from the guide to reach the outlet, As a result, it is presumed that the thermal history of the produced aromatic polycarbonate can be reduced.
• step (IV) is a guide contact flow type polymerization reactor satisfying the equations (19), (20), (21), (22) and (23). Therefore, the facility cost can be reduced as an industrial production facility.
• a more preferable range of the internal cross-sectional area A (m 2 ) in the horizontal plane of the side casing of the polymerization reaction zone is 0.8 ⁇ A ⁇ 250, more preferably 1 ⁇ A ⁇ 200.
• a more preferable range of the ratio to (m 2 ) is 25 ⁇ A / B ⁇ 900, and more preferably 30 ⁇ A / B ⁇ 800.
• the more preferable range of the angle C degrees formed inside the tapered bottom casing constituting the bottom of the polymerization reaction zone with respect to the upper side casing is 125 ⁇ C ⁇ 160, and more preferably Is 135 ⁇ C ⁇ 165.
• the corresponding angles are Cl, C2, C3, ..., C1 ⁇ C2 ⁇ C3 ⁇ ... is preferable
• the required length h (cm) of the guide depends on factors such as the degree of polymerization of the raw material prepolymer, the polymerization temperature and pressure, the degree of polymerization of the aromatic polycarbonate or prepolymer to be produced in the polymerization vessel, and the production amount. More preferred range of forces depending on the difference is 200 ⁇ h ⁇ 3000, more preferably 250 ⁇ h ⁇ 2500. It is particularly preferable when h satisfies the formula (31).
• the total external surface area S (m 2 ) of the entire guide required also varies depending on the same factors as above.
• the more preferable range is 4 ⁇ S ⁇ 40000, more preferably 10 ⁇ S ⁇ 30000. 15 ⁇ S ⁇ 20000 °, the preferred range.
• the external total surface area of the entire guide referred to in the present invention means the entire surface area of the guide that flows down in contact with the molten polymer.
• a guide such as a pipe
• it means the outer surface area.
• the surface area of the inner surface of the pipe that does not allow the prepolymer to flow down is not included.
• the shape of the internal cross section in the horizontal plane of the side casing of the polymerization reaction zone may be any shape such as a polygon, an ellipse, and a circle. . Since the polymerization reaction zone is usually operated under reduced pressure, it may be of any type as long as it can withstand it, but preferably it is circular or has a shape close to it. Therefore, the side casing of the polymerization reaction zone of the present invention is preferably cylindrical. In this case, it is preferable that a tapered bottom casing is connected to the lower part of the cylindrical side casing, and a cylindrical aromatic polycarbonate discharge port is provided at the lowermost part of the bottom casing.
• a more preferable range of D (cm) is 150 ⁇ D ⁇ 1500, and more preferably 200 ⁇ D ⁇ 1200. Further, a more preferable range of D / d is 6 ⁇ D / d ⁇ 45, and more preferably 7 ⁇ D / d ⁇ 40. Further, a more preferable range of L / D is 0.6 ⁇ L / D ⁇ 25, and more preferably 0.7 ⁇ L / D ⁇ 20. Further, a more preferable range of L (cm) is h—10 ⁇ L ⁇ h + 250, and more preferably h ⁇ L ⁇ h + 200. If D, d, L, and h do not satisfy these relationships at the same time, it is difficult to achieve the object of the present invention.
• process (IV) a high-quality, high-performance aromatic polycarbonate with high polymerization rate, no coloration, and excellent mechanical properties is produced stably on an industrial scale with no molecular weight variation over a long period of time.
• the exact reason for this is not clear, but the following are possible.
• the molten precursor polymer is guided from the receiving port 1 to the guide 4 via the supply zone 3 and the perforated plate 2, and along the guide.
• the degree of polymerization increases while flowing down.
• the molten prepolymers are effectively agitated and renewed while flowing down along the guide, and phenol and the like are extracted effectively, so that the polymerization proceeds at a high speed.
• the melt viscosity increases, so that the adhesive strength to the guide increases, and the amount of the melt sticking to the guide increases as it goes to the bottom of the guide.
• the residence time of the molten prepolymer on the guide that is, the polymerization reaction time is increased.
• the melted polymer that flows down under its own weight while being supported by the guide has a very large surface area per mass, and its surface is renewed efficiently.
• the high molecular weight in the latter half of the polymerization, which was possible, can be easily achieved. This is one of the excellent features of the polymerization vessel used in step (IV).
• Aromatic polycarbonate accumulated at the bottom of the tapered bottom casing is continuously withdrawn by the discharge pump 8 through the discharge port 7, and is normally pelletized continuously through an extruder. In this case, additives such as stabilizers and weathering agents can be added by an extruder.
• the perforated plate constituting the guided contact flow type polymerization reactor used in step (IV) is usually selected from a flat plate, a corrugated plate, a plate with a thick central portion, etc.
• a shape force such as circular, oval, triangular or polygonal is selected.
• the holes of the perforated plate are usually selected from shapes such as a circle, an ellipse, a triangle, a slit, a polygon, and a star.
• the cross-sectional area of the hole is usually from 0.01 to 100 cm 2 , preferably from 0.05 to 10 cm 2 , particularly preferably from 0.;! To 5 cm 2 .
