WO2016104532A1 - Procédé de production de polycarbonate - Google Patents

Procédé de production de polycarbonate Download PDF

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WO2016104532A1
WO2016104532A1 PCT/JP2015/085880 JP2015085880W WO2016104532A1 WO 2016104532 A1 WO2016104532 A1 WO 2016104532A1 JP 2015085880 W JP2015085880 W JP 2015085880W WO 2016104532 A1 WO2016104532 A1 WO 2016104532A1
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polycarbonate
reaction
unbranched
branched
branching agent
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PCT/JP2015/085880
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English (en)
Japanese (ja)
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和宏 関口
幸子 長尾
高橋　雅之
佐々木　健志
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出光興産株式会社
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    • 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
    • C08G64/22—General preparatory processes using carbonyl halides
    • C08G64/24—General preparatory processes using carbonyl halides and phenols

Definitions

  • the present invention relates to a method for producing polycarbonate, and more particularly to a method for producing polycarbonate when switching from unbranched polycarbonate to branched polycarbonate or switching from branched polycarbonate to unbranched polycarbonate.
  • Polycarbonate has excellent characteristics such as transparency, heat resistance, and mechanical properties, and is used in a wide range of applications such as OA / consumer housings, electrical / electronic components, and optical materials such as lenses.
  • Many of the polycarbonates used in this wide range of applications are usually unbranched polycarbonates (linear polymers) obtained by reacting dihydric phenols with carbonate precursors such as phosgene.
  • the unbranched polycarbonate exhibits Newtonian flow behavior under melt processing conditions.
  • drawdown due to its own weight is likely to occur, and a problem particularly occurs in large molding.
  • a branched polycarbonate which exhibits non-Newtonian fluidity under melt processing conditions and hardly causes drawdown during melting is preferably employed in the above molding applications.
  • an interfacial polymerization method or a transesterification method is known as a method for producing the unbranched polycarbonate or the branched polycarbonate.
  • a polycarbonate is produced using the transesterification method, since the raw material components are melted at a high temperature and subjected to a transesterification reaction for polymerization, the resulting polycarbonate is easily colored due to the influence of the polymerization catalyst used. Therefore, it is not preferable to produce an unbranched polycarbonate or a branched polycarbonate using an ester exchange method in an application where transparency is required.
  • a method of producing using an interfacial polymerization method is preferably used.
  • Patent Document 1 As a method for producing the branched polycarbonate by the interfacial polymerization method, as known in Patent Document 1 and Patent Document 2, a divalent phenol and a branching agent for having a branched nucleus structure in the molecular chain are used. It is known to manufacture.
  • the same production apparatus is used to continuously use the unbranched polycarbonate and the branched polycarbonate in order to efficiently use the polycarbonate production apparatus to be used.
  • the manufacturing method is used. That is, after a non-branched polycarbonate is produced for a certain period, a branching agent is introduced to produce a branched polycarbonate, and after a branched polycarbonate is produced for a certain period of time, the introduction of the branching agent is stopped to produce an unbranched polycarbonate. It has been broken.
  • the obtained branched polycarbonate is used from the relationship of residence time in the production apparatus.
  • the branching agent content gradually rises until the branching agent content becomes, thereby obtaining a branched polycarbonate having the desired branching agent content.
  • the branched polycarbonate produced between the start of the increase in the branching agent content and the target branching agent content is treated as a transitional product because the predetermined branching agent content is not reached. Usually, it is transferred as a polycarbonate powder or the like into another container for transition products.
  • transition product when switching from the production of branched polycarbonate to the production of unbranched polycarbonate, a transition product is generated, and the transition product is transferred as a polycarbonate powder or the like into the container for the transition product.
  • These transition products can be used as a branched polycarbonate with a low branching agent content by mixing and making the branching agent content uniform, or by mixing with a branched polycarbonate with a high branching agent content.
  • the branching agent content can be further increased.
  • the present invention when switching to the production of branched polycarbonate by introducing a branching agent from the production of unbranched polycarbonate, or when switching to the production of unbranched polycarbonate by stopping the introduction of the branching agent from the production of branched polycarbonate, It is an object of the present invention to provide a method for producing a polycarbonate with a small change in molecular weight of a generated polycarbonate transition product (hereinafter sometimes referred to as a transition product).
  • the present inventors have found that the above object can be achieved by devising the introduction position of the branching agent and the introduction method of the terminal terminator used in the polycondensation step. It came to complete. That is, the present invention relates to the following [1] to [10].
  • the steps (a) to (d) are continuously performed, and the reaction liquid containing the polycarbonate is switched from the reaction
  • a method for producing polycarbonate that switches to a reaction liquid containing branched polycarbonate When switching from a reaction solution containing unbranched polycarbonate to a reaction solution containing branched polycarbonate, a branching agent is introduced into the step (a), When switching from a reaction liquid containing a branched polycarbonate to a reaction liquid containing an unbranched polycarbonate, the introduction of the branching agent is stopped in the step (a), And the manufacturing method of a polycarbonate which increases or decreases the terminal terminator introduce
  • the method includes a step (e) of separating the reaction liquid containing the polycarbonate obtained in the step (d) into an organic solvent phase containing polycarbonate and an aqueous phase containing unreacted dihydric phenol, Any one of the above [1] to [3], wherein the aqueous phase containing the unreacted dihydric phenol separated in the step (e) is used as the alkaline aqueous solution of the dihydric phenol introduced into the step (b).
  • the terminal terminator is selected from phenol, p-cresol, p-tert-butylphenol, p-tert-octylphenol, p-cumylphenol, 3-pentadecylphenol, bromophenol, tribromophenol, and nonylphenol.
  • the polycarbonate production method of the present invention when switching from the production of unbranched polycarbonate to the production of branched polycarbonate by introducing a branching agent, or by stopping the introduction of the branching agent from the production of branched polycarbonate,
  • branching agent when changing to production, there is little variation in the molecular weight of the transferred product, so it is possible to reduce the efficiency and reduce the complicated work required to adjust the molecular weight required when using the transferred product. Can do.
