WO2002042355A1 - Procede de production de polycarbonate - Google Patents

Procede de production de polycarbonate Download PDF

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Publication number
WO2002042355A1
WO2002042355A1 PCT/JP2001/010163 JP0110163W WO0242355A1 WO 2002042355 A1 WO2002042355 A1 WO 2002042355A1 JP 0110163 W JP0110163 W JP 0110163W WO 0242355 A1 WO0242355 A1 WO 0242355A1
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polycarbonate
group
bis
prepolymer
compound
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PCT/JP2001/010163
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English (en)
Japanese (ja)
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Mitsunori Ito
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Idemitsu Petrochemical Co., Ltd.
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Publication of WO2002042355A1 publication Critical patent/WO2002042355A1/fr

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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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids

Definitions

  • the present invention relates to a method for producing polycarbonate. More specifically, the present invention relates to a method for producing a polycarbonate having excellent thermal stability.
  • Polycarbonate is used in a wide range of industrial fields as an engineering plastic.
  • the method for producing this polycarbonate includes an interfacial polymerization method in which an aromatic dihydroxy compound such as 2,2-bis (4-hydroxypropyl) propane is directly reacted with phosgene, and a method for producing 2,2-bis.
  • the melt polymerization method does not have the same problems as the interfacial polymerization method, but in the production process, it removes the hydroxy compound and the carbonic acid diester from the high-viscosity polycarbonate melt, so that high temperature and high temperature are required. It is necessary to perform the reaction for a long time under vacuum. Therefore, special equipment that can withstand long-term reactions under high temperature and high vacuum as production equipment, Due to the high viscosity of the product, a particularly powerful stirring device is required.
  • the resulting product polycarbonate has a branched structure and a cross-linked structure due to side reactions accompanying the reaction at high temperatures, resulting in poor quality and poor stability and prolonged residence at high temperatures. There is a problem that coloring is easier.
  • the polycarbonate obtained by this melt polymerization method has a high content of low molecular weight components such as residual monomeric acetone soluble components, which results in a reduction in impact strength and a reduction in metallurgy during molding. There is a problem of adhesion to the mold surface.
  • the solid-state polymerization method can solve the problems of the melt polymerization method, there is a problem in the crystallization step of the amorphous prepolymer when preparing the polycarbonate prevolimer in the production process.
  • the amorphous prepolymer obtained here has a melting point lower than the polymerization temperature at which solid-state polymerization can be performed. Become. Therefore, when performing polymerization in the solid state, it is necessary to crystallize this amorphous prepolymer in advance.
  • the method for crystallizing the prepolymer for example, in Japanese Patent Application Laid-Open No.
  • An object of the present invention is to provide a method for producing a polycarbonate having substantially no residual solvent and excellent in thermal stability.
  • the present inventor has found that in a method for producing polycarbonate by solid-state polymerization of polycarbonate prepolymer, the polycarbonate prepolymer is converted to a liquid, subcritical or It has been found that the above object can be achieved by solid phase polymerization after contacting with supercritical carbon dioxide for crystallization, and the present invention has been completed based on these findings.
  • the gist of the present invention is as follows.
  • the crystal is obtained by contacting the polycarbonate prepolymer with carbon dioxide in a liquid, subcritical or supercritical state. And then subjecting the solid phase polymerization to a method for producing polycarbonate.
  • Polycarbonate prepolymer is crystallized by contacting it with liquid, subcritical or supercritical carbon dioxide and then depressurized.
  • the present invention provides a method for producing a polypropionate by increasing the molecular weight of a polycarbonate prepolymer in a solid state, by contacting the polycarbonate prepolymer with carbon dioxide in a liquid, subcritical or supercritical state.
  • This is a method for producing polycarbonate, which comprises crystallizing and then performing solid-phase polymerization. Therefore, the method for producing the polycarbonate of the present invention comprises: (1) a step of preparing a polycarbonate prepolymer, (2) a step of crystallizing the prepolymer, and (3) a solid phase polymerization step. It is a manufacturing method of.
  • the polymerization method for the step of preparing the polystyrene prepolymer may be a conventional interfacial polymerization reaction, a method based on an oxidative carbonylation reaction between a dihydroxy compound and carbon monoxide.
  • a method capable of producing a polycarbonate prepolymer such as a method based on a reaction between a dihydroxy compound and carbon dioxide or a melt polymerization method based on an ester exchange reaction may be employed.
  • non-halogen solvents such as ether solvents such as tetrahydrofuran, paraxylene, toluene, etc. It is desirable to carry out the interfacial polymerization reaction using a hydrocarbon solvent or a ketone solvent such as methylethyl ketone.
  • polycarbonate prepolymers were prepared by the reaction of dihydroxy compounds with carbon monoxide or carbon dioxide.
  • a dihydroxy compound and (b) a carbonic acid diester are used as raw materials, and if necessary, (c) a terminal stopper or ( d) Prepare a prepolymer by using a branching agent and (e) an antioxidant.
  • a nitrogen-containing organic basic compound is suitably used as a polymerization catalyst.