• the distance between the holes is usually 1 to 500 mm, preferably 25 to 100 mm, based on the distance between the centers of the holes.
• the hole in the perforated plate may be a hole penetrating the perforated plate or may be a case where a tube is attached to the perforated plate. Further, it may be tapered.
• the guide constituting the guide contact flow type polymerization reactor used in the step (IV) has a very high ratio of the length in the vertical direction to the average length of the outer periphery of the horizontal cross section. It represents a large material.
• the ratio is usually in the range of 10-; 1,000,000, preferably 50-; 100,000.
• the shape of the cross section in the horizontal direction is usually selected from shapes such as a circle, an ellipse, a triangle, a quadrangle, a polygon, and a star.
• the shape of the cross section may be the same or different in the length direction.
• the guide may be hollow.
• the guide has no wire or thin rod, and the melted prepolymer does not enter inside.
• a single one such as a thin pipe-like one may be used, or a plurality of such may be combined by a method such as twisting. Further, a net-like one or a punching plate-like one may be used.
• the surface of the guide may be smooth or uneven, or may have a projection or the like partially.
• a preferable guide is a cylindrical shape such as a wire shape or a thin rod shape, a net shape such as the above-mentioned thin pipe shape, or a punching plate shape.
• the guide itself may have a heat source such as an electric heater or a heat source inside the guide.
• a heat source such as an electric heater or a heat source inside the guide.
• ⁇ ⁇ A guide that does not have a heat source has no concern about thermal denaturation of the prepolymer or aromatic polycarbonate on its surface. , So especially preferred.
• the guided contact flow type polymerizer of the present invention that enables production of high-quality aromatic polycarbonate on an industrial scale (production amount, long-term stable production, etc.), it is particularly preferable to use a plurality of wires. / Or rod-shaped or the above-mentioned narrow! /, A guide of the type of pipe that connects the guides at appropriate intervals above and below using a horizontal support material from the top to the bottom of the pipe-shaped guide. is there.
• a plurality of wire-like or thin rod-like or wire-like nets fixed at appropriate intervals above and below, for example, lcm to 200 cm, using a horizontal support material from the top to the bottom of the thin pipe-shaped guide.
• a guide a three-dimensional guide in which a plurality of wire mesh guides are arranged at the front and back, and they are joined at a suitable distance above and below using a lateral support material, for example, a distance of lc m to 200 cm, or a plurality of wires
• a lateral support material for example, a distance of lc m to 200 cm, or a plurality of wires
• a jungle-gym standing body that is fixed at appropriate intervals above and below, for example, 1 cm to 200 cm, using horizontal support materials on the front and back, left and right of the rod-shaped or thin pipe-shaped guide.
• the support material in the horizontal direction not only helps to keep the distance between the guides approximately the same, but also helps to strengthen the guides that are flat or curved as a whole or three-dimensional guides. These supporting materials may be the same material as the guide, or may be different.
• r is represented by the formula (3 2 ) Satisfied! /, Preferable to!
• This guide advances the polymerization reaction while flowing the molten prepolymer, but also has a function of holding the molten prepolymer for a certain period of time.
• This holding time is related to the polymerization reaction time, and as described above, the holding time and the holding amount increase as the melt viscosity increases as the polymerization proceeds.
• the amount that the guide retains the melted prepolymer varies depending on the external surface area of the guide, that is, in the case of a cylindrical shape or a pipe shape, even if the melt viscosity is the same.
• the guide installed in the polymerization vessel of the present invention needs to be strong enough to hold and support the weight of the molten prepolymer.
• the thickness of the guide is important. In the case of a columnar shape or a pipe shape, it is preferable that the formula (32) is satisfied. If r is less than 0.1, it will be difficult to perform stable operation for a long time in terms of strength. When r is larger than 1, the guide itself becomes very heavy, and the melted prepolymer has only the inconvenience, for example, the thickness of the perforated plate has to be very thick in order to hold them in the polymerizer. There are inconveniences such as an increase in the portion where the amount of retention increases too much and the variation in molecular weight increases. In this sense, the more preferred range of r is 0.15 ⁇ r ⁇ 0.8, and even more preferred is 0.2 ⁇ r ⁇ 0.6.
• a preferable material for such a guide is selected from metals such as stainless steel, carbon steel, hastelloy, nickel, titanium, chromium, aluminum and other alloys, and a polymer material having high heat resistance. Particularly preferred is stainless steel.
• the surface of the guide may be subjected to various treatments such as plating, lining, passivation treatment, acid washing, and phenol washing as necessary.
• the positional relationship between the guide and the perforated plate and the positional relationship between the guide and the hole in the perforated plate are not particularly limited as long as the molten polymer pre-guide flow is possible! /, .
• the guide and the perforated plate may or may not be in contact with each other.
• the guide is preferably installed in correspondence with the holes of the perforated plate, but is not limited thereto. This is because the molten pre-bolimer falling from the perforated plate may be designed to come into contact with the guide at an appropriate position.
• (1) The upper end of the guide is fixed to the upper inner wall surface of the polymerization vessel, etc.
• a method of flowing down the molten prepolymer through the perforated plate along the guide a method of flowing down with a liquid head or its own weight, or by pressurizing with a pump or the like, the perforated plate force is also reduced.