  • the load on the apparatus due to molecular weight fluctuations can be reduced.
  • steps (a) to (e) for producing an unbranched polycarbonate are shown.
  • steps (a) to (e) for producing a branched polycarbonate are shown.
  • the polycarbonate production method of the present invention is obtained from the step (a) of obtaining a reaction solution by subjecting a mixture containing an alkaline aqueous solution of dihydric phenol and phosgene to a phosgenation reaction in the presence of an organic solvent, and the step (a).
  • a step (d) for obtaining a reaction liquid containing the reaction solution the steps (a) to (d) are continuously performed,
  • a method for producing a polycarbonate wherein a reaction solution containing a catalyst is switched from a reaction solution containing an unbranched polycarbonate to a reaction solution containing a branched polycarbonate, or a reaction solution containing a branched polycarbonate is switched to a reaction solution containing an unbranched polycarbonate.
  • a branching agent is introduced into the step (a), and when switching from a reaction solution containing branched polycarbonate to a reaction solution containing unbranched polycarbonate
  • the introduction of the branching agent is stopped in the step (a), and the terminal terminator introduced in the step (d) is increased or decreased in a plurality of stages.
  • the manufacturing method of the polycarbonate of this invention is demonstrated in detail. In the present specification, it is possible to arbitrarily adopt provisions that are preferable, and it can be said that a combination of preferable ones is more preferable.
  • Step (a) is a step of obtaining a reaction solution by subjecting a mixture containing an alkaline aqueous solution of dihydric phenol and phosgene to a phosgenation reaction in the presence of an organic solvent.
  • the raw materials and reaction conditions used in this step (a) will be described.
  • dihydric phenol used for the production of polycarbonate is used.
  • dihydric phenol it is preferable to use a dihydric phenol represented by the following general formula (1).
  • R 11 and R 12 each independently represent a halogen atom, an alkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms.
  • Z is a single bond, an alkylene group having 1 to 8 carbon atoms, an alkylidene group having 2 to 8 carbon atoms, a cycloalkylene group having 5 to 15 carbon atoms, a cycloalkylidene group having 5 to 15 carbon atoms, a fluorenediyl group, a carbon
  • the dihydric phenol represented by the general formula (1) is not particularly limited, but 2,2-bis (4-hydroxyphenyl) propane [common name: bisphenol A] is preferable.
  • bisphenol A 2,2-bis (4-hydroxyphenyl) propane
  • the unbranched polycarbonate can be a homopolycarbonate produced using bisphenol A
  • the branched polycarbonate is a branched polycarbonate produced using bisphenol A. be able to.
  • dihydric phenols other than bisphenol A include bis (4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) ethane, 2,2-bis (4-hydroxyphenyl) butane, 2,2 -Bis (4-hydroxyphenyl) octane, bis (4-hydroxyphenyl) phenylmethane, bis (4-hydroxyphenyl) diphenylmethane, 2,2-bis (4-hydroxy-3-methylphenyl) propane, bis (4- Hydroxyphenyl) naphthylmethane, 1,1-bis (4-hydroxy-3-tert-butylphenyl) propane, 2,2-bis (4-hydroxy-3-bromophenyl) propane, 2,2-bis (4- Hydroxy-3,5-dimethylphenyl) propane, 2,2-bis (4-hydroxy-3-chlorophene) Bis (hydroxyaryl) alkanes such as propane, 2,2-bis (4-hydroxy-3,5-dichlorophenyl) propane, 2,2-bis (4-hydroxy-3,
  • the dihydric phenol is used as an alkaline aqueous solution.
  • the alkali used include alkali hydroxides, particularly strong basic hydroxides such as sodium hydroxide and potassium hydroxide.
  • As the alkali concentration of the alkaline aqueous solution usually 1 to 15% by mass is preferably used.
  • the content of the dihydric phenol in the alkaline aqueous solution is usually selected in the range of 0.5 to 20% by mass.
  • the phosgene used in step (a) is usually obtained by reacting chlorine and carbon monoxide with a ratio of 1.01 to 1.3 moles of carbon monoxide per mole of chlorine using activated carbon as a catalyst. Compound.
  • phosgene gas when used as phosgene gas, phosgene gas containing about 1 to 30% by volume of unreacted carbon monoxide can be used. Also, phosgene in a liquefied state can be used.
  • a branching agent is used when obtaining a reaction liquid containing a branched polycarbonate, and no branching agent is used when obtaining a reaction liquid containing an unbranched polycarbonate.
  • the branching agent is introduced into the step (a). The branching agent when used in step (a) will be described.
  • the branching agent used in step (a) is not particularly limited, and a known branching agent can be used. Among known branching agents, it is preferable to use a branching agent having three or more functional groups.
  • a branching agent for example, phloroglucide, pyromellitic acid, 1,1,2,2-tetrakis (4-hydroxyphenyl) ethane, ⁇ , ⁇ , ⁇ ′, ⁇ ′-tetrakis (4-hydroxy) Phenyl) -p-xylene, ⁇ , ⁇ , ⁇ ', ⁇ '-tetrakis (2-methyl-4-hydroxyphenyl) -p-xylene, ⁇ , ⁇ , ⁇ ', ⁇ '-tetrakis (2,5-dimethyl) -4-hydroxyphenyl) -p-xylene, ⁇ , ⁇ , ⁇ ', ⁇ '-tetrakis (2,6-dimethyl
  • a compound represented by the following chemical formula (A) may be used as a tetrafunctional or more functional branching agent.
  • R 7 and R 8 represent an alkyl group having 1 to 8 carbon atoms or an aryl group having 6 to 20 carbon atoms.
  • n is an integer of 1 to 100, preferably an integer of 1 to 50.
