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    • 专利摘要:
    The present invention, when producing an aromatic polycarbonate by a polycondensation reaction or a solid state polymerization reaction under inert gas flow, the production of an aromatic polycarbonate that separates by-product alcohols or phenols in the inert gas by using a scrubber It is about a method. According to the present invention, by-products can be separated efficiently, and aromatic polycarbonate can be produced by an efficient and simplified method under inert gas flow.
    公开号:KR20030031897A
    申请号:KR1020027014673
    申请日:2001-07-18
    公开日:2003-04-23
    发明作者:하가히로노리；가쯔다다께시；스즈끼히로따까
    申请人:데이진 가부시키가이샤；
    IPC主号:
    专利说明:

    Method for producing aromatic polycarbonate {METHOD FOR PRODUCING POLYCARBONATE}
    [2] In the method for producing a polycarbonate by a polycondensation reaction, it is necessary to remove the byproducts produced by the reaction from the reaction system. In such a case, the method of suction and pressure reduction in the polymerization reactor is generally performed most frequently. However, this method requires a high-density polymerization reaction apparatus in order to maintain the inside of the reaction system at high vacuum, and there is a problem that the load is increased in terms of cost of manufacturing equipment.
    [3] In addition, instead of the method of suctioning the inside of the polymerization reactor under reduced pressure, an inert gas is passed through the polymerization reactor, and the by-products generated by the reaction are entrained with the inert gas to be removed from the reaction system, thereby condensing under low vacuum or atmospheric pressure. Reaction methods are well known.
    [4] JP-A-6-206996 discloses an aromatic polycarbonate by transesterifying a melt containing diphenols, diaryl carbonates, and then a branching agent in a temperature range of 130 ° C to 400 ° C in the presence of a catalyst. In preparing a, it is described to mix an inert gas into the melt or to pass it over the melt.
    [5] This method has the advantage that the polymerization reaction apparatus does not need to be maintained at high vacuum, while it is necessary to separate and remove the by-product from the mixed gas of the by-product and the inert gas by the reaction.
    [6] However, in order to separate condensable substances such as by-products generated by the reaction of aromatic polycarbonates in non-condensable gases such as inert gases, a device having a huge heat transfer area is required.
    [7] In the conventional method, since a surface condenser having a jacket and / or a coil is used, a large heat transfer area is required, and a very large condenser or a plurality of condensers must be used in combination, thereby increasing the installation cost.
    [8] As a solution to the above problem, Japanese Unexamined Patent Application Publication No. Hei 6-65367 discloses a process for producing an aromatic polycarbonate from an aromatic dihydroxy compound and an aromatic diester carbonate, by-product phenol compound vapor and accompanying unreacted substances, and And / or a method of using a scrubber using a compound having a vapor pressure of 10 mmHg or less at 190 ° C. as a scrubbing liquid as a method for separating by-products, unreacted substances and low polymers by condensation from steam containing a low polymer. have.
    [9] Japanese Laid-Open Patent Publication No. 2000-128975 discloses a method for producing an aromatic polycarbonate by a transesterification method, wherein (a) the vapor pressure at 190 ° C is 50 to 500 mmHg, and (b) the melting point is 30 ° C or less. and (c) A scrubber having a compound for a scrubbing liquid which dissolves at least 5% by weight of an aromatic polycarbonate having a number average molecular weight of 2,500 at 25 ° C.
    [10] U.S. Patent No. 5,444,148 also discloses a method for producing an aromatic polycarbonate by a transesterification method, in which an inert gas is removed with phenol or residual monomer, and the inert gas used for the removal is washed with diphenyl carbonate. Is described.
    [11] However, even in these methods, it was not possible to efficiently separate the reaction by-products and produce an aromatic polycarbonate.
    [1] The present invention relates to a method for producing an aromatic polycarbonate, and more particularly, in the method for producing an aromatic polycarbonate under an inert gas flow, in the inert gas, alcohols or phenols produced by reaction using a scrubber are By separating and removing, it is related with the method which can manufacture aromatic polycarbonate efficiently.
    [104] BRIEF DESCRIPTION OF THE DRAWINGS It is a figure which shows the outline of an example of the process which performed the manufacture of aromatic polycarbonate using the scrubber of this invention by melt polymerization.
    [105] It is a figure which shows the outline of an example of the process which performed manufacture of aromatic polycarbonate using the scrubber of this invention by solid state polymerization.
    [106] 3 is a view schematically showing one embodiment of a spray scrubber.
    [12] SUMMARY OF THE INVENTION An object of the present invention is to overcome the above problems in polymerization of conventional aromatic polycarbonates under inert gas flow, and to provide a method for producing polycarbonates more efficiently.
    [13] MEANS TO SOLVE THE PROBLEM As a result of earnestly examining the method of manufacturing an aromatic polycarbonate by polycondensation reaction under inert gas circulation, by using a scrubber under specific conditions, the alcohol or phenol byproduced by reaction is isolate | separated in inert gas, It has been found that aromatic polycarbonates can be produced by a more efficient and simplified method and have completed the present invention.
    [14] That is, this invention consists of two main inventions corresponding to two different starting materials, as described in detail below. That is, it is the two main invention as described in following 1 and 6 which uses an aromatic dihydroxy compound and diester carbonate as a raw material, or uses an oligomer of aromatic polycarbonate as a raw material, or corresponds to these.
    [15] The 1st invention in this invention is as follows.
    [16] 1. A method for producing an aromatic polycarbonate by polycondensation of an aromatic dihydroxy compound and a diester carbonate under a reaction pressure of 15 kPa or more and 1,000 kPa or less under inert gas flow, wherein by-products are produced by reaction using a scrubber. Alcohol or phenol is isolate | separated in this inert gas, The manufacturing method of the aromatic polycarbonate characterized by the above-mentioned.