• a method such as extrusion is exemplified. It is preferable to supply a predetermined amount of the raw molten polymer to the polymerizer supply zone under pressure using a supply pump, and the molten polymer delivered to the guide through the perforated plate flows down along the guide under its own weight. It is a method.
• the molten prepolymer is usually continuously supplied to the guide contact flow type polymerization reactor while being heated to a predetermined polymerization temperature.
• a jacket or the like is usually provided on the outer wall surface of the guide contact flow type polymerization reactor, and it is preferable to heat the jacket to a predetermined temperature through a heating medium or the like. Accordingly, it is preferable to heat / preheat the molten prepolymer, the prepolymer supply zone and the perforated plate, and heat the polymerization reaction zone, the side casing, and the tapered bottom casing.
• the temperature of the reaction for producing an aromatic polycarbonate by polymerizing a molten polymer obtained from an aromatic dihydroxy compound and diaryl carbonate in a guide contact flow type polymerization reactor is usually It is in the range of 80-350 ° C.
• the polymerization apparatus of the present invention since efficient surface renewal with internal stirring is performed, the polymerization reaction can proceed at a relatively low temperature. Therefore, the preferred reaction temperature is 100 to 290 ° C, and more preferred is 150 to 270 ° C. In conventional reactors for horizontal biaxial stirring type ultra-high viscosity polymers, it was necessary to stir for a long time under a high vacuum of 133 Pa or less, usually at a high temperature of 300 ° C or higher.
• the polymerizer of the present invention does not have mechanical stirring, there is no seal portion of the stirrer, so that leakage of air or the like is very small.
• the polymerization can proceed sufficiently at a temperature as low as about 20 to 50 ° C. as compared with a conventional reactor for a horizontal biaxial stirring type ultrahigh viscosity polymer. This also means that the present invention produces a high-quality aromatic polycarbonate with no coloring or deterioration of physical properties. It is a big cause that can be.
• step (IV) an aromatic monohydroxy compound is produced as the polymerization reaction proceeds, and the reaction rate can be increased by removing this from the reaction system. Therefore, an inert gas that does not adversely influence the reaction, such as nitrogen, argon, helium, carbon dioxide, or lower hydrocarbon gas, is introduced into the polymerization reactor, and the aromatic monohydroxy compounds that are produced are introduced into these gases.
• an inert gas that does not adversely influence the reaction such as nitrogen, argon, helium, carbon dioxide, or lower hydrocarbon gas
• a method in which the reaction is carried out together with the solvent and a method in which the reaction is carried out under reduced pressure are preferably used.
• a method in which these are used in combination is also a force that can be preferably used. In these cases, it is not necessary to introduce a large amount of inert gas into the polymerization vessel, and the inside may be maintained in an inert gas atmosphere.
• the preferable reaction pressure in the polymerization vessel in the step (IV) varies depending on the type of aromatic polycarbonate to be produced, the molecular weight, the polymerization temperature, etc. For example, from a molten polymer from bisphenol A and diphenyl carbonate to an aromatic In the case of producing polycarbonate, when the number average molecular weight is 5,000 or less, 400 to 3, OOOPa range force S is preferable, and when the number average molecular weight is 5,000 to 10,000, the range is 50 to 500 Pa. preferable. When the number average molecular weight is 10,000 or more, 300 Pa or less is preferable, and a range force of 20 to 250 Pa is preferably used.
• step (IV) it is possible to produce an aromatic polycarbonate having the desired degree of polymerization with only one guided contact flow type polymerizer, but it is possible to produce a solution as a raw material.
• each polymerizer is a preferred method because guides and reaction conditions suitable for the degree of polymerization of the prepolymer or aromatic polycarbonate to be produced can be adopted separately.
• a guide contact flow type first polymerization device For example, use a guide contact flow type first polymerization device, a guide contact flow type second polymerization device, a guide contact flow type third polymerization device, and a guide contact flow type fourth polymerization device.
• the force S can be obtained as S1 ⁇ S2 ⁇ S3 ⁇ S4 ⁇ '—.
• the polymerization temperature may be the same in each polymerization vessel, or may be raised in order.
• the polymerization pressure can also be lowered in each polymerization vessel in turn.
• S1 / S2 is less than 1, there will be inconveniences such as large variations in molecular weight, making stable production difficult for a long period of time, and difficulty in obtaining a predetermined production amount.
• S 1 / S2 is more than 20 If it is large, the flow rate of the molten polymer that flows down the guide in the second polymerization vessel increases, and as a result, the residence time of the molten polymer is reduced and the aromatic polycarbonate having the required molecular weight can be obtained. Inconvenience occurs. In this sense, it is a more preferable range (or 1.5 ⁇ S 1 / S2 ⁇ 15.
• step (IV) 1 ton or more of aromatic polycarbonate is produced per hour, but since the aromatic monohydroxy compound by-produced by the polymerization reaction is discharged out of the system, More than 1 ton of molten prepolymer polymerizer needs to be fed. Therefore, the amount of melted polymer to be supplied varies depending on the degree of polymerization and the degree of polymerization of the aromatic polycarbonate to be produced, but it is usually 10-500 kg / per 1 ton / hr of aromatic polycarbonate production. hr more, 1. 01 ⁇ ; 1.5 in the range of 5 tons / hr is there.