  • the alkyl group include a methyl group, an ethyl group, a propyl group, and a butyl group.
  • the aryl group include a phenyl group.
  • R 7 and R 8 are each independent and may be the same or different.
  • tetra (4-hydroxyphenylpropyl-polymethylsiloxane) silicon in which R 7 and R 8 are methyl groups is preferable.
  • R 13 represents HO—A—R 17 —
  • A represents an arylene group having 6 to 12 carbon atoms
  • R 17 represents an alkylene group having 1 to 6 carbon atoms
  • R 17 represents an Si atom.
  • A may further have a substituent.
  • a plurality of R 13 may be the same or different.
  • R 14 , R 15 and R 16 each independently represent an alkyl group having 1 to 6 carbon atoms, a phenyl group and / or a trimethylsiloxy group, and a plurality of R 14 , R 15 and R 16 may be the same or different. It may be.
  • x represents a number from 1 to less than 2
  • y represents a number from 0 to 1
  • x + y is from 1 to 2.
  • c is a number from 4 to 16
  • d is a number from 0 to 8.
  • a cyclic siloxane structure can be taken.
  • c preferably has a structural unit of 4 or more and 8 or less, and d is 0, more preferably c is 4 and d has a structural unit of 0.
  • a in the general formula (II) represents an arylene group having 6 to 12 carbon atoms, preferably orthophenylene, metaphenylene, or paraphenylene.
  • substituent include an alkyl group, an alkoxy group, and / or a hydroxyl group.
  • examples of the alkyl group include an alkyl group having 3 to 6 carbon atoms, and examples of the alkoxy group include a methoxy group.
  • R 17 (bonded to the Si atom) in the general formula (II) represents an alkylene group having 1 to 6 carbon atoms, and examples thereof include a methylene group, an ethylene group, a propylene group, and a butylene group.
  • a C 1-4 alkylene group is preferred, and a propylene group is more preferred.
  • Examples of the alkyl group having 1 to 6 carbon atoms represented by R 14 to R 16 in the general formula (II) include a methyl group, an ethyl group, a propyl group, and a butyl group.
  • An alkyl group is preferred, and a methyl group is more preferred.
  • branching agent having a cyclic siloxane structure branching agents represented by the following general formulas (III) to (XI) can be used.
  • c each independently represents an integer of 4 to 16, preferably an integer of 4 to 8, and d represents 0 or an integer of 1 to 8.
  • R 15 independently represents a methyl group, an ethyl group, a propyl group, a butyl group, or a phenyl group.
  • c is 4 or more and 8 or less, d is more preferably 0, c is 4, and d is more preferably 0.
  • R represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms
  • R 1 to R 6 each represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a halogen atom.
  • examples of the alkyl group having 1 to 5 carbon atoms represented by R include a methyl group, an ethyl group, an n-propyl group, an n-butyl group, and an n-pentyl group.
  • examples of the alkyl group having 1 to 5 carbon atoms represented by R 1 to R 6 include a methyl group, an ethyl group, an n-propyl group, an n-butyl group, and an n-pentyl group.
  • examples thereof include a chlorine atom, a bromine atom, and a fluorine atom.
  • branching agent represented by formula (I) examples include 1,1,1-tris (4-hydroxyphenyl) methane; 1,1,1-tris (4-hydroxyphenyl) ethane; -Tris (4-hydroxyphenyl) propane; 1,1,1-tris (2-methyl-4-hydroxyphenyl) methane; 1,1,1-tris (2-methyl-4-hydroxyphenyl) ethane; 1,1-tris (3-methyl-4-hydroxyphenyl) methane; 1,1,1-tris (3-methyl-4-hydroxyphenyl) ethane; 1,1,1-tris (3,5-dimethyl- 4-hydroxyphenyl) methane; 1,1,1-tris (3,5-dimethyl-4-hydroxyphenyl) ethane; 1,1,1-tris (3-chloro-4-hydroxyphenyl) methane; 1,1 , 1- Lis (3-chloro-4-hydroxyphenyl) ethane; 1,1,1-tris (3,5-dichloro-4-hydroxy)
  • branching agents of the general formula (I) 1,1,1-tris (4-hydroxyphenyl) ethane [hereinafter sometimes referred to as THPE]. It is particularly preferable from the viewpoint of the branching property of the branched polycarbonate.
  • the said branching agent may be used individually by 1 type, and may use 2 or more types together.
  • organic solvent used in the step (a) examples include a solvent that dissolves the polycarbonate oligomer and the polycarbonate resin.
  • organic solvent used in the step (a) examples include halogenated hydrocarbon solvents such as dichloromethane (methylene chloride), dichloroethane, trichloroethane, tetrachloroethane, pentachloroethane, hexachloroethane, dichloroethylene, chlorobenzene, and dichlorobenzene, with dichloromethane (methylene chloride) being particularly preferred.
  • step (a) other raw materials can be used as necessary in addition to the above raw materials.
  • a catalyst such as a tertiary amine such as triethylamine or a quaternary ammonium salt such as tetraethylammonium chloride used in the polycondensation reaction can be used to promote the reaction.
  • the alkaline aqueous solution of dihydric phenol and the branching agent and phosgene react vigorously and generate heat. Therefore, it is desirable to cool the reaction product to 0 to 50 ° C. in order to suppress side reactions. . Therefore, as the reactor used in the step (a), it is preferable to use a reactor equipped with a cooling facility for cooling the reaction product.
  • the phosgenation reaction may be performed in such a state that the reaction solution becomes a turbulent state in the reactor. preferable.
  • the mixed reactor is preferably a static mixer, that is, a static mixer.
  • the static mixer is preferably a tubular reactor having therein an element having an action of dividing, converting, and inverting the fluid, and the element generally has a shape obtained by twisting a rectangular plate by 180 degrees. .