  • the dihydroxy compound used as a raw material in the present invention there are an aromatic dihydroxy compound and an aliphatic dihydroxy compound. Of these, an aromatic dihydroxy compound is preferable, and an aliphatic dihydroxy compound is used. In this case, it is preferable to use the mixture with an aromatic dihydroxy compound.
  • the aromatic dihydroxy compound is represented by the general formula (1)
  • R 1 and R 2 each independently represent a halogen atom, an alkyl group having 1 to 8 carbon atoms or a phenyl group, and m and n each represent 0 to 4 Indicates an integer.
  • 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, one S-, - SO-, - S 0 2 -, one O-, one CO- or formula (2) is properly following formula (3)
  • the halogen atom represented by R 1 and R 2 may be any of a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and may have 1 to 8 carbon atoms.
  • the alkyl group include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, t-butyl, pentyl, hexyl, and cyclyl. Examples include a hexyl group, a heptyl group and an octyl group.
  • the alkylene group having 1 to 8 carbon atoms and the alkylidene group having 2 to 8 carbon atoms represented by Z in the formula include methylene group, ethylene group, propylene group, butylene group, pentylene group, hexylene group, Examples include an ethylidene group and an isopropylidene group.
  • cycloalkyl having 5 to 15 carbon atoms The cycloalkylidene group having 5 to 15 carbon atoms includes a cyclopentylene group, a cyclohexylene group, a cyclopentylidene group, a cyclohexylidene group and the like.
  • Examples of the aromatic dihydroxy compound represented by the general formula (1) include bis (4-hydroxyphenyl) methane, bis (3-methyl-4-hydroxyphenyl) methane, and bis (3 —Cro- mouth-1 4 —Hydroxyphenyl) methane, bis (3,5_dibromo-14-hydroxyphene) methane, 1,1 —Bis (4-hydroxyphenyl) phene-noremetan, 1, 1-bis (2-hydroxybutyrene), 1, 1-bis (2-t-butynole) 4-bis-doxy-3-methinolephenylethane, 1,1-bis (2-t-butynole 4-) Hydroxy 1 3 — methinolephne 1, 1 — fujinole 1, 1 — bis (3 — fuzoreo 1 4 — hydroxy 1 5 — methinolephne 2) bis, 2, 2 _ bis
  • aromatic dihydroxy compounds represented by the general formula (1) 2,2-bis (4-hydroxypheninole) propane (hereinafter sometimes abbreviated as bisphenol) may be used. Is a particularly preferred compound.
  • aromatic dihydroxy compound other than the compound represented by the general formula (1) include, for example, resorcin, 3-methylresorcin, 3-ethylinoresolenosin, and 3-propinoresolezolesin.
  • ethoxylated or propoxylated dihydric alcohols and phenols for example, bis-oxicetyl bispheno-I / re A, bis-ioxicetinole-tetrachlorobisphenenole A, bis-oxenose / letetrachlorohydroquinone And the like.
  • diesters of dihydroxy compounds such as diester acetate of bisphenol A, diester of dipropionate of bisphenol A, diester of dibutylate of bisphenol A, dibenzoate of bisphenol A, and diesters of bisphenol are also available.
  • Dicarbonates of dihydroxy compounds such as bis-methylenoleate carbonate of bisphenol A, bisphenolate carbonate of bisphenol A, bisphenyl carbonate ester of bisphenol A, bisphenol A monomethyl carbonate, and bisphenol A monomethyl carbonate
  • ester include monocarbonates of dihydroxy compounds such as esters, bisphenol A monopropynole carbonate, and bisphenol A monophenyl carbonate.
  • aliphatic dihydric Dorokishi compounds such as butane one 1, 4-diol, 2, 2 - dimethyl Pro Bruno, 0 down _ 1, 3 - diol key monobasic 1 to, 6 - Jionore, diethylene glycidyl Cole, triethylene glycol / tetraethylene glycol, octaethylene glycol cone, dipropylene glycol ⁇ ⁇ , ⁇ , ⁇ -methinoresietananolamine, cyclo Hexane-1,3-diolone, cyclohexane-1,4-diol, .1,4-dimethylolcyclohexane, p-xylylene glycol, 2,2-bis (4-hydroxycyclo) Hexyl) propane and the like.
  • diester carbonate for example, at least one compound selected from diaryl carbonate compounds, dialkyl carbonate compounds and alkylaryl carbonate compounds can be used.
  • the diaryl carbonate compound has the general formula (4)
  • a r ', A r 2 are each independently a ⁇ re Ichiru group, their these may be the same or different from each other.
  • Ar 3 and Ar 4 each independently represent an aryl group, which may be the same or different, and D 1 is the aromatic diphenyl group. This shows the residue obtained by removing two hydroxyl groups from the hydroxy compound. ] It is a compound represented by these.
  • the dialkyl carbonate compound has the general formula (6)
  • R 3 and R 4 each independently represent an alkyl group having 1 to 6 carbon atoms or a cycloalkyl group having 4 to 7 carbon atoms, which may be the same or different.