• the reaction for producing an aromatic polycarbonate from an aromatic dihydroxy compound and diaryl carbonate in step (IV) can be carried out without adding a catalyst.
• a catalyst In order to increase the polymerization rate, in the presence of a catalyst, if necessary. Done.
• the catalyst is not particularly limited as long as it is used in this field, but alkali metal and alkaline earth metal hydroxides such as lithium hydroxide, sodium hydroxide, potassium hydroxide, and calcium hydroxide are used.
• Alkali metal salts, alkaline earth metal salts, quaternary ammonium salts of hydrides of boron and aluminum such as lithium aluminum hydride, sodium borohydride, tetramethylammonium borohydride; lithium hydride, sodium hydride, hydrogen Hydrogenation of alkali metals and alkaline earth metals such as russia; alkali metals and alkaline earth metal alkoxides such as lithium methoxide, sodium ethoxide and calcium methoxide; lithium phenoxide, sodium phenoxide Cid, magnesium phenoxy Alkali metal and alkaline earth metal alkoxides such as LiO—Ar—OLi and NaO—Ar—ONa (Ar is aryl); Alkali metals and alkaline earth such as lithium acetate, calcium acetate and sodium benzoate Organic acid salts of metals, zinc compounds such as zinc oxide, zinc acetate, zinc phenoxide; boron oxide, boric acid, sodium boric
• Boron compounds such as) oxides; sodium oxides, sodium silicates, tetraalkyl cages, tetraaryl cages, diphenylethyl ethoxy ketones; germanium oxides, tetrachlorides Genolenium compounds such as genoremanium, genoremanium ethoxide, genoremanium phenoxide; alkoxy groups such as tin oxide, dialkyltin oxide, dialkyltin carboxylate, tin acetate, ethyltin tributoxide Or tin compounds bonded to aryloxy groups, tin compounds such as organic tin compounds; lead oxides such as lead oxide, lead acetate, lead carbonate, basic carbonates, lead and organic lead alkoxides, Compound: Onium compound such as quaternary ammonium salt, quaternary phosphonium salt, quaternary arsonium salt, etc.
• Antimony compounds such as antimony oxide and antimony acetate;
• Manganese compounds such as manganese acetate, manganese carbonate, and manganese borate; titanium compounds such as titanium oxide, alkoxide of titanium, and aryl-toxide; zirconium acetate, zirconium oxide, alkoxide or aryloxide of zirconium, Catalysts such as zirconium compounds such as zirconium acetylacetone can be mentioned.
• these catalysts may be used alone or in combination of two or more.
• the amount of these catalysts, the aromatic dihydroxy compound of the raw materials usually 10_ 1 () to 1 wt%, preferably from 10_ 9 ⁇ ; ⁇ mass. /. , Rather more preferably is 10 8 ⁇ ; selected at 10- 2% by weight range.
• the polymerization catalyst used is the force remaining in the aromatic polycarbonate of the product.
• These polymerization catalysts usually have an adverse effect on the physical properties of the polymer. Therefore, it is preferable to reduce the amount of catalyst used as much as possible. In the method of the present invention, since the polymerization can be performed efficiently, the amount of the catalyst used can be reduced. This is another feature of the present invention that enables the production of high-quality aromatic polycarbonate.
• step (IV) There are no particular restrictions on the material of the guide contact flow type polymerizer and piping used in step (IV). Usually stainless steel, carbon steel, hastelloy, nickel, titanium, chromium, and other alloys Metals such as manufactured products and medium heat resistant polymer materials are selected. In addition, the surface of these materials may be subjected to various treatments such as plating, lining, passivation treatment, pickling, and phenol washing as necessary. Particularly preferred are stainless steel, nickel, glass lining and the like.
• a large amount of aromatic monohydroxy compound by-produced by the reaction is usually continuously extracted in the form of a gas during the production of the prepolymer in step (IV) and the polymerization in the guide contact flow type polymerization reactor. It is condensed into a liquid and recovered.
• the by-product aromatic monohydroxy compound by-produced and recovered in step (IV) of the present invention usually contains diaryl carbonate.
• the aromatic polycarbonate produced by carrying out the system of the present invention has a repeating unit represented by the following chemical formula 9.
• aromatic polycarbonate containing 85 mol% or more of a repeating unit represented by the following chemical formula 10 among all repeating units.
• the terminal group of the aromatic polycarbonate produced by carrying out the method of the present invention is usually composed of a hydroxy group or an aryl carbonate group represented by the following formula.
• the ratio of hydroxy group to aryl carbonate group is not particularly limited, but is usually in the range of 95: 5 to 5:95, preferably in the range of 90:10 to 10:90, and more preferably in the range of 80:20 to The range is 20:80.
• Particularly preferred is an aromatic polycarbonate in which the proportion of the phenyl carbonate group in the terminal group is 60 mol% or more.
• the aromatic polycarbonate produced by carrying out the method of the present invention may be partially branched with respect to the main chain via a hetero bond such as an ester bond or an ether bond.