    [17] In addition, in this invention, "reaction pressure" means the internal pressure of the polycondensation reactor in aromatic polycarbonate manufacture.
    [18] In the following, the main preferred embodiments of the first invention are listed.
    [19] 2. The manufacturing method of said 1 in which the scrubbing liquid used for a scrubber mainly consists of the compound X same as any of alcohols or phenols by-produced by reaction of this aromatic dihydroxy compound and this diester carbonate.
    [20] 3. The said manufacturing method of 2 whose temperature of this scrubbing liquid supplied to a scrubber is more than the freezing point of compound X, and the vapor pressure of compound X becomes 40 kPa or less.
    [21] 4. The production method according to any one of 1 to 3, wherein the diester carbonate is an aromatic diester carbonate.
    [22] 5. Manufacturing method of said 2 or 3 whose compound X is phenol.
    [23] The second invention in the present invention is as follows.
    [24] 6. A method for producing an aromatic polycarbonate by polycondensation of a crystallized aromatic polycarbonate under a reaction pressure of 15 kPa or more and 1,000 kPa or less under inert gas flow, wherein an alcohol or a phenol produced by reaction by using a scrubber is used. A method for producing an aromatic polycarbonate, characterized by separating in this inert gas.
    [25] In the following, the main preferred embodiments of the second invention are listed.
    [26] 7. The manufacturing method of said 6 in which the scrubbing liquid used for a scrubber mainly consists of the compound Y which is the same as any of alcohols or phenols by-produced by reaction of this crystallized aromatic polycarbonate.
    [27] 8. The manufacturing method of said 7 whose temperature of this scrubbing liquid supplied to a scrubber is more than the freezing point of compound Y, and the vapor pressure of compound Y will be 40 kPa or less.
    [28] 9. Manufacturing method of said 7 or 8 whose compound Y is phenol.
    [29] Best Mode for Carrying Out the Invention
    [30] Next, the 1st and 2nd invention in this invention is described in detail based on drawing.
    [31] In the case of producing the aromatic polycarbonate by the melt polymerization method according to the first invention, examples of the process for producing the aromatic polycarbonate of the present invention or the method of manufacturing the reaction by-products using the scrubber, which are the characteristics of the present invention, in particular It shows in FIG. 1 and shows the case where an aromatic polycarbonate is manufactured by the solid state polymerization method which is 2nd invention.
    [32] In addition, an example of a spray scrubber is shown in FIG.
    [33] In addition, these figures show only one embodiment of this invention, Needless to say, the other embodiment which carried out design change suitably is also included in the scope of the present invention. For example, the polymerization reactor includes a horizontal polymerization reactor in addition to the vertical polymerization reactor shown in FIG. 1 or 2, and the case where the rectification column shown in FIG. 1 is not used is also included in the scope of the present invention. The polycondensation reaction can be applied to the present invention in either batch or continuous mode, and in either of these batch or continuous mode, it is not essential to apply the present invention to every step from the supply of raw materials to the obtaining of the product. And at least part of the production steps of the aromatic polycarbonate.
    [34] One embodiment of the manufacturing method of the aromatic polycarbonate by melt polymerization method is shown in FIG.
    [35] The production process by the melt polymerization method mainly consists of a polymerization reactor 1, a rectification tower 2, and a scrubber 3. The raw material of aromatic dihydroxy compound, diester carbonate and catalyst and / or low molecular weight polycarbonate (when the present invention is applied during the step of polymerization) is a polymerization reactor from the raw material supply pipe (4). It is supplied to (1) continuously or at once. As for the temperature of a polymerization reaction, 150 degreeC-350 degreeC is preferable. At temperatures below that, the reaction is less likely to proceed smoothly, and at temperatures above 350 ° C, undesirable side reactions such as branching reactions are likely to occur, which is not preferred.
    [36] When the raw materials are continuously supplied to the polymerization reactor, the reaction mixture which has been polycondensed to some extent in the polymerization reactor is discharged continuously or all at once from the reactant discharge pipe 5.
    [37] The oligomer of the aromatic polycarbonate discharge | released here can be used for the manufacturing method which uses a crystallized aromatic polycarbonate as a raw material.
    [38] The inert gas circulated in the polymerization reactor 1 is circulated in the reaction apparatus through the rectifying tower 2 and the scrubber 3 by the gas circulation pump 6. The inert gas may be replenished in the circulation system as necessary. The inert gas is heated by the heater 7 and flowed into the polymerization reactor. The temperature of the inert gas to be heated is preferably 350 ° C. or lower while being higher than the reaction temperature of the polycondensation. If the temperature of the inert gas is lower than the reaction temperature, the reaction rate is slowed, which is not preferable. At temperatures exceeding 350 ° C., undesirable side reactions such as branch reactions are likely to occur, as in the case of the reaction temperature, and therefore not preferable. In addition, there is no restriction | limiting in particular in the method of making inert gas circulate in a polymerization reactor, Preferably the method of inject | pouring directly into a reaction mixture is preferable.
    [39] The reaction pressure (pressure inside the polycondensation reactor) is preferably 15 kPa or more and 1,000 kPa or less, preferably 90 kPa or more and 300 kPa, more preferably 90 kPa or more and 200 kPa in order to take advantage of characteristics such as conduction of an inert gas. Do. At a pressure lower than the lower limit, high vacuum is generated, and the apparatus for maintaining the same is large scale. At a pressure higher than the upper limit, a load is applied to a pump that distributes an inert gas such as a compressor, a blower, and the like to distribute the inert gas.
    [40] In addition, in this invention, an "inert gas" means the gas which does not affect the polycondensation reaction of aromatic polycarbonate, and can mention the rare gas, such as helium and argon, other than nitrogen gas.