  • R 5 and R 6 each independently represent an alkyl group having 1 to 6 carbon atoms or a cycloalkyl group having 4 to 7 carbon atoms, which may be the same or different from each other; D 2 represents the aromatic dihydric Dorokishi compounds force 3 et two hydroxyl excluding residues. ] It is a compound represented by these.
  • Ar 5 represents an aryl group
  • R 7 represents an alkyl group having 1 to 6 carbon atoms or a cycloalkyl group having 4 to 7 carbon atoms.
  • Ar 6 represents an aryl group
  • R 8 represents an alkyl group having 1 to 6 carbon atoms or a cycloalkyl group having 4 to 7 carbon atoms
  • D 3 represents the aromatic dihydroxy compound. Shows the residue from which two hydroxyl groups have been removed. ] It is a compound represented by these.
  • ⁇ Li represented A r ' ⁇ A r 6 in the general formulas (4) - (9) - is as Honoré group, phenyl group, preparative drill group, xylyl group, naphthyl group, etc. click Rejiru group and the like
  • Examples of the alkyl group having 1 to 6 carbon atoms or the alkyl group having 4 to 7 carbon atoms represented by R 3 to R 8 include a methyl group, an ethyl group, an n_propyl group, an isopropyl group, Examples include n-butyl group, isobutyl group, sec-butyl group, t-butyl group, pentyl group, hexyl group, and cyclohexyl group.
  • the diaryl carbonate compounds include, for example, diphenyl carbonate, di-trinore carbonate, bis (clo-fernole) carbonate, m-cresyl carb, dinaphthyl carb, Bis (carbon) carbonate, bis phenol (A), bis bon bon (bonus), etc.
  • dialkyl carbonate compound examples include, for example, getylcapone, dimethylcarbonate, dibutylcarbonate, and dicyclohexane.
  • Silk carbonate bisphenol A bismethyl carbonate, and the like.
  • alkylaryl carbonate compound examples include, for example, methylpheninole carbonate, echinolefe-norrecarbonate, fu, 'tinolefeninole carbonate, cyclohexinolefeninolecarbonate, and bisphenol A methylphenyl carbonate. And the like.
  • one or more compounds selected from the above compounds can be used, and among these, diphenyl carbonate is particularly preferable.
  • examples of the terminal terminator include o_ ⁇ -butylphenol, m— ⁇ —butynolepheno, ⁇ — ⁇ —butizolepheno / re, ⁇ —isobtinolenoenole, m—isobutinolepheno
  • p I sobutinorefeno, one o, t — Petinolefe nonore, m — t — Bu, Chi / Refue nonole, ⁇ — t — Butinolefenogre, o — n — Pentinolefeno one, m — n — pliers / refnole, p— n — pentynolephenore, o—n—hexinolephenore, m—n—hexinolephenore, p—n—hexenolepheno, o—cyclone M-cyclohexyl /
  • a polyfunctional organic compound having three or more functional groups is used as a branching agent.
  • a compound having three or more functional groups such as a hydroxyl group, a carboxyl group, an amino group, an imino group, a formyl group, an acid halide group, and a haloformate group in one compound is preferably used.
  • branching agents include, for example, phloroglucin, meritic acid, trimellitic acid, trimellitic chloride, trimellitic anhydride, N-propyl gallic acid, n-propyl gallate, procatechuic acid, pyromellitic acid, pyromellitic dianhydride, ⁇ _resorcinic acid,) 3-resorcinic acid, resorcinaldehyde, trimethyllic acid , Trimethyltrichloride, 4-chloroformylphthalic anhydride, benzophenone tetracarboxylic acid olevonic acid, 2,4,4'-trihydroxybenzobenzophenone, 2,2 ', 4,4' -Tetrahydroxybenzophenone, 2,4,4 '-Trihydroxyhydroxyenoline, 2,2', 4,4 '-Tetrahydroxyphenyrene, 2,4,4 '— Tridroxydifie -Noreichi 2 — Purono ⁇ 0 emissions, 2, 2 '
  • antioxidant a phosphorus-based antioxidant is preferable, for example, trianolalkyl phosphite, tricycloalkyl phosphite, triaryl phosphite, monoalkyl Preferred are, for example, phosphoryl phosphate, triphosphorinol phosphate, trichloroanolequinol phosphate, and triphenyl phosphate.
  • examples of the nitrogen-containing organic basic compound used as a catalyst in the reaction between the dihydroxy compound and the carbonic acid diester include an aliphatic tertiary amine compound, an aromatic tertiary amine compound, and a nitrogen-containing complex. Ring compounds and the like.
  • R 9 represents a hydrocarbon group
  • X 1 represents a halogen atom, a hydroxyl group, an alkyloxy group, an aryloxy group or a monovalent anion-forming group.
  • the hydrocarbon group represented by R 9 includes an alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group and an octyl group, and a cyclopentyl group and a hexyl group.
  • aryl groups such as aryl groups such as cycloalkyl groups, phenyl groups, tolyl groups, naphthyl groups, and bifuunyl groups, and benzyl groups.
  • These four R 9 's may be the same or different from each other, or two R 9' s may combine to form a ring structure.