• the amount of the heterologous binding to carbonate bonds is usually 0.005 to 2 mol%, good Mashiku is 0. 01 ;! Monore 0/0, a, more preferred, 0.05 -0. 5 Monore is 0/0.
• This amount of dissimilar bonds improves flow characteristics during melt molding without deteriorating other polymer properties, making it suitable for precision molding and molding with relatively low temperature and excellent performance. Can be manufactured.
• the molding cycle can be shortened, contributing to energy saving during molding.
• the aromatic polycarbonate produced by carrying out the method of the present invention contains almost no impurities, but an alkali metal and / or alkaline earth metal is used as the metal element.
• An aromatic polycarbonate containing! ⁇ Lppm can be produced.
• this content power is 0.005-0.5 ppm, more preferably (0.01-0.1 ppm).
• Such a metal element is 1 ppm or less, preferably 0.5 ppm or less, more preferably In the case of 0. lp pm, since the physical properties of the product aromatic polycarbonate are not adversely affected, the aromatic polycarbonate produced in the present invention is of high quality.
• aromatic polycarbonates produced by carrying out the method of the present invention particularly preferred are those produced by using a halogen-free aromatic dihydroxy compound and diaryl carbonate,
• the halogen content is usually less than lOppb.
• those having a halogen content of 5 ppb or less can be produced, and more preferably, aromatic polycarbonates having a halogen content of 1 ppb or less can be produced, resulting in a very high quality product. It will be.
• Mn 'Number average molecular weight (Mn): Measured by gel permeation chromatography (GPC) method using tetrahydrofuran as a carrier solvent, and calculated using the converted molecular weight calibration curve of the following formula obtained using standard monodisperse polystyrene. Average molecular weight (Mn) was determined.
• M is the molecular weight of the aromatic polycarbonate and M is the molecular weight of polystyrene.
• the catalyst is ⁇ ⁇ 1 (48% by weight aqueous solution) 2.
• This catalyst solution was continuously introduced into the distillation column T from the inlet (3-e) provided at the 54th stage from the bottom (K concentration: 0.1 with respect to the supplied ethylene carbonate).
• Reactive distillation was carried out continuously under the conditions that the temperature at the bottom of the column was 98 ° C., the pressure at the top of the column was about 1.118 ⁇ 10 5 Pa, and the reflux ratio was 0.42.
• the actual production amount of dimethyl carbonate per hour was 3.340 tons, and excluding ethylene glycol contained in the catalyst solution, the actual production amount of ethylene glycol per hour was 2. It was 301 tons.
• the reaction rate of ethylene carbonate was 99.88%, the selectivity of dimethyl carbonate was 99.99% or more, and the selectivity of ethylene glycol was 99.99% or more.
• the reaction rate of ethylene carbonate 99.90%, 99.89%, 99.89%, 99.88%, 99.88%, and the selectivity of dimethyl carbonate is 99.99% or more, 99.99% or more, 99.99% Less than 99.99% or more, 99.99% or more, ethylene glycol selectivity is 99.99% or more, 99.99% or more, 99.99% or more, 99.99% or more, 99.99% That was all.
• Diphenyl carbonate was produced by reactive distillation using an apparatus in which the first continuous multistage distillation column 101 and the second continuous multistage distillation column 201 were connected as shown in FIG.
• the catalyst is Pb (OPh)
• the reaction solution was about lOOppm.
• the temperature at the bottom of the column was 225 ° C, and the reactive distillation was performed continuously under the conditions of the pressure at the top of the column S7 X 10 5 Pa.
• the first tower low boiling point reaction mixture containing methyl alcohol, dimethyl carbonate, phenol, etc. is added to the top of the first tower 13
• the gas was continuously extracted in a gaseous state, passed through the heat exchanger 14, and extracted from the extraction port 16 at a flow rate of 34 tons / hr.
• the first tower high boiling point reaction mixture containing methyl phenyl carbonate, dimethyl carbonate, phenol, diphenyl carbonate, catalyst and the like was continuously extracted in liquid form from the bottom 17 of the first tower.
• the reaction distillation was continuously performed under the conditions that the temperature at the bottom of the column was 210 ° C, the pressure at the top of the column was 3 ⁇ 10 4 Pa, and the reflux ratio was 0.3. After 24 hours, stable steady operation was achieved.
• the second tower low boiling point reaction mixture containing 35% by mass of dimethyl carbonate and 56% by mass of phenol was continuously withdrawn from the top 23 of the second column, and the flow rate at the outlet 26 was 55.6 tons / hr.
• the second tower high boiling point reaction mixture containing 38.4% by weight of methyl phenyl carbonate and 55.6% by weight of diphenyl carbonate was continuously withdrawn from the bottom 27 of the second tower.
• the second column low boiling point reaction mixture was continuously supplied from the inlet 11 to the first continuous multistage distillation column 101. At this time, the amount of dimethyl carbonate and phenol to be newly supplied is adjusted so as to maintain the composition and amount of raw material 1 and raw material 2 in consideration of the composition and amount of the second tower low boiling point reaction mixture. Arranged. Diphenyl carbonate production was found to be 5.74 tons per hour. The selectivity for diphenyl carbonate was 98% with respect to the reacted phenol.