    [41] About the amount (A (unit: kg / hr)) which distribute | circulates an inert gas in a polymerization reactor, it is preferable that ratio of A and diester carbonate injection amount (B (unit: kg / hr)) is 0.07-7. If it is less than 0.07, the effect of inert gas flow is too small and the reaction rate is too slow, and it is not preferable. If it is larger than 7, the capacity of equipment such as a scrubber becomes huge and there is a fear of becoming unrealistic.
    [42] Alcohols or phenols (hereinafter referred to as reaction by-products) produced by the reaction are discharged from the vent pipe 8 of the polymerization reactor together with the inert gas together with the unreacted products in the polymerization reactor and led to the rectification tower 2. do. In the rectification column 2, the reaction byproduct and the unreacted substance are separated, and the unreacted substance having a high boiling point fraction is returned to the polymerization reactor again. On the other hand, the mixed gas of the inert gas and the reaction by-product flows out from the top of the tower of the rectifying tower 2 and is led to the scrubber 3 through the rectifying tower-scrubber connecting pipe 9.
    [43] 2 shows one embodiment of a method for producing an aromatic polycarbonate by solid phase polymerization.
    [44] The manufacturing method by the solid-phase polymerization method mainly consists of a polymerization reactor 1 and the scrubber 3, as shown in FIG. In the case of the solid phase polymerization method, it is necessary to use a crystallized aromatic polycarbonate (in the present invention, simply referred to as "crystallized aromatic polycarbonate") at least partially crystallized. Although there is no restriction | limiting in particular in the viscosity average molecular weight of a crystallized aromatic polycarbonate, 3,000-50,000 are preferable, More preferably, it is 5,200-22,000. The crystallinity of the crystallized aromatic polycarbonate may be about 10% to about 70%. The said crystallized aromatic polycarbonate which is a raw material is supplied continuously or all at once from the raw material supply piping 4 to the polymerization reactor 1. (Polymerization temperature is more than +20 degreeC of glass transition temperature of a crystallized aromatic polycarbonate) Moreover, melting | fusing point of this crystallized aromatic polycarbonate-5 degrees C or less is preferable. At temperatures below the lower limit, the reaction is less likely to proceed smoothly, and at temperatures exceeding the upper limit, the crystals melt and the crystallized aromatic polycarbonate is difficult to maintain a solid phase.
    [45] When the crystallized aromatic polycarbonate which is a raw material is continuously supplied to the polymerization reactor, the reaction mixture subjected to some degree of polycondensation reaction in the polymerization reactor is discharged continuously or all at once from the reactant discharge pipe 5.
    [46] The inert gas circulated in the polymerization reactor 1 is circulated through the scrubber 3 by the gas circulation pump 6, and further, if necessary, through the organic gas adsorption device 15. In addition, the inert gas may be newly replenished in the circulation system as necessary. The inert gas is heated by the heater 7 and flowed into the polymerization reactor. The temperature of the inert gas to be heated is preferably (glass transition temperature of crystallized aromatic polycarbonate + 20 ° C or more) and (melting point of this crystallized aromatic polycarbonate-5 ° C or less). At temperatures below that, the reaction is less likely to proceed smoothly, and at temperatures exceeding this, the crystals melt and it is difficult for the crystallized aromatic polycarbonate to maintain a solid phase. In addition, there is no restriction | limiting in particular in the method to distribute an inert gas in a polymerization reactor, Preferably the method of flowing from the lower part to the upper part of a polymerization reactor is preferable.
    [47] The pressure (reaction pressure) inside the polymerization reactor is preferably 15 kPa or more and 1,000 kPa or less, preferably 90 kPa or more and 500 kPa, more preferably 90 kPa or more and 200 kPa in order to make use of characteristics such as conduction of an inert gas. . At a pressure lower than the lower limit, high vacuum is generated, and the apparatus for maintaining the same is large scale. At a pressure higher than the upper limit, a load is applied to a pump that distributes an inert gas such as a compressor, a blower, and the like to distribute the inert gas.
    [48] About the amount (A (unit: kg / hr)) which distribute | circulates an inert gas in a polymerization reactor, it is preferable that ratio of A and the crystallization aromatic polycarbonate injection amount (C (unit: kg / hr)) is 0.07-7. If it is less than 0.07, the effect of inert gas flow is too small and the reaction rate is too slow, and it is not preferable. If it is larger than 7, the capacity of equipment such as a scrubber becomes huge and there is a fear of becoming unrealistic.
    [49] Alcohols or phenols (hereinafter referred to as reaction byproducts) produced by the reaction are led to the scrubber 3 through the vent pipe 8 of the polymerization reactor together with the inert gas together with the unreacted products in the polymerization reactor.
    [50] In the present invention, the reaction by-product is separated in an inert gas using a scrubber.
    [51] In this invention, it is preferable that the scrubbing liquid used for a scrubber mainly consists of the compound X or Y which is the same as any of alcohols or phenols which are reaction byproducts. Here, "consisting mainly of" means that the reaction by-product is a main component in the scrubbing liquid composition, preferably 50 mol% or more, and more preferably 80 mol% or more. In this case, which of the alcohols or phenols can be selected by experiment or the like, but it is often advantageous to select the compound having the larger amount of outflow since the post-treatment is easy.
    [52] This simplifies the process of separating and purifying the scrubbing liquid and the reaction byproduct that absorbed the reaction byproduct. In addition, the scrubbing liquid may be used as it is or by mixing the condensation liquefaction reaction product. There is no restriction | limiting in particular in mixing ratio.