  • Examples of these quaternary ammonium salts include alkyl groups such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrabutylammonium hydroxide, trimethylbenzylammonium hydroxide, and aryl groups.
  • Examples include basic salts such as borate.
  • nitrogen-containing organic basic compounds tetramethylammonium hydroxide, tetraptylammonium hydroxide, tetramethylammonium borohydride and tetrabutylammonium borohydride are preferable. Particularly, tetramethylammonium hydroxide is preferred. Because these compounds have high catalytic activity and are easy to thermally decompose, they are unlikely to remain in polycarbonate. These nitrogen-containing organic basic compounds may be used alone or in a combination of two or more.
  • a raw material dihydroxy compound and a carbonic acid diester and if necessary, a terminating agent, a branching agent, an antioxidant, and the like are added, and the mixture is heated and treated to obtain an aromatic compound.
  • Polycarbonate prepolymer can be prepared while the group monohydroxy compound is eliminated. And this pre-bollima made It is preferable that the viscosity average molecular weight of the prepolymer obtained in the manufacturing process be in the range of 2,000 to 20,000.
  • the above nitrogen-containing organic basic compound is used as a polymerization catalyst.
  • a phosphorus-containing basic compound of a catalyst for solid phase polymerization described later may be added.
  • the phosphorus-containing basic compound is dispersed and remains in the formed poly-carbonate prepolymer, and is used as a catalyst in the subsequent solid-phase polymerization.
  • the reaction it is preferable to carry out the reaction without using any solvent.
  • the solvent include diphenyl ether, nodogen genji jifeninole ethere, benzophenone, benzophenone, polyphenylene ether, and diphenyl ether.
  • aromatic compounds such as chlorobenzene and methylnaphthalene
  • gases such as carbon dioxide, nitrous oxide and nitrogen (including supercritical state); alkanes such as fluorofluorohydrocarbons, ethane and propane; Solvents that are inert to the reaction of cycloalkanes such as xane, tricyclo (5,2,10) decane, cyclooctane, and cyclodecane, and alkenes such as ethylene and propylene can be used.
  • gases such as carbon dioxide, nitrous oxide and nitrogen (including supercritical state)
  • alkanes such as fluorofluorohydrocarbons, ethane and propane
  • Solvents that are inert to the reaction of cycloalkanes such as xane, tricyclo (5,2,10) decane, cyclooctane, and cyclodecane, and alkenes such as ethylene and propylene
  • the ratio of the starting material hydroxy compound to the carbonate diester varies depending on the type of compound used, the reaction temperature, the reaction pressure, and other reaction conditions.However, the diester carbonate is based on 1 mole of the dihydroxy compound. It is usually used at a ratio of 0.9 to 2.5 mol, preferably 0.95 to 2.0 mol, more preferably 0.98 to 1.5 mol.
  • the terminal stopping agent is used with respect to 1 mol of the dihydroxy compound.
  • the branching agent is a dihydroxy compound. It is used in an amount of usually from 0.001 to 20 mol, preferably from 0.0025 to 15 mol, more preferably from 0.005 to 10 mol, per 1 mol.
  • yo Ri favored properly is 1 0- 3 ⁇ ; I 0 - 7 use a molar Rere Is desirable. If the amount of the catalyst used is less than 10 to 8 mol, the catalytic activity in the initial stage of the reaction may be insufficient, and if it is more than 10 to 2 mol, the quality of the polycarbonate is deteriorated and economic disadvantages occur. It is not desirable because it may be.
  • the reaction temperature, reaction pressure, and reaction time vary depending on various conditions such as the type of the starting compound used, the type of the catalyst and the amount used thereof, and the molecular weight required for the obtained prepolymer.
  • the reaction time is selected in the range of 1 minute to 100 hours, preferably 2 minutes to 10 hours. In setting these reaction conditions, it is desirable to carry out this reaction at a temperature as low as possible and in a short time so as to avoid coloring of the prepolymer.
  • a reactor used in the prepolymer production step a conventionally known polymerization reactor can be used. This reaction step may be performed in one step or may be performed by dividing into more steps. When a plurality of reactors are used, the reactors can be connected in series or in parallel.
  • the prepolymer may be manufactured by a batch method, a continuous method, or a method using both of them.
  • the hydroxyl group is added to the aryl group of the polyester carbonate as the reaction proceeds. To form an aromatic monohydroxyl compound in the form of a bond.
  • the reaction rate can be increased by removing the generated aromatic monohydroxy compound out of the reaction system.
  • an inert gas such as nitrogen gas, argon gas, helium gas or carbon dioxide or a lower hydrocarbon gas is introduced to convert the generated aromatic monohydroxy compound into these. It is advisable to remove with accompanying gas.
  • the pressure in the reactor may be reduced to reduce the pressure of the aromatic monohydroxyl compound, and the pressure in the reactor may be reduced to introduce the above-mentioned inert gas and the like, thereby obtaining the aromatic monohydroxyl compound.
  • the compound may be removed.