• a long-term continuous operation was performed under these conditions. After 500 hours, 2000 hours, 4000 hours, 5000 hours, and 6000 hours, the production of diphenyl carbonate (excluding diphenyl carbonate contained in the raw material) is 5 ⁇ 74 tons per hour, 5 75 tons, 5.74 tons, 5.74 tons, 5.75 tons, and the selection rates were 98%, 98%, 98%, 98%, and were very stable. In addition, the produced aromatic carbonate was substantially free of halogen! / And not (lppb or less).
• Step of obtaining high-purity diphenyl carbonate The second high boiling point reaction mixture extracted from the bottom of the second continuous multistage distillation column is continuously fed to a high boiling point material separation column (length 1700 cm, inner diameter 340 cm, 30 stages). Distillation was continuously performed at a temperature of 206 ° C, a pressure at the top of the column of 3800 Pa, and a reflux ratio of 0.6.
• the top component extracted continuously from the top of the high-boiling-point material separation tower is directly used as a diaryl carbonate purification tower having a side cut outlet (length: 2200 cm, inner diameter: 280 cm, the upper part from the inlet is 12 stages, 18 stages between the inlet and the side cut installed at the bottom, and 5 stages below the side cut.
• the diaryl carbonate purification tower distillation was continuously performed at a temperature of 213 ° C. at the bottom of the tower, a pressure of 5000 Pa at the top of the tower, and a reflux ratio of 1.5.
• the purity of diphenyl carbonate continuously extracted from the side cut outlet was 99.999% or more and the halogen content was 1ppb or less.
• the high purity diphenyl carbonate thus obtained was once stored in a molten state in a storage tank.
• Aromatic polycarbonate was produced using a guide contact flow type polymerizer as shown in Fig. 6.
• the material of this polymerization vessel is all stainless steel.
• the molten polymer supplied from the supply port 1 is uniformly distributed to each guide 4 by the perforated plate 2.
• An inert gas supply port 9 is provided at the lower part of the polymerization vessel, and a vacuum vent port 6 is provided at the upper part.
• the outside of the reactor is a jacket that is heated by a heating medium!
• the produced aromatic polycarbonate that has entered the bottom 11 of the polymerization vessel from the bottom of the guide 4 is discharged from the discharge port 7 at a flow rate of 5.5 tons / hr by the discharge pump 8 so that the amount at the bottom becomes constant. Continuously I left.
• the number average molecular weight Mn of the aromatic polycarbonate extracted from the extraction port 50 after 50 hours from the start of operation was 10,500, indicating a good color (b * value 3.2). .
• the tensile elongation was 98%. 60 hours, 100 hours, 500 hours, 1,000 hours, 2,000 hours, 3,000 hours, 4,000 hours, 5,000 hours and 5,000 hours after the start of operation
• the Mn values of the extracted aromatic polycarbonates are 10, 500, 10, 550, 10, 500, 10, 550, 10, 500, 10, 500, 10, 550, and 10, 500, respectively. there were.
• the aromatic polycarbonate produced in this way has an alkali metal and / or alkaline earth metal compound content of 0.04-0.05ppm in terms of these metal elements and a chlorine content. Was less than lppb.
• the content of heterogeneous bonds was 0.12 to 0.15 monole%.
• the phenol recovered from the top of the column was once stored in a tank and then recycled to step (II).
• the diphenyl carbonate recovered from the side cut portion was supplied to the high boiling point substance separation column in step (III) and recovered as high purity diphenyl carbonate.
• Liquid ethylene carbonate 2.61 tons / hr was continuously introduced into the distillation column at the inlet (3-a) force installed at the 55th stage from the bottom.
• the catalyst was continuously fed to the distillation column in the same manner as in Example 1. Reactive distillation was continuously carried out under the conditions that the temperature at the bottom of the column was 93 ° C, the pressure at the top of the column was about 1.04 6 X 10 5 Pa, and the reflux ratio was 0.48.
• the actual production amount of dimethyl carbonate per hour was 2.669 tons, and excluding ethylene glycol contained in the catalyst solution, the actual production amount of ethylene glycol per hour was 1. It was 839 tons.
• the reaction rate of ethylene carbonate was 99.99%, the selectivity of dimethyl carbonate was 99.99% or more, and the selectivity of ethylene glycol was 99.99% or more.
• the catalyst is Pb (OPh)
• the reaction solution was about 250 ppm.
• the temperature at the bottom of the column was 235 ° C, and the reactive distillation was continuously carried out under the pressure of S9 X 10 5 Pa at the top of the column.
• the first tower low boiling point reaction mixture containing methyl alcohol, dimethyl carbonate, phenol, etc. is continuously withdrawn from the top 13 of the first tower in the form of gas, passed through the heat exchanger 14, and from the outlet 16 to 43 tons / hr. It was extracted at a flow rate of.
• the first tower high boiling point reaction mixture containing methyl phenyl carbonate, dimethyl carbonate, phenol, diphenyl carbonate, catalyst and the like was continuously extracted in liquid form from the bottom 17 of the first tower.
• the high-boiling reaction mixture in the first column was passed through the raw material inlet 21 installed between the melapack and the perforated plate tray in the second continuous multistage distillation column 201 as it was.
