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WO2011024732A1 - Procédé de production de polycarbonate - Google Patents

Procédé de production de polycarbonate Download PDF

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Publication number
WO2011024732A1
WO2011024732A1 PCT/JP2010/064118 JP2010064118W WO2011024732A1 WO 2011024732 A1 WO2011024732 A1 WO 2011024732A1 JP 2010064118 W JP2010064118 W JP 2010064118W WO 2011024732 A1 WO2011024732 A1 WO 2011024732A1
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Prior art keywords
group
producing
carbon atoms
polycarbonate according
polycarbonate
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English (en)
Japanese (ja)
Inventor
順平 野村
隆 岡添
秀一 岡本
伸元 笠原
今日子 山本
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AGC Inc
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Asahi Glass Co Ltd
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Priority to JP2011528770A priority Critical patent/JPWO2011024732A1/ja
Publication of WO2011024732A1 publication Critical patent/WO2011024732A1/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
    • C08G64/26—General preparatory processes using halocarbonates
    • C08G64/266—General preparatory processes using halocarbonates and alcohols

Definitions

  • the present invention relates to a method for producing polycarbonate.
  • Polycarbonate is widely used in many fields as engineering plastics with excellent heat resistance, impact resistance and transparency.
  • the transesterification reaction between bisphenol A and diphenyl carbonate has a slow reaction rate and requires polycondensation for a long time at a high temperature; the boiling point of phenol separated by the transesterification reaction is high, and a high temperature is required for removal.
  • a side reaction or the like occurs during polycondensation at a high temperature, and the polycarbonate is colored.
  • Aliphatic polycarbonates having a relatively low molecular weight are widely used as the main raw material constituting polyurethane. Therefore, an aliphatic polycarbonate diol having a molecular weight of about 1000 to about 10,000 is industrially useful.
  • the present invention provides a method capable of producing a high-purity and high-quality polycarbonate without coloration in a relatively short time and in a simple process without using a toxic compound such as phosgene.
  • the polycarbonate production method of the present invention comprises a compound represented by the following formula (1), a compound represented by the following formula (2), and a compound represented by the following formula (3) in the presence of a Lewis acid catalyst.
  • a polycarbonate is obtained by transesterification of at least one fluorine-containing carbonate selected from the group consisting of and a diol.
  • R 1 is a group represented by CX 1 Y 1 R 4, 2 two R 1 may be the same or different, R 2 is a hydrogen atom or a group represented by CX 2 Y 2 R 5 , and two R 2 may be the same or different, R 3 is a hydrogen atom or a group represented by CX 3 Y 3 R 6 , and two R 3 may be the same or different, X 1 to X 3 are each independently a hydrogen atom, a fluorine atom or R f , Y 1 to Y 3 are each independently a fluorine atom or R f , R 4 to R 6 are each independently a fluorine atom, R f , OR f or an alkyl group having 1 to 6 carbon atoms, R f is a fluoroalkyl group having 1 to 4 carbon atoms (provided that also may contain an etheric oxygen), and if the R f there are a plurality, a plurality of R f is may be the same or different from each
  • R 1 is a group represented by CX 1 Y 1 R 4
  • R 2 is a hydrogen atom or a group represented by CX 2 Y 2 R 5
  • R 3 is a hydrogen atom or a group represented by CX 3 Y 3 R 6
  • R 7 is a perfluoroalkylene group having 1 to 5 carbon atoms (however, it may contain etheric oxygen)
  • X 1 to X 3 are each independently a hydrogen atom, a fluorine atom or R f
  • Y 1 to Y 3 are each independently a fluorine atom or R f
  • R 4 to R 6 are each independently a fluorine atom, R f , OR f or an alkyl group having 1 to 6 carbon atoms
  • R f is a fluoroalkyl group having 1 to 4 carbon atoms (provided that also may contain an etheric oxygen)
  • R 7 is a perfluoroalkylene group having 1 to 5 carbon atoms (however, it may contain etheric oxygen), and the two R 7 may be the same or different.