  • the reaction mixture introduced into the reactor is divided into two parts each time it passes through one element. Further, the reaction mixture fluid or the reaction product fluid is rearranged from the tube center to the wall and from the tube wall to the center along the twisted surface in the element. In addition, the direction of rotation of the fluid is changed for each element, and the fluid is agitated by turbulent flow due to a sudden reversal of inertial force.
  • the tubular static mixer described above bubbles in the liquid are miniaturized in the reactor, and the contact interface becomes larger, thereby dramatically increasing the reaction efficiency.
  • phosgene should be used in an excess amount so that the amount of phosgene used is usually 1.05 to 1.5 mol, preferably 1.1 to 1.3 mol, per mol of dihydric phenol. Is preferred.
  • the molar ratio of dihydric phenol and branching agent is usually a molar ratio of dihydric phenol: branching agent within the range of 99.8: 0.2 to 95: 5. Preferably, it is used in a molar ratio within the range of 99.7: 0.3 to 97: 3.
  • the branching agent represented by the general formula (I) can be dissolved in an alkaline aqueous solution, so that it is desirable to introduce it by dissolving it in an alkaline aqueous solution. Moreover, it is desirable to introduce the branching agent that is difficult to dissolve in an alkaline aqueous solution after being dissolved in an organic solvent such as methylene chloride.
  • step (a) heat is generated due to a reaction in which the terminal group of the dihydric phenol or the terminal group of the dihydric phenol and the branching agent is chloroformated with phosgene or the reaction in which phosgene is decomposed with alkali. Since the temperature of the reaction product becomes high, it is preferable to cool the reaction product so that the temperature of the reaction product is 0 to 80 ° C., preferably 5 to 70 ° C.
  • an exothermic reaction occurs from the confluence of an alkaline aqueous solution of dihydric phenol and phosgene, or from the confluence of an alkaline aqueous solution of dihydric phenol, a branching agent and phosgene. Also, it is preferable to cool at this junction. As the reaction product flows through the reactor of the tubular static mixer to the outlet of the reactor, phosgene is consumed and no intense reaction heat is generated.
  • the main purpose of the reaction in this step (a) is to chloroformate the terminal group of the dihydric phenol or the terminal group of the dihydric phenol and the branching agent with phosgene, and the oligomerization reaction hardly proceeds. .
  • Step (b) is a step of introducing an alkaline aqueous solution of a dihydric phenol into the reaction solution obtained from the step (a), and obtaining a reaction solution containing a polycarbonate oligomer in the presence of a polymerization catalyst as necessary. .
  • the raw materials and reaction conditions used in this step (b) will be described.
  • the molecular weight is increased by the oligomerization reaction in the step (b), and preferably a polycarbonate oligomer having a weight average molecular weight of 5000 or less is used.
  • a polycarbonate oligomer having a weight average molecular weight of 5000 or less is used.
  • the alkaline aqueous solution of the dihydric phenol used in this step (b) the alkaline aqueous solution of the dihydric phenol described in the step (a) is used.
  • a known catalyst used during the interfacial polymerization of the polycarbonate resin can be used.
  • Phase transfer catalysts such as tertiary amines or salts thereof, quaternary ammonium salts, quaternary phosphonium salts and the like can be preferably used.
  • the tertiary amine include triethylamine, tributylamine, N, N-dimethylcyclohexylamine, pyridine, dimethylaniline and the like, and examples of the tertiary amine salt include hydrochlorides and bromates of these tertiary amines. Etc.
  • Examples of the quaternary ammonium salt include trimethylbenzylammonium chloride, triethylbenzylammonium chloride, tributylbenzylammonium chloride, trioctylmethylammonium chloride, tetrabutylammonium chloride, and tetrabutylammonium bromide.
  • Examples thereof include butylphosphonium chloride and tetrabutylphosphonium bromide.
  • These catalysts may be used alone or in combination of two or more. Among the catalysts, tertiary amines are preferable, and triethylamine is particularly preferable. These catalysts can be introduced as they are in a liquid state or dissolved in an organic solvent or water. Moreover, a solid-state thing can be dissolved and introduce
  • a stirring tank is generally used as the reactor used in the step (b).
  • the stirring tank is not particularly limited as long as it is a tank-type stirring tank having a stirrer.
  • the reaction liquid obtained from the step (a) is introduced into the reactor for proceeding with the oligomerization reaction.
  • the reaction solution obtained from step (a) the remaining amount of unreacted dihydric phenol and the remaining alkali component is small, and in order to proceed with the oligomerization reaction, dihydric phenol and alkali component are added. It is necessary to react.
  • the oligomerization reaction of the step (b) is carried out in the reactor used by the branching agent used when producing the end group of the dihydric phenol and the branched polycarbonate contained in the reaction solution obtained from the step (a). It proceeds by reacting a compound having a terminal group chloroformated with phosgene and a dihydric phenol in the presence of an alkali.
  • a compound having a terminal group chloroformated with phosgene and a dihydric phenol in the presence of an alkali.
  • an alkaline aqueous solution of dihydric phenol prepared in advance used in step (a) is introduced into the reactor, or in addition to this,
  • the oligomerization reaction can proceed by introducing the prepared antkari aqueous solution into the reactor.
  • the aqueous phase [the aqueous phase obtained in the step (e) described later] out of the reaction solution containing the polycarbonate obtained after the polycondensation step is separated into an organic solvent phase and an aqueous phase. Then, it can be introduced into the reactor of step (b) to advance the oligomerization reaction.
  • the aqueous phase obtained in the step (e) contains unreacted dihydric phenol and alkali, and the dihydric phenol and alkali can be effectively utilized by recycling the aqueous phase.
  • the aqueous phase after the polycondensation step may include sodium carbonate generated by the decomposition reaction with sodium hydroxide without using the chloroformate group of the polycarbonate oligomer during the polycondensation step.