  • Polycarbonate prepolymers thus obtained include those in which the chemical structure at the molecular chain end is phenyl carbonate or phenolic carbonate having a hydroxyl group. Those having a phenylcarbamate terminal: hydroxyl terminal ratio of 1: 1 to 1: 0.1, preferably those having the same ratio of 1: 0.6 to 1: 0.25 are obtained.
  • the thus obtained polycarbonate prepolymer is mixed with liquid, subcritical or supercritical carbon dioxide, and the liquid, subcritical or supercritical carbon dioxide is decompressed. Crystallize by vaporizing and separating.
  • a method of mixing the polycarbonate prepolymer with carbon dioxide in a liquid, subcritical or supercritical state for example, a method in which molten polycarbonate prepolymer is passed through a line mixer is used. Then, liquefied carbon dioxide can be injected into the upstream pipe of the line mixer, and the polycarbonate prepolymer and liquefied carbon dioxide can be mixed in the line mixer.
  • solid-state polycarbonate pre-polymer is placed in the stirring tank. While stirring, carbon dioxide in a liquid, subcritical or supercritical state may be injected and mixed.
  • the inert gas include carbon dioxide gas, nitrogen gas, and argon gas. Among them, it is economical to circulate and use the carbon dioxide gas recovered after vaporization in the crystallization step using carbon dioxide in the production equipment.
  • the contact time between the polycarbonate prepolymer and carbon dioxide in a liquid, subcritical or supercritical state is 0.5 to 300 minutes, preferably 1 to 180 minutes. In this way, the mixture of the polycarbonate prepolymer that has been mixed and the liquid, subcritical or supercritical carbon dioxide is introduced into, for example, a flash drum, which is vaporized by reducing the pressure and flashing. To separate it from the polycarbonate prepolymer.
  • the degree of crystallinity of the polycarbonate prepolymer is 5 to 50%, and substantially.
  • a polycarbonate prevolimer containing no residual solvent can be obtained.
  • the crystallized polycarbonate prepolymer is subjected to solid-state polymerization.
  • the reaction is performed without using a catalyst or a polymerization catalyst.
  • the polymerization is carried out using a phosphorus-containing basic compound, preferably a quaternary phosphonium salt, as the polymerization catalyst.
  • This polymerization catalyst may be added in the step of preparing the polycarbonate prepolymer, or may be added in the step of crystallization.
  • This solid-phase polymerization step includes a method of performing in a solid state and a method of performing in a swollen solid state.Either method may be used. It is preferable because the amount of residual solvent is small and it is easy to obtain polycarbonate having excellent thermal stability.
  • the quaternary phosphonium salt used in the solid-phase polymerization is not particularly limited, but may be, for example, a compound represented by the following general formula (11) or (12)
  • R 10 represents an organic group, four R 10 s may be the same as or different from each other, and two R ′ ° are bonded to form a ring structure You can do it.
  • X 2 represents a halogen atom, a hydroxyl group, an alkyloxy group, an aryloxy group or a monovalent aion-forming group, and Y 1 represents a divalent anion-forming group.
  • examples of the organic group represented by R ′ ° include a methyl group, an ethyl group, a propyl group, a butyl group, a benzyl group, a hexyl group, and an octyl group.
  • Alkyl groups such as cycloalkyl groups, cycloalkyl groups such as cyclohexyl groups, aryl groups such as phenyl, tolyl, naphthyl and biphenyl groups, and arylalkyl groups such as benzyl. And the like.
  • quaternary phosphonium salts include, for example, tetrahydrophenyl phosphonium hydroxide, tetranaphthyl phosphonimuhydroxide, tetra (phenyl) phosphonimuhydroxide, tetra (biphenyl) phosphonimuhydroxide, tetratra Tetra (aryl) phosphonimide hydroxoxides, such as trinolephosphonium hydroxide, tetramethylphosphonium hydroxoxide, tetranolephosphonium hydroxoxide, and tetratrapinolephosphonium hydroxoxide ) Phosphonium hydroxides, tetramethylphosphoforme tetrafluorodiene / reporate, tetrafluorodiene / lephosphonium bromide, tetraphenylphosphonium phenolate, tetrafluorophenolate Sofunimute triphenyleneborate,
  • phosphonium salts having an alkyl group specifically, tetramethylphosphonium methyl triphenyl Volatile, tetraethylphosphonium methinolate revolinolate, tetrapropylphosphonium propyl triphenylborate, tetrabutylinolephosphonium butyrate / retriene / Reporate, tetrabutinolephos, homophenyl tetraphenylborate, tetraethylphosphonium tetraphenyl / reporate, trimethinoleethylphosphonium trimethylphenotrioleborate, trimethylinobenzene / rephospho Numerous benzene / retretinole borate and the like are particularly preferably used because they have high catalytic activity, are easily thermally decomposed, and hardly remain in polycarbonate.
  • tetraalkylphosphonium salts such as tetramethylphosphonium hydroxide, tetraethylphosphonium hydroxide, tetrabutylphosphonium hydroxide, etc. have relatively low decomposition temperatures, so that they are easily decomposed. However, there is little risk of remaining as impurities in the product's polycapsule. In addition, since these compounds have a small number of carbon atoms, the unit consumption in the production of polycarbonate can be reduced, which is preferable in terms of cost.