• the liquid supplied to the second continuous multistage distillation column 201 contained 20.7% by mass of methyl phenyl carbonate and 1.0% by mass of diphenyl carbonate.
• reactive distillation was continuously performed under the conditions that the temperature at the bottom of the column was 205 ° C, the pressure at the top of the column was 2 ⁇ 10 4 Pa, and the reflux ratio was 0.5.
• the second tower low boiling point reaction mixture is continuously withdrawn from the second tower top 23, and the second tower bottom 27 contains 36.2% by weight methylphenyl carbonate and 60.8% by weight diphenyl carbonate.
• Two towers high boiling point reaction mixture was continuously withdrawn.
• the second column low boiling point reaction mixture was continuously supplied to the first continuous multistage distillation column 101 from the inlet 11.
• the amount of dimethyl carbonate and phenol to be newly supplied should be such that the composition and amount of raw material 1 and raw material 2 are maintained in consideration of the composition and amount of the second tower low boiling point reaction mixture. It was adjusted. Production of diphenyl carbonate was found to be 4.03 tonnes per hour. The selectivity for diphenyl carbonate was 97% with respect to the reacted phenol.
• an aromatic polycarbonate melt prepolymer (number average molecular weight Mn is 3,5) produced from bisphenol A and high-purity diphenyl carbonate (molar ratio of bisphenol A to 1 ⁇ 05). 500) Continuously supplied from supply port 1 to supply zone 3 by 1S supply pump. An aromatic polycarbonate was produced by polymerization in the same manner as in Example 1 except that the pressure in the polymerization reaction zone was maintained at l OOPa.
• the Mn of the aromatic poly-bonate discharged from the outlet 19 is 7,600, 7,600, 7,650 7,600, 7,650, 7,65 0, respectively. 7, 600, 7, 600 and stable.
• the aromatic polycarbonate produced in this manner has an alkali metal and / or alkaline earth metal compound content of 0.03 force, et al.
• the content was lppb or less. Further, the content of heterogeneous bonds was 0.08 to 0.1 monole%.
• Liquid ethylene carbonate 3.773 tons / hr was continuously introduced into the distillation column from the inlet (3-a) installed at the 55th stage from the bottom.
• the catalyst was continuously fed to the distillation column in the same manner as in Example 1. Reactive distillation was continuously carried out under the conditions that the temperature at the bottom of the column was 98 ° C., the pressure at the top of the column was about 1.118 ⁇ 10 5 Pa, and the reflux ratio was 0.42.
• the actual production amount of dimethyl carbonate per hour was 3,854 tons, and excluding ethylene glycol contained in the catalyst solution, the actual production amount of ethylene glycol per hour was 2. It was 655 tons.
• the reaction rate of ethylene carbonate was 99.88%, the selectivity of dimethyl carbonate was 99.99% or more, and the selectivity of ethylene glycol was 99.99% or more.
• a long-term continuous operation was performed under these conditions. After 1000 hours, 2000 hours, 3000 hours, and 5000 hours, the actual production volume per hour is 3.854 tons, 3.854 tons, 3.854 tons, and 3.854 tons for dimethyl carbonate.
• the ethylene glycol power is 2.655, 2.655, 2.655, 2.655 and the reaction rate of ethylene carbonate is 99.9%, 99. 99%, 99.99% and 99.99 0/0, the selectivity of dimethylol Honoré carbonate (or 99.99% or more, 99.99% or more, with 99.99% or more, 99.99% or more, ethylene Glycol selection rates were 99 ⁇ 99% or higher, 99.99% or higher, 99.99% or higher, 99.99% or higher.99% or higher.
• Reactive distillation was performed under the following conditions using the same apparatus as in Example 1 except that the cross-sectional area per hole of the perforated plate tray in the second continuous multistage distillation column 201 was about 1.8 cm 2 .
• the catalyst is Pb (OPh)
• the reaction solution was about 150 ppm.
• the temperature at the bottom of the column was 220 ° C., and the reactive distillation was continuously carried out under the conditions of the pressure at the top of the column of S8 ⁇ 10 5 Pa.
• the first tower low boiling point reaction mixture containing methyl alcohol, dimethyl carbonate, phenol, etc. is continuously withdrawn in the form of a gas from the top 13 of the first tower, passed through the heat exchanger 14, and from the outlet 16 to 82 tons / hr. It was extracted at a flow rate of.
• the first tower high boiling point reaction mixture containing methyl phenyl carbonate, dimethyl carbonate, phenol, diphenyl carbonate, catalyst and the like was continuously extracted in liquid form from the bottom 17 of the first tower.
• the high-boiling reaction mixture in the first column was passed through the raw material inlet 21 installed between the melapack and the perforated plate tray in the second continuous multistage distillation column 201 as it was.
• the liquid supplied to the second continuous multistage distillation column 201 contained 16.0% by mass of methylphenyl carbonate and 0.5% by mass of diphenyl carbonate.
• the reaction distillation is continuously performed under the conditions that the temperature at the bottom of the column is 215 ° C, the pressure at the top of the column is 2.5 X 10 4 Pa, and the reflux ratio is 0.4. It was broken.