    [53] 1 or 2, the scrubbing liquid is used under temperature control by a scrubbing liquid temperature regulator 10 such as a heat exchanger. It is preferable that the temperature of a scrubbing liquid is the temperature which the vapor pressure of the compound X of a scrubbing liquid becomes 40 kPa or less at the inlet of a scrubber more than the freezing point of the compound X or Y in a scrubbing liquid. If it is less than that, the liquid will solidify, and at the temperature exceeding it, it is not preferable because sufficient separation treatment capacity of the scrubber cannot be obtained. Therefore, when X or Y is phenol, the freezing point is 43 degreeC, and the temperature at which the vapor pressure becomes 40 kPa is 150 degreeC.
    [54] In FIG. 1 or FIG. 2, the temperature-regulated scrubbing liquid is supplied to the scrubber through the scrubbing liquid feeding pipe 12 by the scrubbing liquid circulation pump 11, and is in contact with the mixed gas of the inert gas and the reaction byproduct, and inert Absorb and separate the reaction byproducts in the gas. The scrubbing liquid that absorbed the reaction by-product is again temperature-controlled by the scrubbing liquid temperature regulator 10 and supplied to the scrubber, but a part of the scrubbing liquid is discharged from the scrubbing liquid circulation system through the scrubbing liquid discharge pipe 13 as necessary. In addition, since the scrubbing liquid is the same component as the reaction by-product, a part of the scrubbing liquid can be used as the reflux liquid of the rectifying tower, and the required amount is supplied from the reflux liquid feeding pipe 14 to the rectifying tower.
    [55] 3 schematically shows an embodiment of a spray scrubber. In the scrubber tower 1 ', the scrubbing liquid B injected by the spray nozzle 2' and the mixed gas A of the reaction by-product and the inert gas come into contact with each other, and the scrubbing liquid that absorbs the reaction by-product ( D) and reaction by-products become reduced inert gas (C).
    [56] There is no restriction | limiting in particular as a scrubber used by this invention, The scrubber liquid can contact well with the mixed gas of an inert gas and a reaction by-product, and the structure of which pressure loss is small is used, for example, spray type, packed column type, flowing water The splash type, the surface collision type, the Venturi type, the cyclone type, etc. can be considered.
    [57] The pressure of the scrubber in the present invention is preferably about the same as the reaction pressure, preferably 15 kPa or more and 1,000 kPa or less, preferably 90 kPa or more and 500 kPa, more preferably 90 kPa or more and 200 kPa.
    [58] It goes without saying that the present invention may be used in combination with other separation techniques, such as surface capacitors, in addition to scrubbers.
    [59] The aromatic polycarbonate targeted by the first invention of the present invention is an ester containing a mixture mainly containing an aromatic dihydroxy compound and a diester carbonate, for example, a nitrogen-containing basic compound and an alkali metal compound and / or an alkaline earth metal compound. It is an aromatic polycarbonate condensation-polymerized in presence of an exchange catalyst.
    [60] Moreover, the aromatic polycarbonate made into object of 2nd invention is an aromatic polycarbonate obtained by making low molecular weight aromatic polycarbonate, ie, oligomer or prepolymer of aromatic polycarbonate, a starting material, and crystallizing this, and then solid-phase-polymerizing.
    [61] The aromatic dihydroxy compound, diester carbonate, polycondensation reaction catalyst, etc. of the raw material used for the manufacturing method of the aromatic polycarbonate which is 1st invention are demonstrated in detail below.
    [62] Specific examples of such aromatic dihydroxy compounds include bis (4-hydroxyphenyl) methane, 2,2-bis (4-hydroxyphenyl) propane, and 2,2-bis (4-hydroxy-3- Methylphenyl) propane, 4,4-bis (4-hydroxyphenyl) heptane, 2,2-bis (4-hydroxy-3,5-dichlorophenyl) propane, 2,2-bis (4-hydroxy-3 , 5-dibromophenyl) propane, bis (4-hydroxyphenyl) oxide, bis (3,5-dichloro-4-hydroxyphenyl) oxide, p, p'-dihydroxydiphenyl, 3,3 '-Dichloro-4,4'-dihydroxydiphenyl, bis (hydroxyphenyl) sulfone, resorcinol, hydroquinone, 1,4-dihydroxy-2,5-dichlorobenzene, 1,4- Dihydroxy-3-methylbenzene, bis (4-hydroxyphenyl) sulfide, bis (4-hydroxyphenyl) sulfoxide, and the like, but in particular 2,2-bis (4-hydroxyphenyl) propane This is preferred.
    [63] Specific examples of the diester carbonate include diphenyl carbonate, ditolyl carbonate, bis (chlorophenyl) carbonate, m-cresyl carbonate, dinaphthyl carbonate, bis (diphenyl) carbonate, dimethyl carbonate, diethyl carbonate and di Butyl carbonate, dicyclohexyl carbonate and the like are used. Among these, diphenyl carbonate is preferable also in terms of reactivity, stability to coloring of the resin obtained, and cost.
    [64] Moreover, the polycarbonate of this invention is dicarboxylic, for example, as an aliphatic dihydroxy compound, for example, ethylene glycol, 1, 4- butanediol, 1, 4- cyclohexane dimethanol, 1, 10-decanediol, etc. As the acid, for example, succinic acid, isophthalic acid, 2,6-naphthalenedicarboxylic acid, adipic acid, cyclohexanecarboxylic acid, terephthalic acid and the like; Oxyacids such as lactic acid, P-hydroxybenzoic acid, 6-hydroxy-2-naphthoic acid and the like may be contained.
    [65] As the catalyst of the polycondensation reaction, an alkali metal compound or an alkaline earth metal compound is preferably used, and an alkali metal compound is particularly preferably used.
    [66] Examples of the alkali metal compound used as the catalyst include hydroxides, carbonates, carbonates, acetates, nitrates, nitrites, sulfites, cyanates, thiocyanates, stearates, borohydrides, benzoates, and phosphates of alkali metals. And salts of bisphenols and phenols.