  • quaternary phosphonium salt having an aryl group and / or a branched alkyl group can also be used.
  • R 11 represents at least one group selected from an aryl group or a branched alkyl group
  • R 12 represents an alkyl group or an alkyl having a substituent.
  • X 3 has the same meaning as X 2
  • Y 2 has the same meaning as Y 1
  • n represents an integer of 1 to 4.
  • the branched alkyl group represented by R 11 in the above general formulas (13) and (14) has a chemical structure represented by R 3 C—, where R is a hydrogen atom, an alkyl group, At least one group selected from an alkyl group having a substituent, an aryl group and an aryl group having a substituent, and at least two groups except for two of the three Rs being a hydrogen atom May combine with each other to form a ring structure.
  • R is a hydrogen atom, an alkyl group, At least one group selected from an alkyl group having a substituent, an aryl group and an aryl group having a substituent, and at least two groups except for two of the three Rs being a hydrogen atom May combine with each other to form a ring structure.
  • Examples thereof include a branched alkyl group such as a cycloalkyl group, an isopropyl group, and a t-butyl group, and an arylalkyl group such as a
  • Examples of such a quaternary phosphonium salt include, for example, tetraphenyl phosphonium hydroxide, tetranaphthyl phosphonium hydroxide, tetra (phenyl) phosphonium hydroxide, tetra (biphenyl) phosphonium hydroxide, and tetrathoxide.
  • Tetra (aryl) phospho-demihydroxides and tetra (alkyl) phosphonimidoxides such as rilphosphonium hydroxide and tetrahexylphosphonium hydroxide, methyltriphenylphosphonidium hydroxide, ethyltriphenylphosphonide Muhidroxide, propinoletri-pheninolephosphonium hydroxide, butinoletri-fen-reno-phosphonium hydroxoxide, octinoletri-feninole-phospho-denuhydropoxide Sid, Te Toradeshiruto re-phenylalanine phosphonyl ⁇ Muhi Dorokishido, benzylidene belt Li Hue two Norre phosphonyl ⁇ Muhi Dorokishido, et butoxy benzylidene Roh Leto Li off Enizolephosphonium hydroxide, methoxymethy / retrifenolen
  • Mono (aryl) trianorex / lephos benzodihydroxides Mono (aryl) trianorex / lephos benzodihydroxides, dimethyldiphenylphosphonium hydroxide, getyl diphenylphosphonium hydroxide, di (biphenyl) phosphine benzodihydroxide
  • Nolephosphoniumte trifoenolevolate Bromomethinolate trifle-nolephosphoniumte trifurenorevolate, bifénénole triflenet / lephosphoniemute trifleine revolate, naphtinole trifleenolenolefolate ⁇ ⁇ Rate, black mouth ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ , ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ Mono (aryl) triphenyl phosphonimute traphenylborate and mono (anolequinolate), such as nijute trifunorevolate, naphthinorefeinole trifoieinole phosphonimute trafuinolevorate, etc.
  • an aryloxy group such as phenoxide, an alkyloxy group such as methoxide and ethoxide, and an alkylcarboxy group such as acetate.
  • quaternary phosphonium salts having a halogen atom such as an aryl carboxy / reoxy group such as benzoate and benzoate.
  • a compound having a divalent counter anion represented by the general formula (14) for example, bis (tetrafluoroquinonephosphonium) carbonate , Bis (biphenyl phosphate), quaternary phosphonium salts such as sodium carbonate, and 2,2-bis (4-hydroxyphene) bis-tetrafluorophene / Lephosphonium salts, ethylene bis (triphenylphosphonium) dibromide, trimethylene bis (triphenylphosphonium) -bis (tetraphenylborate) and the like can also be mentioned.
  • bis (tetrafluoroquinonephosphonium) carbonate for example, bis (tetrafluoroquinonephosphonium) carbonate , Bis (biphenyl phosphate), quaternary phosphonium salts such as sodium carbonate, and 2,2-bis (4-hydroxyphene) bis-tetrafluorophene / Lephosphonium salts, ethylene bis (triphenylphosphon
  • R 13 represents an organic group
  • X 4 represents a halogen atom, a hydroxyl group, an alkyloxy group, an aryloxy group, an alkylcarbonyloxy group, an arylcarbonyloxy group, HCO 3 — Or one BR 4 (where R represents a hydrogen atom or a hydrocarbon group, and four Rs represent each other May be the same or different. ).
  • P h denotes a phenyl group
  • Y 3 is - C 0 3 _ are shown
  • n is an integer of 1-4.
  • quaternary phosphonium compounds include, for example, tetraphenylphosphonium hydroxyhydroxide, bipheninole triphenylenolefoshonium hydroxide, methoxyphenyl triphenylphosphonium hydroxyhydroxide. , Phenoxy phenol, phenol phenol, naphthol phenol, phenol, phenol, phenol, phenol, biphenyl, phenol, etc.