  • the Lewis acid catalyst is preferably at least one selected from compounds represented by the following formula (7), or at least one selected from compounds represented by the following formula (8).
  • M is a metal element or a metalloid element
  • X j ⁇ is a conjugate base of an organic acid group
  • R 8 is a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms which may have a functional group, or a polyfluoroalkyl group having 1 to 10 carbon atoms which may have a functional group;
  • Y k ⁇ is an inorganic anion excluding halogen ions.
  • X j ⁇ in the formula (7) is preferably COO ⁇ , SO 3 ⁇ , OSO 3 ⁇ , OPO 3 2 ⁇ , or O ⁇ .
  • M p + s (R 8 X q ⁇ ) t (Y r ⁇ ) u (8)
  • p ⁇ s q ⁇ t + r ⁇ u
  • p and q are each an integer of 1 or more
  • r is an integer greater than or equal to 2
  • s is an integer greater than or equal to 2
  • t and u are each an integer of 0 to 4
  • M is a metal element or a metalloid element
  • X q ⁇ is a conjugate base of an organic acid group
  • R 8 is a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms which may have a functional group, or a polyfluoroalkyl group having 1 to 10 carbon atoms which may have a functional group
  • Y r ⁇ is an inorganic anion excluding halogen ions.
  • X q ⁇ in the formula (8) is preferably COO ⁇ , SO 3 ⁇ , OSO 3 ⁇ , OPO 3 2 ⁇ , or O ⁇ .
  • the Lewis acid catalyst is preferably a metal alkoxide compound, a metal triflate compound, or a metal oxide.
  • the metal alkoxide compound is preferably a metal alkoxide compound selected from Ti, Zr, Si and Sn.
  • the metal triflate compound is preferably a metal triflate compound selected from Ce, Hf, La, Nd, Sc, Tm, Yb and Y.
  • the metal oxide is preferably a metal oxide selected from Al, Zn, Sn, and Pb.
  • the fluorine-containing carbonate is obtained by a reaction using as a starting material at least one fluorine-containing alcohol selected from the group consisting of a compound represented by the following formula (4) and a compound represented by the following formula (5): Is preferred.
  • R 1 is a group represented by CX 1 Y 1 R 4
  • R 2 is a hydrogen atom or a group represented by CX 2 Y 2 R 5
  • R 3 is a hydrogen atom or a group represented by CX 3 Y 3 R 6
  • R 7 is a perfluoroalkylene group having 1 to 5 carbon atoms (however, it may contain etheric oxygen)
  • X 1 to X 3 are each independently a hydrogen atom, a fluorine atom or R f
  • Y 1 to Y 3 are each independently a fluorine atom or R f
  • R 4 to R 6 are each independently a fluorine atom, R f , OR f or an alkyl group having 1 to 6 carbon atoms
  • R f is a fluoroalkyl group having 1 to 4 carbon atoms (provided that also may contain an etheric oxygen)
  • the fluorine-containing alcohol preferably has 2 to 10 carbon atoms.
  • R 2 in the formula (4) is preferably a group represented by CX 2 Y 2 R 5 .
  • the pKa of the fluorinated alcohol is preferably less than 15, and more preferably less than 10.
  • Examples of the fluorine-containing alcohol include 1,1,1,3,3,3-hexafluoro-2-propanol, perfluoro (t-butyl) alcohol, and 2,2,3,3,4,4,5,5. , 6,6-decafluorocyclohexanol is preferably at least one selected from the group consisting of.
  • the diol is preferably an aliphatic diol or an aromatic diol.
  • the aromatic diol is preferably bisphenol A.
  • the aliphatic diol is preferably an aliphatic diol having 2 to 10 carbon atoms.
  • the aliphatic diol is at least one selected from the group consisting of 3-methyl-1,5-pentanediol, 1,6-hexanediol, 1,3-propanediol, and 1,4-butanediol. preferable.
  • a high-purity and high-quality polycarbonate without coloring can be produced in a relatively short time and with a simple process without using a toxic compound such as phosgene.
  • a compound represented by the formula (1) is referred to as a compound (1).