    [67] Specific examples include sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium hydrogen carbonate, potassium hydrogen carbonate, lithium bicarbonate, sodium carbonate, potassium carbonate, lithium carbonate, sodium acetate, potassium acetate, lithium acetate, sodium nitrate, potassium nitrate, and nitric acid Lithium, sodium nitrite, potassium nitrite, lithium nitrite, sodium sulfite, potassium sulfite, lithium sulfite, sodium cyanate, potassium cyanate, lithium cyanate, sodium thiocyanate, potassium thiocyanate, lithium thiocyanate, sodium stearate Potassium stearate, lithium stearate, sodium borohydride, potassium borohydride, lithium borohydride, sodium phenyl borate, potassium phenyl borate, lithium phenyl borate, sodium benzoate, potassium benzoate, lithium benzoate, sodium hydrogen phosphate, Dipotassium hydrogen phosphate, dilithium hydrogen phosphate, disodium salt of bisphenol A, dipotassium salt, dilithium salt, sodium salt of phenol, potassium salt, lithium salt and the like. , The sodium salt of the disodium salt of bisphenol A and phenol is most preferred.
    [68] Examples of alkaline earth metal compounds used as catalysts include hydroxides, carbonates, carbonates, acetates, nitrates, nitrites, sulfites, cyanates, thiocyanates, stearates, borohydrides, benzoates, bisphenols, and phenols of alkaline earth metals. Salts; and the like.
    [69] Specifically, calcium hydroxide, barium hydroxide, strontium hydroxide, calcium hydrogen carbonate, barium hydrogen carbonate, strontium hydrogen carbonate, calcium carbonate, barium carbonate, strontium carbonate, calcium acetate, barium acetate, strontium acetate, calcium nitrate, barium nitrate, nitrate Strontium, calcium nitrite, barium nitrite, strontium nitrite, calcium sulfite, barium sulfite, strontium sulfite, calcium cyanide, barium cyanate, strontium cyanate, calcium thiocyanate, barium thiocyanate, strontium thiocyanate, calcium stearate , Barium stearate, strontium stearate, calcium borohydride, barium borohydride, strontium borohydride, calcium benzoate, barium benzoate, strontium benzoate, calcium salt of bisphenol A, barium salt, strontium salt, calcium salt of phenol, barium salt, Strontium salt etc. are mentioned.
    [70] The alkali metal compound or alkaline earth metal compound as the catalyst is preferably used in a ratio such that the alkali metal element or alkaline earth metal element in the catalyst is 1 × 10 −8 to 5 × 10 −5 equivalents per mole of aromatic diol compound. A more preferable ratio is the ratio used as 5 * 10 <-7> -1 * 10 <-5> equivalent with respect to the same reference | standard.
    [71] When the amount of alkali metal elements or alkaline earth metal elements in the catalyst deviates from the range of 1 × 10 −8 to 5 × 10 −5 equivalents per mole of aromatic dihydroxy compound, adversely affects various physical properties of the aromatic polycarbonate resin obtained. It is not preferable because there is a problem such as not being able to obtain a high molecular weight aromatic polycarbonate resin, or the transesterification reaction does not proceed sufficiently.
    [72] Moreover, as a nitrogen-containing basic compound as a catalyst, for example, tetramethylammonium hydroxide (Me 4 NOH), tetraethylammonium hydroxide (Et 4 NOH), tetrabutylammonium hydroxide (Bu 4 NOH), benzyltrimethyl Ammonium hydroxides having alkyl, aryl, alkylaryl groups such as ammonium hydroxide (Ph-CH 2 (Me) 3 NOH), hexadecyltrimethylammonium hydroxide, triethylamine, tributylamine, dimethylbenzyl Tertiary amines such as amines and hexadecyldimethylamine, or tetramethylammonium borohydride (Me 4 NBH 4 ), tetrabutylammonium borohydride (Bu 4 NBH 4 ), tetramethylammonium tetraphenylborate (Me 4 NBPh 4), tetrabutylammonium tetraphenylborate (Bu 4 NBPh 4) there may be mentioned basic salt, such as.
    [73] It is preferable to use the said nitrogen-containing basic compound in the ratio whose ammonium nitrogen atom in a nitrogen-containing basic compound becomes 1 * 10 <-5> -5 * 10 <-4> equivalent per mole of aromatic dihydroxy compound. A more preferable ratio is the ratio used as 2x10 <-5> -5 * 10 <-4> equivalent with respect to the same reference | standard. A particularly preferable ratio is the ratio which becomes 5x10 <-5> -5 * 10 <-4> equivalent with respect to the said reference | standard.
    [74] In addition, in the specification of the present invention, the ratio of the alkali metal compound, the alkaline earth metal compound and the nitrogen-containing basic compound to the injected aromatic diol compound (which has the same meaning as the "aromatic dihydroxy compound") is referred to as "aromatic dihydroxy compound 1". Molar amount of W (value) equivalents of Z (compound name) as metal or basic nitrogen '' relative to mole, but this is, for example, Z is sodium phenoxide or 2,2-bis (4-hydroxyphenyl) propanemono sodium salt. When there is one sodium atom as in the above, or one basic nitrogen such as triethylamine, it means that the amount of Z is equivalent to W mole, and the 2,2-bis (4-hydroxyphenyl) propanedisodium salt If it is two together, it means that it is an quantity corresponded to W / 2 mole.
    [75] In the present invention, as the alkali metal compound of the catalyst, an alkali metal salt of an (ate) complex of an element of Group 14 of the periodic table or an alkali metal salt of oxo acid of an element of the Group 14 of the periodic table can be used, if necessary. . Here, the 14th group element of the periodic table means silicon, germanium, and tin.