  • quaternary phosphonium salt containing a branched alkyl group are, for example, isopropyltrimethylphosphonium, isopropyltriethylphosphonium, isopropylinoleliptinolephosphonium, isopropyltriphenylphosphonium, tetrisopropylphosphonium, cyclohexinoleto Lietinolephosphonium, cyclohexinoletrimethinolephosphonium, cyclohexenolebutyribenolephosphonium, cyclohexyl / retriene / lephosphonium, tetracycline hexinolephosphonium, 1 , 1,1—Triphenylmethinoletrimeth / lephosphonium, 1,1,1,1-triphenylenomethinolate trietinolephosphonium, 1,1,1—Triphenylmethyltribut
  • the salt comprising a quaternary phosphonium (cation) containing a branched alkyl group and X or Y (anion) include various combinations of the above specific examples.
  • cyclohexyl triphenylphosphonium methylene triborate and cyclopentyl triphenylphosphonium methylene triphenylborate are preferably used.
  • the quaternary phosphonium salt is preferably one having a small content of metal impurities, particularly an alkali metal compound. And those having a content of alkaline earth metal compound of 50 ppm or less, preferably 30 ppm or less, more preferably 10 ppm or less are suitably used.
  • the proportion of the catalyst, relative dihydric mud alkoxy compounds 1 mole of the raw material, 1 0 2 to 1 0 8 mol is preferably used.
  • this catalyst When the use ratio of this catalyst is less than 10 to 8 mol, the catalytic activity in the latter half of the reaction may be insufficient, and when it exceeds 10 to 2 mol, polycarbonate may be used. This is because there is a case where the quality of the product is deteriorated or the economy becomes disadvantageous.
  • a polymerization reaction is performed on the solid-state polycarbonate prepolymer subjected to the crystallization treatment using a quaternary phosphonium salt as a catalyst.
  • the reaction is promoted by extracting an aromatic monohydroxyl compound, dialkyl carbonyl, or both, which are by-produced by the polymerization reaction, out of the system. Therefore, an inert gas such as carbon dioxide gas, nitrogen gas, argon gas, and helium gas, or a hydrocarbon gas or poor solvent vapor that can be completely removed is introduced into the reaction system, and aromatic gas is accompanied by these gases.
  • a method of removing a group monohydroxy compound or the like, a method of performing a polymerization reaction under reduced pressure, or a method of using these in combination can be employed. Further, it is desirable to introduce the accompanying gas by heating it to a temperature close to the reaction temperature. When a hydrocarbon gas or a poor solvent vapor is used, the solubility of the polycarbonate is low, the hydrocarbon does not participate in the reaction, and has a low boiling point and can be completely removed and has 4 to 18 carbon atoms. Are preferred.
  • the shape of the crystallized prepolymer in carrying out this solid-state polymerization reaction is not particularly limited, but is preferably in the form of powder, granule, pellet, bead, or the like. is there.
  • the catalyst may be added in the prepolymer production step and the remaining one may be used as it is or may be added in the crystallization step .
  • the reaction temperature and reaction time for the solid-state polymerization reaction are as follows: the chemical structure and molecular weight of the crystallized pre-polymer, the crystallinity, the particle shape, the type and amount of catalyst, and the product polycarbonate.
  • the reaction temperature depends on the properties of the product polycarbonate, etc.
  • the temperature is preferably higher than the transition temperature and in a range where the crystallized prepolymer during the solid phase polymerization is not melted and the solid state is maintained. More preferably, the temperature is at least 50 ° C. lower than the melting temperature of the crystallized prepolymer and lower than the melting temperature.
  • the temperature is 150 to 260 ° C, It is preferably 180 to 245 ° C. It is also preferable to raise the solid-state polymerization temperature in accordance with the increase in the melting temperature of the crystallized prepolymer during the solid-state polymerization.
  • the reaction time is 1 minute to 100 hours, preferably 0.1 to 50 hours.
  • the polycarbonate of the product obtained in this way has a viscosity average molecular weight of 100,000 to 40,000, and has a molecular weight equivalent to that of polycarbonate generally used industrially. It is. Further, the crystallinity of this product polycarbonate is higher than that of the prepolymer used as the raw material. Since this product polycarbonate is obtained as a powder of crystalline polycarbonate, the powder may be supplied to an extruder without cooling, and may be pelletized, or may be directly formed. It may be supplied to a molding machine and molded.
  • the additive powder When various additives are blended, the additive powder may be mixed, or the additive liquid may be sprayed or gas may be absorbed. Further, additives may be mixed with an extruder when the polycarbonate is pelletized.
  • the blending of this product with the polycarbonate There are no particular restrictions on the additives that can be used, and commonly used additives such as plasticizers, pigments, lubricants, release agents, stabilizers, and inorganic fillers that are commonly used can be used.
  • the polycarbonate is blended with a polymer such as polyolefin-polystyrene, polyester, polysulfonate, polyamide, polyphenylene ether, or polyacrylate to form a resin composition. Can be used.