  • the concentration of the dihydric phenol added to the step (b) is usually 0.05 to 0.15 mol / liter, preferably 0.06 to 0.12 mol / liter, more preferably 0.06 to 0.08 mol.
  • the alkali concentration added in step (b) is usually 0.03 to 0.25 mol / liter, preferably 0.05 to 0.21 mol / liter, more preferably 0.00. It is preferably 12 to 0.15 mol / liter.
  • the amount of the organic solvent used in the reaction solution in this step (b) is usually such that the volume ratio of the organic phase to the aqueous phase is preferably 5/1 to 1/7, more preferably 2/1 to 1/4. Is selected.
  • Step (b) is a step of obtaining a reaction solution containing a polycarbonate oligomer, and the upper limit of the weight average molecular weight is preferably 5000, and the lower limit is usually about 500.
  • a terminal terminator in order to make the preferable weight average molecular weight of the polycarbonate oligomer be 5000 or less. It becomes easy to adjust the weight average molecular weight of the polycarbonate oligomer in the step (b) to 5000 or less by adding the terminal stopper.
  • the end terminator is not particularly limited, and those used for the production of polycarbonate can be used.
  • examples of the compound used for the terminal stopper include phenol, p-cresol, p-tert-butylphenol, p-tert-octylphenol, p-cumylphenol, 3-pentadecylphenol, bromophenol, Mention may be made of at least one monohydric phenol selected from tribromophenol and nonylphenol. Of these, p-tert-butylphenol, p-cumylphenol and phenol are preferred from the viewpoints of economy and availability. These end terminators may be dissolved in an organic solvent such as methylene chloride, added to the reaction solution obtained from step (a), and introduced into step (b) or used in step (b). May be added directly to the reactor to be introduced.
  • an organic solvent such as methylene chloride
  • the temperature in the reactor is usually 5 to 50 ° C., preferably 5 to 40 ° C., and the reaction is carried out. Stirring is performed under relatively gentle conditions of laminar flow.
  • the residence time of the reaction solution in the reactor varies depending on the molecular weight of the target polycarbonate oligomer, the properties of the reaction solution obtained from step (a), etc., but is generally 15 to 60 minutes.
  • Step (c) is a step of separating the reaction solution containing the polycarbonate oligomer obtained from the step (b) into an aqueous phase and an organic solvent phase containing the polycarbonate oligomer.
  • a stationary separation tank is preferably used as a device used in the step (c).
  • the reaction solution obtained in the step (b) is introduced into a stationary separation tank and separated into an aqueous phase and an organic solvent phase containing a polycarbonate oligomer due to a specific gravity difference.
  • the organic solvent phase containing the lower layer polycarbonate oligomer is continuously or intermittently extracted from the lower side of the stationary separation tank.
  • the upper water phase is withdrawn continuously or intermittently, and the level of each phase in the stationary separation tank is kept within a certain level range.
  • Step (d) is a step of obtaining a reaction solution containing polycarbonate by reacting the organic solvent phase containing the polycarbonate oligomer separated in the step (c), an alkali aqueous solution of dihydric phenol, and a terminal terminator.
  • a polycarbonate oligomer and a dihydric phenol are subjected to a polycondensation reaction in the presence of a terminal terminator to adjust the molecular weight to the target molecular weight range.
  • the polycondensation reaction is carried out until the molecular weight of the obtained polycarbonate is a viscosity average molecular weight, usually in the range of about 10,000 to 100,000, preferably in the range of 10,000 to 50,000.
  • the organic solvent phase containing the polycarbonate oligomer separated in step (c) and an alkaline aqueous solution of a dihydric phenol are mixed with a terminal terminator, and usually in the range of 0 to 50 ° C., preferably in the range of 5 to 40 ° C. Interfacial polycondensation at temperature.
  • a terminal terminator for example, those described in the steps (a) and (b) can be used, and as the terminal terminator, those described in the step (b) can be used.
  • the above-mentioned polymerization catalyst, organic solvent, and aqueous alkali solution may be added to cause interfacial polycondensation.
  • a polycarbonate in this step (d), can be obtained as a branched polycarbonate by introducing a branching agent into the step (a). Moreover, if a branching agent is not introduced into the step (a), a polycarbonate can be obtained as an unbranched polycarbonate.
  • the steps (a) to (d) are continuously performed using the polycarbonate continuous production apparatus having the steps (a) to (d), and the reaction liquid containing the polycarbonate is obtained.
  • a non-branched polycarbonate having substantially the same molecular weight is produced by switching from a reaction solution containing a branched polycarbonate to a reaction solution containing an unbranched polycarbonate
  • a plurality of terminal terminators introduced into the step (d) are used. It is preferable to decrease in stages.
  • the target molecular weight may not be achieved. In this case, it is necessary to reduce the end terminator. Even in such a case, it is preferable to reduce the end terminator in a plurality of stages.
  • the reasons for increasing or decreasing the above-mentioned end terminator in multiple stages include the following.
  • the target contains a branching agent in step (d).
  • a target amount of branching agent is introduced in step (a) in order to obtain a branched polycarbonate having a high rate, it can be obtained in step (d) due to the influence of residence time from step (a) to step (d).
  • the increase in the content of the branching agent in the polycarbonate in the reaction liquid containing the polycarbonate gradually proceeds and reaches a certain content after a predetermined time from the start of the increase. Since the branching agent is trifunctional or higher, when producing the unbranched polycarbonate, the molecular weight of the branched polycarbonate obtained in the step (d) is not changed unless the amount of the terminal stopper used in the step (d) is changed. It will increase. Therefore, it is necessary to prevent the molecular weight from increasing by increasing the amount of the end terminator used in the step (d).
  • step (d) When the amount of the end terminator used in this step (d) is increased to the amount of the end terminator which becomes the target molecular weight at a time, the fluctuation of the molecular weight of the transition product becomes large and has a certain molecular weight range. This results in the inability to obtain a transitional product.