    [76] By using these alkali metal compounds as a polycondensation reaction catalyst, it has the advantage that a polycondensation reaction can be advanced quickly and fully. In addition, undesirable side reactions, such as branching reactions generated during the polycondensation reaction, can be suppressed at low levels.
    [77] (a) As an alkali metal salt of the eight complex of an element of group 14 of a periodic table, what is described in Unexamined-Japanese-Patent No. 7-268091, Specifically, the compound of germanium (Ge); NaGe (OMe) 5 , NaGe (OEt) 3 , NaGe (OPr) 5 , NaGe (OBu) 5 , NaGe (OPh) 5 , LiGe (OMe) 5 , LiGe (OBu) 5 , LiGe (OPh) 5 have.
    [78] Examples of the compounds of tin (Sn) include NaSn (OMe) 3 , NaSn (OMe) 2 (OEt), NaSn (OPr) 3 , NaSn (OnC 6 H 13 ) 3 , NaSn (OMe) 5 , NaSn (OEt) 5 , NaSn (OBu) 5 , NaSn (OnC 12 H 25 ) 5 , NaSn (OEt) 3 , NaSn (OPh) 5 , NaSnBu 2 (OMe) 3 .
    [79] (B) Alkali metal salts of oxo acids of periodic table Group 14 elements include, for example, alkali metal salts of silicic acid, alkali metal salts of tartaric acid, alkali metal salts of germanium (II) acid, and alkali metal salts of germanium (IV) acid. Can be mentioned.
    [80] The alkali metal salts of silicic acid are, for example, acidic or neutral alkali metal salts of monosilicic acid or a condensate thereof, and examples thereof include monosodium orthosilicate, disodium orthosilicate, trisodium orthosilicate and tetrasodium silicate.
    [81] Alkali metal salts of tartaric acid are, for example, acidic or neutral alkali metal salts of monotartrate or its condensates, for example monodiartite disodium salt (Na 2 SnO 3 xH 2 O, x = 0 to 5), monotartrate sodium A salt (Na 4 SnO 4 ) can be mentioned.
    [82] The alkali metal salt of germanium (II) acid is, for example, an acidic or neutral alkali metal salt of monogermanic acid or a condensate thereof, and examples thereof include monosodium germanium salt (NaHGeO 2 ).
    [83] Alkali metal salts of germanium (IV) acid are, for example, acidic or neutral alkali metal salts of monogermanium (IV) acid or condensates thereof, such as orthogermanic acid monolithic acid (LiH 3 GeO 4 ), orthogermanic acid disodium salt , Tetrasodium salt of orthogermanic acid, disodium salt of digermanic acid (Na 2 Ge 2 O 5 ), disodium tetragermanic acid salt (Na 2 Ge 4 O 9 ), disodium pentagermanic acid salt (Na 2 Ge 5 O 11 ) Can be mentioned.
    [84] The polycondensation reaction catalyst as described above is preferably used in a proportion such that the alkali metal element in the catalyst is 1 × 10 −8 to 5 × 10 −5 equivalents per mole of aromatic dihydroxy compound. A more preferable ratio is the ratio used as 5 * 10 <-7> -1 * 10 <-5> equivalent with respect to the same reference | standard.
    [85] In the polycondensation reaction of the present invention, at least one cocatalyst selected from the group consisting of an oxo acid and an oxide of an copper element of the Periodic Table 14 element can coexist with the catalyst as necessary.
    [86] By using these cocatalysts in a specific ratio, such as branching reactions that are likely to occur during the polycondensation reaction, generation of foreign matter in the apparatus during the molding process, and combustion, without impairing the terminal blocking reaction and the polycondensation reaction rate. It is possible to more effectively suppress undesirable side reactions.
    [87] Examples of the oxo acid of the Periodic Table 14 element include silicic acid, tartaric acid and germanium acid.
    [88] Examples of the oxide of the Group 14 element of the periodic table include silicon monoxide, silicon dioxide, tin monoxide, tin dioxide, germanium monoxide, germanium dioxide, and condensates thereof.
    [89] The cocatalyst is preferably present at a rate such that the metal element of Group 14 of the periodic table in the cocatalyst is 50 mol (atoms) or less per 1 mol (atoms) of the alkali metal element in the polycondensation reaction catalyst. When the cocatalyst is used in a proportion of more than 50 mol (atoms) of copper metal elements, the polycondensation reaction rate is slowed, which is not preferable.
    [90] The cocatalyst is more preferably present at a rate such that 0.1 to 30 moles (atoms) of the metal elements of Group 14 of the periodic table of the cocatalyst are present per mole of alkali metal elements (atoms) of the polycondensation reaction catalyst.
    [91] These catalyst systems have the advantage of being able to advance the polycondensation reaction and the terminal sealing reaction quickly and sufficiently by using in the polycondensation reaction. In addition, undesirable side reactions such as branching reactions generated in the polycondensation reaction system can be suppressed to a low level.
    [92] The method of solidifying a low molecular weight aromatic polycarbonate after crystallizing it is known, for example, it is described in Unexamined-Japanese-Patent No. 2001-11171.
    [93] The crystallized aromatic polycarbonate which is a starting material of the present invention is obtained by crystallizing an oligomer of a low molecular weight aromatic polycarbonate, that is, an aromatic polycarbonate.
    [94] Moreover, although various polymerization methods can be employ | adopted for manufacture of low molecular weight aromatic polycarbonate, melt polymerization method can be used preferably. Moreover, a well-known solvent treatment method, heat crystallization method, etc. are mentioned as a method of crystallizing the oligomer of aromatic polycarbonate. The crystallization method in the present invention is preferably a heat crystallization method.