• the second tower low boiling point reaction mixture is continuously withdrawn from the second tower top 23, and the second tower bottom 27 contains 35.5% by weight of methyl phenyl carbonate and 59.5% by weight of diphenyl carbonate.
• Second column The high boiling point reaction mixture was continuously withdrawn.
• the second column low boiling point reaction mixture was continuously supplied to the first continuous multistage distillation column 101 from the inlet 11. At this time, the amount of dimethyl carbonate and phenol to be newly supplied should be such that the composition and amount of raw material 1 and raw material 2 are maintained in consideration of the composition and amount of the second tower low boiling point reaction mixture. It was adjusted. Diphenyl carbonate production was found to be 7.28 tons per hour. Reacted eno The selectivity for diphenyl carbonate was 98%.
• the production volume of diphenyl carbonate was 7.28, 7.29, and 7.29, compared to the reacted phenol.
• the selectivity was 98%, 98% and 98%, and was very stable.
• the produced aromatic carbonate contained substantially no halogen (lppb or less).
• Aromatic polycarbonate was produced using a polymerization apparatus in which two guided contact flow type polymerization reactors as shown in Fig. 6 were arranged in series.
• the material of these polymerization vessels is all stainless steel.
• the second polymerization vessel is the same as that used in Example 1.
• An aromatic polycarbonate melt polymer (number average molecular weight Mn is 2,500) made from bisphenol A and high-purity diphenyl carbonate (molar ratio of bisphenol A to 1.06) is supplied by a feed pump. 1 Continuously fed to feed zone 3 from feed port 1 of the polymerization vessel. The molten prepolymer, which was continuously supplied to the polymerization reaction zone through the perforated plate 2 in the first polymerization vessel, proceeded with the polymerization reaction while flowing down along the guide 4. The polymerization reaction zone of the first polymerization vessel is maintained at a pressure of 800 Pa through the vacuum vent 6.
• An aromatic polycarbonate molten prepolymer (number average molecular weight Mn is 5,500) having increased degree of polymerization that has entered the bottom 11 of the polymerization vessel from the bottom of the guide 4 so that the amount at the bottom is constant. Then, it was continuously extracted from the discharge port 7 at a constant flow rate by the discharge pump 8. This molten prepolymer was continuously fed to feed zone 3 from feed port 1 of the second polymerization vessel by a feed pump. The molten prepolymer, which was continuously supplied to the polymerization reaction zone through the perforated plate 2 in the second polymerization vessel, proceeded with the polymerization reaction while flowing down along the guide 4.
• the polymerization reaction zone of the second polymerization vessel is maintained at a pressure of 50 Pa through the vacuum vent 6.
• Aroma produced from the bottom of the guide 4 into the bottom 11 of the second polymerization vessel The group polycarbonate was continuously extracted from the discharge port 7 at a flow rate of 6 tons / hr by the discharge pump 8 so that the amount at the bottom was constant.
• the number average molecular weight Mn of the aromatic polycarbonate extracted from the outlet 12 of the second polymerization vessel 50 hours after the start of operation was 11,500, indicating a good color (b * value 3.2). ) Met.
• the tensile elongation was 99%. 60 hours, 100 hours, 500 hours, 1,000 hours, 2,000 hours, 3,000 hours, 4,000 hours, 5,000 hours and 5,000 hours after the start of operation Mn of the extracted aromatic polycarbonate is 11, 500, 11, 550, 11, 500, 11, 550, 11, 500, 11, 500, 11, 550, 11, 500 and stable Met.
• the aromatic polycarbonate produced in this manner has an alkali metal and / or alkaline earth metal compound content of 0.03 force, et al.
• the content was lppb or less.
• the content of heterogeneous bonds was 0.11 to 0.16 monole%.
• a high-quality, high-performance aromatic polycarbonate that is not colored and has excellent mechanical properties from a cyclic carbonate and an aromatic dihydroxy compound is 1 ton or more per hour at a high polymerization rate.
• a high-quality aromatic polycarbonate can be stably produced for a long period of time with little variation in molecular weight, for example, 2000 hours or longer, preferably 3000 hours or longer, more preferably 5000 hours or longer. Therefore, the present invention is a method having an extremely excellent effect as an industrial production method of high-quality aromatic polycarbonate.
• FIG. 1 is a schematic view of a continuous reaction distillation column preferable for carrying out the present invention. Inside the torso
• FIG. 2 is a schematic view of a first continuous reaction distillation column preferable for carrying out the present invention.
• An internal is installed inside the torso.
• 3 It is a schematic view of a second continuous reaction distillation column preferable for carrying out the present invention.
• Inside the barrel is an internal packing consisting of regular packing at the top and a perforated plate tray at the bottom.
• FIG. 4 is a schematic view of an apparatus in which a first continuous reactive distillation column and a second continuous reactive distillation column are connected, which is preferable for carrying out the present invention.
• FIG. 5 is a schematic view of a preferred guide contact flow type polymerization apparatus for carrying out the present invention.
• 6] is a schematic view of a guide contact flow type polymerizer having a cylindrical side casing and a tapered bottom casing which are preferable for carrying out the present invention.

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• 2007
  • 2007-07-23 JP JP2008546891A patent/JP5320071B2/ja active Active
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