  • step (d) if the timing of increasing the amount of the end terminator used in step (d) is delayed, the molecular weight increases rapidly, adversely affecting equipment such as pumps and motors used for transfer and agitation, and a manufacturing apparatus. There is also a risk of causing a malfunction. Accordingly, it is necessary to increase the amount of the end terminator in the step (d) in a plurality of stages.
  • the plurality of stages are desirably two or more stages, preferably three or more stages, and more preferably four or more stages.
  • the amount may be continuously increased until the target amount of the end stopper is reached.
  • the increase in the initial stage of the end terminator in the step (d) is that the branching agent content of the polycarbonate in the reaction solution containing the polycarbonate obtained in the step (d) is relative to the target branching agent content.
  • the ratio is preferably up to 30%, preferably up to 25%.
  • the starting point of the increase in the branching agent content of the polycarbonate in the reaction liquid containing the polycarbonate obtained in the step (d) is from the addition position of the branching agent [step (a)] to the inlet to the step (d).
  • the residence time can be calculated and obtained.
  • the branching agent content in the branched polycarbonate after switching or before switching is:
  • the content is usually constant, preferably 0.2 to 3.0 mol%, more preferably 0.5 to 2.0 mol%, and 0.8 to 1.0 mol%. Is more preferable.
  • the content of the branching agent refers to the total mol of the structural unit derived from the dihydric phenol used as a raw material, the structural unit derived from the terminal terminator, and the structural unit derived from the branching agent, contained in the entire PC resin.
  • the mol% of the structural unit derived from the branching agent with respect to the number, that is, the content of the branching agent (mol%) is [the structural unit derived from the branching agent (mol) / [the structural unit derived from the dihydric phenol (mol) + terminal termination.
  • Each of the structural units (mol) can be measured by 1 H-NMR by separating the reaction solution containing the polycarbonate obtained in step (d).
  • the target molecular weight may not be achieved even if the introduction of the branching agent is stopped. In this case, it is necessary to increase the terminal terminator, but it is preferable to increase the terminal terminator in a plurality of stages.
  • a branched polycarbonate is produced by switching from a reaction solution containing unbranched polycarbonate to a reaction solution containing branched polycarbonate, or a reaction solution containing branched polycarbonate is changed to a reaction solution containing unbranched polycarbonate.
  • a transition product having a low branching agent content is generated at the time of switching between the two, but the fluctuation range of the molecular weight of the transition product can be reduced. Therefore, the molecular weight of the transition product can be within the target range, and the fluctuation range of the viscosity average molecular weight can be within the range of ⁇ 10%.
  • a reaction liquid containing polycarbonate is obtained by steps (a) to (d).
  • the aqueous phase containing the unreacted dihydric phenol from the following process (e) is alkaline aqueous solution of the bihydric phenol added to a process (b).
  • the step (e) will be described.
  • Step (e) is a step of separating the reaction solution containing the polycarbonate obtained in the step (d) into an organic solvent phase containing polycarbonate and an aqueous phase containing unreacted dihydric phenol.
  • Examples of the equipment used for the separation in this step (e) include a stationary separation tank and a centrifuge.
  • the organic solvent phase containing polycarbonate separated in the step (e) can be made into an organic solvent phase containing purified polycarbonate by performing alkali washing, acid washing and pure water washing in order.
  • the organic solvent phase containing the purified polycarbonate can be concentrated as necessary to obtain an organic solvent solution containing the purified polycarbonate, which can be kneaded or subjected to hot water granulation to obtain a polycarbonate powder.
  • a polycarbonate powder from which the organic solvent has been removed can be obtained by performing a drying treatment such as a heat treatment.
  • the obtained polycarbonate powder can be pelletized using a pelletizer or the like to form various molded bodies.
  • polycarbonate production method of the present invention three types of unbranched polycarbonate powder, polycarbonate transition product powder, and branched polycarbonate powder are produced in succession.
  • Polycarbonate transition product powder generated when changing from non-branched polycarbonate production to production of branched polycarbonate and when changing from branched polycarbonate production to non-branched polycarbonate production transfers the transition product powder to the container for the transition product. Is done.
  • the branched polycarbonate powder having a certain branching agent content is transferred to a container for the branched polycarbonate. In this way, by transferring the polycarbonate transition product powder only to the transition product container, a polycarbonate containing only the transition product powder can be obtained.
  • the container for transition products may contain some degree of unbranched polycarbonate powder before and after transition and branched polycarbonate powder having a certain branching agent content. Since the branching agent content is different in the upper layer portion, middle layer portion, and lower layer portion in the transition product container, a portion of the branching agent is taken out from the container or from the container and stirred uniformly to maintain a certain low branching agent.
  • a branched polycarbonate powder having a content rate can be used, or a branched polycarbonate powder having a high branching agent content can be mixed to increase the branching agent content.
  • the weight average molecular weight (Mw) was determined by using THF (tetrahydrofuran) as a developing solvent, GPC [column: TOSOH TSK-GEL MULTIPIORE HXL-M (2) + Shodex KF801 (1), temperature 40 ° C., flow rate 1.0 mL / Minute, detector: RI], and measured as a standard polystyrene equivalent molecular weight (weight average molecular weight: Mw).
  • Branching agent content (mol%) [constituent unit derived from branching agent (mol) / [constituent unit derived from dihydric phenol (mol) + constituent unit derived from terminal terminator (mol) + constituent unit derived from branching agent ( mol)]] ⁇ 100
  • Example 1 The steps from the step (a) of obtaining a reaction solution by phosgenation reaction to the step (e) of obtaining an organic solvent phase containing an unbranched polycarbonate were produced according to the flow shown in FIG. First, a 6.0% by mass sodium hydroxide aqueous solution was prepared, and further bisphenol A (BPA) was dissolved therein to prepare a 13.5% by mass (converted to solid matter) BPA sodium hydroxide aqueous solution. Next, p-tert-butylphenol (PTBP) was dissolved in methylene chloride to prepare a 24 mass% solution.