  • a polyphenylene ether / polyethernitrile having a functional group such as a hydroxyl group, a carbonyl group, or an amino group at the molecular chain terminal a terminal-modified polysiloxane compound
  • Use of modified polypropylene, modified polystyrene, etc. is effective because the compatibility is improved.
  • diphenyl mosquito one Boneto 2 2 5 g as a carbonic diester (1. 1 to 5 mol)
  • Pureborima hand as one catalyst for production Toramechiruanmo two Umuhi Dorokisai aqueous solution with a concentration 2 0 mass 0/0 de 0. 23 milliliters (0.5 millimoles) and 0.066 g (0.01 millimoles) of tetraphenylphosphonium tetraflate as a catalyst for solid-phase polymerization were added.
  • Argon replacement was performed 5 times.
  • the mixture in the autoclave was heated to 190 ° C. by a calo-heat and reacted in an argon atmosphere for 30 minutes. Then, the temperature was gradually increased to 235 ° C, and at the same time, the degree of vacuum was increased to 8.00 kPa and the reaction was performed for 60 minutes.The temperature was gradually increased to 270 ° C. At the same time, vacuum The temperature was increased to 1.33 kPa and the reaction was performed for 120 minutes. Then the temperature was 270. Increase the degree of vacuum to 0.133 kPa and react for 30 minutes while keeping the temperature at C, then increase the degree of vacuum to 0.0665 kPa and react for another 30 minutes. Was.
  • the viscosity average molecular weight of the obtained polycarbonate prepolymer was 8,600, and the terminal fraction of hydroxyl groups determined by ' ⁇ ⁇ ⁇ -NMR measurement was 30 mol%.
  • the crystallinity of the crystallized polycarbonate prepolymer obtained was measured by measuring the endothermic enthalpy at the melting point with a differential scanning calorimeter.
  • the endothermic enthalpy of this crystallization see Reference! Polly mErLett er s, 8645 (1970)]], which is the endothermic enthalpy at the time of 100% crystallization, which is calculated based on 1109.7 Jg.
  • the measurement by the differential scanning calorimeter was performed with the sample amount being 10 mg and the temperature rising rate being 40 ° C / min from 50 ° C to 300 ° C. As a result, it was confirmed that the crystallinity of the crystallized poly-carbonate prepolymer was 25%.
  • the yellow index (shown as YI in Table 1) of the polycarbonate obtained in (3) above was measured using the initial measurement values and the polycarbonate index.
  • the difference from the measured value after heat treatment for 90 minutes at 34 ° C. was determined and used as an index of thermal stability.
  • measurement takes the 8 mass 0/0 methylene chloride 'solution of polycarbonate Bok in a quartz cell having a height 5 7 mm, manufactured by Suga test Instruments Co., Ltd. color meter - was measured using a SM- 3.
  • Example 1 was the same as Example 1 except that the crystallization time in (2) was changed to 60 minutes.
  • Table 1 shows the physical properties and evaluation results of polycarbonate pre-bore polymer and product polycarbonate.
  • Example 1 was the same as Example 1 except that the crystallization time in (2) was changed to 120 minutes.
  • Table 1 shows the physical properties and evaluation results of polycarbonate prepolymers and products.
  • Polycarbonate prepolymer was prepared in the same manner as (1) in Example 1. The obtained polycarbonate prepolymer was extracted in a molten state, and then cooled to room temperature and solidified.
  • Polycarbonate prepolymer was prepared in the same manner as in (1) of Example 1.
  • the viscosity average molecular weight of the obtained polycarbonate prepolymer was 8,300, and the terminal fraction of hydroxyl terminal was 32 mol%.
  • the thermal stability of the product polycarbonate was evaluated in the same manner as in (4) of Example 1, except that the product polycarbonate obtained in the above (3) was used.
  • the manufacturing method of the polycarbonate which is excellent in heat stability which does not contain a residual solvent substantially can be provided.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Polyesters Or Polycarbonates (AREA)

Abstract

L'invention concerne un procédé permettant de produire un polycarbonate par polymérisation en phase solide d'un prépolymère de polycarbonate. Ce procédé consiste à mettre en contact le prépolymère de polycarbonate avec un dioxyde de carbone liquide, sous-critique ou supercritique afin de cristalliser le prépolymère, puis à polymériser ce dernier par polymérisation en phase solide. Ainsi, on peut obtenir un polycarbonate ne contenant sensiblement aucun solvants résiduaires et présentant une excellente stabilité thermique.
PCT/JP2001/010163 2000-11-22 2001-11-21 Procede de production de polycarbonate WO2002042355A1 (fr)

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JP2000355510 2000-11-22
JP2000-355510 2000-11-22

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Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH06271659A (ja) * 1993-03-17 1994-09-27 Asahi Chem Ind Co Ltd 結晶性芳香族ポリカーボネートプレポリマーの製造方法及び芳香族ポリカーボネートの製造方法

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH06271659A (ja) * 1993-03-17 1994-09-27 Asahi Chem Ind Co Ltd 結晶性芳香族ポリカーボネートプレポリマーの製造方法及び芳香族ポリカーボネートの製造方法

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