    [95] In the present invention, as the microcrystalline (ie, substantially uncrystallized) low molecular weight aromatic polycarbonate, one having an inherent viscosity [ ] Having an oligomer or prepolymer in the range of 0.05 to 0.25 (dl / g) can be preferably used. In addition, the intrinsic viscosity [(eta)] of the aromatic polycarbonate used in this invention is a value computed from the viscosity measured at the temperature of 20 degreeC by the dichloromethane solution.
    [96] The oligomer of this aromatic polycarbonate is usually in an amorphous state having a crystallinity of approximately 0% or close to this, and when producing a polycarbonate oligomer by a melt polymerization reaction, a polycarbonate oligomer in a molten state immediately after the reaction can be preferably used. have.
    [97] In the present invention, the low molecular weight aromatic polycarbonate is crystallized while being maintained at a temperature range below the melting point while above the glass transition temperature (Tg) thereof. Crystallization hardly proceeds at this temperature below the glass transition temperature (Tg) of the low molecular weight aromatic polycarbonate, and the crystal melts at a temperature above the melting point. Preferred crystallization treatment temperatures are at least (glass transition temperature of this low molecular weight aromatic polycarbonate + 20 ° C) and below the melting point, more preferably (glass transition temperature of this low molecular weight aromatic polycarbonate + 40 ° C) or more ( Melting point-5 DEG C).
    [98] The atmosphere of this crystallization treatment may be in the air, in an inert gas, or in vacuum. The time required for crystallization depends on the degree of polymerization, glass transition temperature (Tg), and amount of low molecular weight aromatic polycarbonate.
    [99] Usually, in such crystallization treatment, granulation of crystallization is also performed at the same time. Examples of the granulation method include a method in which a molten state is dropped to a predetermined size on a hot plate at a predetermined temperature or attached and granulated, a method of taking out a molten mixture in a strand shape from a molten state and cutting it into a predetermined length, from a molten state The method which casts on a film on a hotplate, cut | disconnects after a crystallization, or grind | pulverizes, the method which grind | pulverizes after cooling crystallization to a mass, etc. is employ | adopted.
    [100] In order to promote crystallization, as described in Japanese Laid-Open Patent Publication No. 2001-11171, an oligomer of an already crystallized aromatic polycarbonate may be used as a small amount of crystal nuclei. As another crystallization promotion method, diester carbonate, an aromatic dihydroxy compound, or the like can also be used as a small amount of plasticizer.
    [101] The crystallization of the aromatic polycarbonate which is crystallized by the above method and granulated as necessary, is heated in the inert gas atmosphere at the temperature below melting | fusing point of this crystallization in solid state, solid-phase polymerization is performed, and high degree of polymerization is carried out. To an aromatic polycarbonate. Although a high temperature is preferable in terms of the polymerization rate, in order to prevent fusion of the crystallized product, it is necessary to carry out at a temperature lower than the melting point of the crystallized product. In addition, since the melting point of the crystallization increases with the increase in the degree of polymerization, a method of sequentially raising the solid phase polymerization temperature in accordance with the increase in the melting point is also preferably used. As polymerization time, several hours-several tens of hours are employ | adopted normally.
    [102] The polycarbonate resin produced by the solid-phase polymerization as described above has a polymer intrinsic viscosity [ ] Of about 0.3 to 1.7 (dl / g), good color, low gel component, and excellent moldability. Therefore, since blocking reaction of terminal hydroxyl group and stabilization of melt viscosity can be performed, it is preferable to implement in this way in order to improve the thermal stability and durability stability at the time of shaping | molding of a polycarbonate resin.
    [103] According to the present invention, since the by-products can be efficiently separated, the aromatic polycarbonate can be produced efficiently and in a simplified manner under inert gas flow.
    [107] Examples of the present invention are shown below. However, this invention is not limited by these Examples.
    [108] [Analysis method]
    [109] 1) Phenol Concentration in Inert Gas
    [110] The phenol in the mixed gas of the collected inert gas and phenol was dissolved in acetonitrile, and the phenol concentration in the solution was determined by gas chromatography.
    [111] 2) Viscosity Average Molecular Weight of Polycarbonate
    [112] Indichloromethane was measured at 20 degreeC using the Ubbelohde viscometer, and the intrinsic viscosity [(eta) (dl / g) was measured, and the viscosity average molecular weight (M) was calculated | required by following Formula.
    [113] [η] = 1.23 × 10M 0.83
    [114] 3) melting point
    [115] Melting | fusing point was calculated | required by the Perkin Elmer DSC7 at the temperature increase rate of 20 degree-C / min. The crystal melting enthalpy (ΔH) was calculated from the area of the portion corresponding to the crystal melting.
    [116] 4) crystallinity
    [117] The degree of crystallinity can be determined from [Delta] H of 100% crystallized polycarbonate from [Delta] H obtained by DSC measurement [Journal of Polymer Science; Part B: Polymer Physics (J. Polym. Sci .: Polym. Phys.) 1979, vol. 25, pp. 1511-1517, was calculated as 109.8 J / g.
    [118] Example 1
    [119] A polymerization reactor having a volume of 5 L continuously at a rate of 1,000 g / hr for 2,2'-bis (4-hydroxyphenyl) propane, 967 g / hr for diphenylcarbonate, and 0.60 mg / hr for bisphenol A disodium salt The reaction pressure was reacted while injecting an inert gas directly into the liquid phase of the reaction liquid of the polymerization reactor at a normal pressure. The reacted polycarbonate was continuously discharged from the polymerization reactor at a rate of 1,180 g / hr. In addition, nitrogen gas was used as an inert gas. This nitrogen gas was heated to 240 degreeC, and it supplied to the polymerization reactor at the rate of 20 NL / min. Nitrogen gas was directly supplied to the liquid phase of the reaction liquid of the polymerization reactor.