  • BPA bisphenol A
  • PTBP p-tert-butylphenol
  • Step (a) Subsequently, the above-mentioned BPA sodium hydroxide aqueous solution was flowed at a flow rate of 36 liters / hr, methylene chloride at a flow rate of 15.4 liters / hr, and PTBP solution at 310 ml / hr into a tubular reactor having an inner diameter of 6 mm and a length of 26 m.
  • phosgene was continuously blown at a flow rate of 3.1 kg / hr to perform a phosgenation reaction to obtain a reaction solution containing a phosgenation reaction product.
  • phosgene was separately synthesized from carbon monoxide (CO) and chlorine (Cl 2 ).
  • Step (b) and Step (c) Subsequently, the reaction solution and 210 ml / hr of a 3% by mass aqueous solution of triethylamine (TEA) prepared in advance as a catalyst were continuously supplied to an oligomerization reactor having a stirrer with an internal volume of 100 liters, which will be described later. Then, 15.7 liters / hr of the recycled aqueous phase obtained from the separation step (e) was introduced to carry out the oligomerization reaction.
  • TAA triethylamine
  • the BPA concentration in the aqueous phase before being introduced into the oligomerization reactor [the recycled aqueous phase obtained from the separation step (e) and the aqueous phase after merging water additionally introduced for concentration adjustment]
  • the sodium hydroxide concentration was 0.13 mol / liter, and the sodium carbonate concentration was 0.08 mol / liter.
  • the inside of this oligomerization reactor was rotated at 350 rpm, and the oligomerization reaction was performed in a laminar flow state.
  • the reaction liquid containing the polycarbonate oligomer extracted from the bottom of the oligomerization reactor was passed through a transfer pipe [manufactured by SUS, pipe diameter 12.7 mm (1/2 inch)], a horizontal stationary separation tank (inner diameter 350 mm, internal volume 100). Liter) was continuously fed to separate the aqueous phase from the organic solvent phase containing the polycarbonate oligomer.
  • the organic solvent phase was continuously withdrawn from the horizontal stationary separation tank at a flow rate of 20 l / hr, and the chloroformate group concentration in the withdrawn organic solvent phase was 0.72 mol / l.
  • Step (d) (Production of unbranched polycarbonate) A polycondensation reaction was performed in the step (d) using an organic solvent phase (may be abbreviated as PCO) containing a polycarbonate oligomer separated from the horizontal stationary separation tank.
  • the organic solvent phase (PCO) containing the polycarbonate oligomer is 20 liter / hr
  • the sodium hydroxide solution of bisphenol A (used for the production of the polycarbonate oligomer) is 9.8 liter / hr
  • concentration is 3% by weight of triethylamine as a catalyst.
  • the polycondensation reaction was carried out by introducing into the polycondensation reactor of step (d) at a flow rate of hr.
  • the reactor used for the polycondensation reactor two reactors, a line mixer and a tower reactor, were used.
  • Step (e) [Steps from step (e) to production of polycarbonate powder]
  • the reaction mixture overflowing from the upper part of the tower reactor serving as the outlet of the step (d) was allowed to stand and separated into an aqueous phase and an organic solvent phase containing polycarbonate (step (e)).
  • the entire amount of the aqueous phase separated in step (e) was introduced into the oligomerization reactor in step (b) and recycled.
  • the obtained organic solvent phase was washed with a sodium hydroxide aqueous solution adjusted to a pH of 13.5, a hydrochloric acid aqueous solution adjusted to a pH of 1.5, and pure water in order to obtain a clear polycarbonate.
  • a methylene chloride solution was obtained.
  • the methylene chloride in the methylene chloride solution of the obtained polycarbonate was removed by evaporation using a kneader to obtain a polycarbonate powder. Further, residual methylene chloride was removed by heating to 100 ppm or less, and white polycarbonate powder (BPA homopolycarbonate powder) was obtained at 8 kg / hr. It was 23,000 when the viscosity average molecular weight (Mv) was measured about this powder. The homopolycarbonate powder thus obtained was transferred to a homopolycarbonate container.
  • branched polycarbonate After the unbranched polycarbonate was produced continuously for 12 hours, the branched polycarbonate was produced along the flow shown in FIG.
  • the target of the viscosity average molecular weight (Mv) of the branched polycarbonate was set to 23,000, the same as that of the BPA homopolycarbonate, and the viscosity average molecular weight of the generated transition product was also set to 23,000.
  • the average residence time from the step (a) to the inlet of the step (d) is 3.8 hours, and the residence time from the step (d) to obtaining the white polycarbonate powder after heating and drying is 10 hours.
  • the polycarbonate powder obtained in a total of 13.8 hours after the introduction of the branching agent in the step (a) is mainly the BPA obtained before introducing the branching agent in the step (a).
  • the product was produced as a homopolycarbonate powder and transferred to a homopolycarbonate container.
  • THPE 1,1,1-tris (4-hydroxyphenyl) ethane
  • the PTBP solution introduced into step (d) is increased to 0.18 liter / hr 1.1 hours after the start of THPE introduction in step (a), and then 2.2 hours after the start of THPE introduction. 0.22 liter / hr, after 3.3 hours, 0.26 liter / hr, after 4.5 hours, 0.31 liter / hr, after 6.6 hours, 0.34 liter / hr.
  • the reaction was carried out with the amount increased.
  • the reaction solution obtained from the step (d) was treated in the same manner as described in the steps from the step (e) to the production of the polycarbonate powder.
  • the reaction solution obtained from step (d) was separated every other hour until 14 hours after the start of introduction of THPE in step (a), and separated into an organic phase and an aqueous phase.
  • the viscosity average molecular weight of the polycarbonate was measured.
  • the fluctuation range was ⁇ 2.6 to + 1.7% with respect to the target Mv (23,000).
  • the measurement results are shown in Table 1.
  • the polycarbonate powder obtained in 13.8 hours after the introduction of the branching agent in step (a) is a homopolycarbonate powder.
  • Example 2 In Example 1, during the production of the branched polycarbonate, in step (d), 2 hours after the start of introduction of THPE, the PTBP solution introduced into step (d) was increased to 0.20 liter / hr, and then THPE was introduced. Example 1 except that the introduction amount of the PTBP solution was increased stepwise in three stages, 0.27 liter / hr 3.5 hours after the start of introduction and 0.34 liter / hr after 6 hours. It carried out similarly. The results are shown in Table 1.
  • Example 1 in the production of the branched polycarbonate, the PTBP solution introduced into the step (d) was introduced into the target amount of 0.34 two hours after the introduction of THPE in the step (a). The same operation as in Example 1 was performed except that the amount was increased to 1 liter / hr. The results are shown in Table 1.
  • Example 2 in the production of the branched polycarbonate, the PTBP solution introduced into the step (d) was introduced into the target amount of 3.2 hours after the introduction of THPE in the step (a) and 3.2 hours later. The same procedure as in Example 1 was performed except that the amount was increased to 34 liters / hr. The results are shown in Table 1.
  • the transition width of the viscosity average molecular weight of the obtained polycarbonate powder of the transition product is ⁇ 2.6 to + 1.7% in Example 1, and ⁇ 4 in Example 2. It is within ⁇ 10% at 3 to + 8.3%, and is within a range exceeding ⁇ 10% at ⁇ 16.1 to + 8.3% in Comparative Example 1 and from ⁇ 11.7 to + 18.3% in Comparative Example 2. It is shown.
  • the reaction liquid containing a polycarbonate with a small fluctuation range with respect to the target value of a viscosity average molecular weight is obtained by the process (d). It is shown.
  • Comparative Examples 1 and 2 it is shown that a reaction liquid containing polycarbonate having a large fluctuation range with respect to the target value of the viscosity average molecular weight is obtained.
  • the polycarbonate production method of the present invention when switching from the production of unbranched polycarbonate to the production of branched polycarbonate by introducing a branching agent, or by stopping the introduction of the branching agent from the production of branched polycarbonate, When the production is switched to, a polycarbonate having a small change in the molecular weight of the transferred product can be obtained, so that the molecular weight of the transferred product can be easily controlled within the target molecular weight range.

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  • Polymers & Plastics (AREA)
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Abstract

L'invention concerne un procédé de production d'un polycarbonate, qui comprend une étape a) au cours de laquelle est effectuée une réaction de phosgénation pour obtenir un mélange de réaction liquide, une étape (b) au cours de laquelle est obtenu un mélange de réaction liquide contenant un oligomère de polycarbonate, une étape (c) au cours de laquelle le mélange de réaction liquide est séparé en une phase de solvant organique contenant l'oligomère de polycarbonate et une phase aqueuse, et une étape (d) au cours de laquelle la phase de solvant organique contenant l'oligomère de polycarbonate, une solution aqueuse alcaline d'un phénol dihydrique, et un terminateur de chaîne sont mis à réagir pour obtenir un mélange de réaction liquide contenant un polycarbonate, et au cours de laquelle le mélange de réaction liquide contenant un polycarbonate est commuté d'un mélange de réaction liquide contenant un polycarbonate non ramifié en un mélange de réaction liquide contenant un polycarbonate ramifié ou commuté d'un mélange de réaction liquide contenant un polycarbonate ramifié en un mélange de réaction liquide contenant un polycarbonate non ramifié, la quantité de terminateur de chaîne à introduire dans l'étape d) étant augmentée ou réduite dans une pluralité d'étages.
PCT/JP2015/085880 2014-12-25 2015-12-22 Procédé de production de polycarbonate WO2016104532A1 (fr)

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CN111440304A (zh) * 2020-03-27 2020-07-24 聊城鲁西聚碳酸酯有限公司 光气界面缩聚法pc低聚物废液回收利用的系统及方法

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JPH07278286A (ja) * 1994-04-13 1995-10-24 Idemitsu Petrochem Co Ltd ポリカーボネート重合体及びその製造方法
JP2005336332A (ja) * 2004-05-27 2005-12-08 Teijin Chem Ltd 分岐状ポリカーボネート樹脂の製造方法
JP2009074064A (ja) * 2007-08-28 2009-04-09 Mitsubishi Chemicals Corp 芳香族ポリカーボネート樹脂の製造方法
JP2009249546A (ja) * 2008-04-08 2009-10-29 Mitsubishi Chemicals Corp ポリカーボネート樹脂の製造方法
JP2011246628A (ja) * 2010-05-27 2011-12-08 Mitsubishi Chemicals Corp 芳香族ポリカーボネート樹脂の製造方法

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Publication number Priority date Publication date Assignee Title
JPH07278286A (ja) * 1994-04-13 1995-10-24 Idemitsu Petrochem Co Ltd ポリカーボネート重合体及びその製造方法
JP2005336332A (ja) * 2004-05-27 2005-12-08 Teijin Chem Ltd 分岐状ポリカーボネート樹脂の製造方法
JP2009074064A (ja) * 2007-08-28 2009-04-09 Mitsubishi Chemicals Corp 芳香族ポリカーボネート樹脂の製造方法
JP2009249546A (ja) * 2008-04-08 2009-10-29 Mitsubishi Chemicals Corp ポリカーボネート樹脂の製造方法
JP2011246628A (ja) * 2010-05-27 2011-12-08 Mitsubishi Chemicals Corp 芳香族ポリカーボネート樹脂の製造方法

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111440304A (zh) * 2020-03-27 2020-07-24 聊城鲁西聚碳酸酯有限公司 光气界面缩聚法pc低聚物废液回收利用的系统及方法

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