    [120] Phenol, which is a reaction byproduct, is discharged from the reactor vent pipe together with nitrogen gas together with a small amount of unreacted diphenyl carbonate or oligomer, and separated and recovered by a scrubber. The scrubber used the apparatus shown in FIG. 1 and FIG. 3, The pressure was normal pressure, and the temperature of the scrubbing liquid was operated at 55 degreeC and the flow volume of 1.5 L / min. As a result, the concentration of phenol in the inert gas of the reaction by-product on the scrubber inlet side was 52.48 wt%, whereas the concentration of the phenol in the inert gas on the scrubber outlet side was 2.04 wt%. In addition, in starting continuous production, phenol was injected as a scrubbing liquid, and thereafter, an appropriate increase was discharged from the scrubbing liquid discharge pipe.
    [121] In addition, the viscosity average molecular weight of the polycarbonate obtained by the said method was 5,220, and stable continuous manufacture was possible.
    [122] Example 2
    [123] A part of the low molecular weight aromatic polycarbonate obtained in Example 1 was taken out and heat-processed in nitrogen atmosphere at 180 degreeC for 4 hours. In addition, although crystallization hardly progressed in 1 hour of heat treatment, the thing of 23% of crystallinity was obtained by heat processing of 4 hours. The viscosity average molecular weight of obtained crystallized polycarbonate was 5,650, melting | fusing point was 220 degreeC, and (DELTA) H was 37.9 J / g. After pulverizing this, it classified using the sieve of mesh size of 1 mm and 2 mm, and set it as the powder of particle size 1mm-2mm.
    [124] The powdered crystallized polycarbonate was continuously supplied to a reactor having a capacity of 50 L at 1,000 g / hr, and the reaction temperature was 220 ° C., and the reaction pressure was subjected to a solid phase polymerization reaction while flowing an inert gas through the reactor at normal pressure. At this time, the reacted polycarbonate was continuously discharged from the polymerization reactor at a rate of 970 g / hr. In addition, nitrogen gas was used as an inert gas. This nitrogen gas was heated to 220 ° C. and fed to the polymerization reactor at a rate of 20 NL / min.
    [125] Phenol, which is a reaction by-product, is discharged from the reactor vent pipe together with nitrogen gas together with a small amount of unreacted diphenyl carbonate or oligomer, and separated and recovered by a scrubber. The scrubber used the apparatus of FIG. 2 and FIG. 3, the pressure was normal pressure, the temperature of the scrubbing liquid was 50 degreeC, and it operated at the flow volume of 1.5 L / min. As a result, the concentration of the phenol in the inert gas at the scrubber outlet side was 0.012 wt% while the concentration in the inert gas of the phenol as the reaction by-product on the scrubber inlet side was 0.022 wt%. In addition, in starting continuous production, phenol was injected as a scrubbing liquid, and thereafter, an appropriate increase was discharged from the scrubbing liquid discharge pipe.
    [126] In addition, the viscosity average molecular weight of the polycarbonate obtained by the said method was able to be manufactured stably at 22,300.
    权利要求:
    Claims (9)
    [1" claim-type="Currently amended] In the method of polycondensation-reacting an aromatic dihydroxy compound and a diester carbonate under reaction pressure of 15 kPa or more and 1,000 kPa or less under inert gas circulation, the alcohol produced by reaction using a scrubber is produced by reaction. Or a phenol is separated in an inert gas.
    [2" claim-type="Currently amended] The manufacturing method of Claim 1 in which the scrubbing liquid used for a scrubber consists mainly of the compound X same as any of alcohols or phenols by-produced by reaction of an aromatic dihydroxy compound and diester carbonate.
    [3" claim-type="Currently amended] The method according to claim 2, wherein the scrubbing liquid supplied to the scrubber is at or above the freezing point of the compound X while the vapor pressure of the compound X is 40 kPa or less.
    [4" claim-type="Currently amended] The production method according to any one of claims 1 to 3, wherein the diester carbonate is an aromatic diester carbonate.
    [5" claim-type="Currently amended] The process according to claim 2 or 3, wherein compound X is phenol.
    [6" claim-type="Currently amended] In the method for producing an aromatic polycarbonate by polycondensation reaction of the crystallized aromatic polycarbonate under a reaction pressure of 15 kPa or more and 1,000 kPa or less under an inert gas flow, an alcohol or a phenol produced by reaction using a scrubber is used for inert gas. A process for producing an aromatic polycarbonate, characterized by separating in the middle.
    [7" claim-type="Currently amended] The manufacturing method of Claim 6 in which the scrubbing liquid used for a scrubber mainly consists of the compound Y which is the same as any of alcohols or phenols by-produced by reaction of a crystallization aromatic polycarbonate.
    [8" claim-type="Currently amended] The manufacturing method of Claim 7 whose temperature of the scrubbing liquid supplied to a scrubber is more than the freezing point of compound Y, and the vapor pressure of compound Y becomes 40 kPa or less.
    [9" claim-type="Currently amended] 9. A process according to claim 7 or 8 wherein compound Y is phenol.
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    同族专利:
    公开号 | 公开日
    WO2002008312A1|2002-01-31|
    EP1304344A1|2003-04-23|
    US20040044239A1|2004-03-04|
    JP3615208B2|2005-02-02|
    TW555783B|2003-10-01|
    AU7274901A|2002-02-05|
    CN1174021C|2004-11-03|
    EP1304344A4|2004-11-24|
    CN1426432A|2003-06-25|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    法律状态:
    2000-07-24|Priority to JP2000221984
    2000-07-24|Priority to JPJP-P-2000-00221984
    2001-07-18|Application filed by 데이진 가부시키가이샤
    2003-04-23|Publication of KR20030031897A
    优先权:
    申请号 | 申请日 | 专利标题
    JP2000221984|2000-07-24|
    JPJP-P-2000-00221984|2000-07-24|
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