  • the polycarbonate production method of the present invention is a method for obtaining a polycarbonate by a transesterification reaction between a specific fluorine-containing carbonate and a diol in the presence of a Lewis acid catalyst.
  • the fluorine-containing carbonate is at least one selected from the group consisting of the compound (1), the compound (2) and the compound (3).
  • R 1 is a group represented by CX 1 Y 1 R 4, 2 two R 1 may be the same or different, with R 2 is a hydrogen atom or CX 2 Y 2 R 5 Two R 2 s may be the same or different, R 3 is a hydrogen atom or a group represented by CX 3 Y 3 R 6 , and the two R 3 s are the same X 1 to X 3 are each independently a hydrogen atom, a fluorine atom or R f , Y 1 to Y 3 are each independently a fluorine atom or R f , and R 4 to R 3 6 are each independently a fluorine atom, R f , OR f or an alkyl group having 1 to 6 carbon atoms, and R f is a fluoroalkyl group having 1 to 4 carbon atoms (however, etheric oxygen may be included) , and the case where R f there are multiple there is a plurality of R f identical to one another It may be different from each other.
  • R 1 is a group represented by CX 1 Y 1 R 4
  • R 2 is a group represented by hydrogen or CX 2 Y 2 R 5
  • R 3 is a hydrogen atom or CX 3
  • R 7 is a perfluoroalkylene group having 1 to 5 carbon atoms (which may contain etheric oxygen)
  • X 1 to X 3 are each independently A hydrogen atom, a fluorine atom or R f
  • Y 1 to Y 3 are each independently a fluorine atom or R f
  • R 4 to R 6 are each independently a fluorine atom, R f , OR f or carbon number an alkyl group of 1 ⁇ 6
  • R f is fluoroalkyl group having 1 to 4 carbon atoms (provided that an etheric oxygen may also)
  • R 7 is a perfluoroalkylene group having 1 to 5 carbon atoms (however, it may contain etheric oxygen), and the two R 7 may be the same or different.
  • Fluorocarbonates are often low-viscosity liquids at room temperature, which is advantageous when performing a polycondensation reaction.
  • many of them have a boiling point in the range of 80 to 250 ° C. and have high thermal stability, so it is easy to obtain high-purity fluorinated carbonate by distillation purification, which is advantageous for producing high-quality polycarbonate. is there.
  • the fluorine-containing carbonate can be obtained by a reaction using at least one fluorine-containing alcohol selected from the group consisting of the compound (4) and the compound (5) as a starting material.
  • R 1 is a group represented by CX 1 Y 1 R 4
  • R 2 is a group represented by hydrogen or CX 2 Y 2 R 5
  • R 3 is a hydrogen atom or CX 3
  • R 7 is a perfluoroalkylene group having 1 to 5 carbon atoms (which may contain etheric oxygen)
  • X 1 to X 3 are each independently A hydrogen atom, a fluorine atom or R f
  • Y 1 to Y 3 are each independently a fluorine atom or R f
  • R 4 to R 6 are each independently a fluorine atom, R f , OR f or carbon number an alkyl group of 1 ⁇ 6
  • R f is fluoroalkyl group having 1 to 4 carbon atoms (provided that an etheric oxygen may also)
  • the fluorine-containing alcohol those having an acid dissociation degree higher than the acid dissociation degree of the diol are preferable from the viewpoint of improving the transesterification reaction rate. Accordingly, a compound in which a fluoroalkyl group is directly bonded to the ⁇ -position carbon atom of the hydroxyl group (hereinafter also referred to as ⁇ -carbon) is preferable. However, an alcohol in which a fluorine atom is directly bonded to the ⁇ -carbon is not preferable because a decomposition reaction due to a deHF reaction easily occurs.
  • pKa of a fluorinated alcohol can be used.
  • the pKa of the fluorinated alcohol is preferably less than 10 because the pKa of the phenol is approximately 10.
  • the pKa of the fluorinated alcohol is preferably less than 15 because the pKa of the aliphatic alcohol is about 15 to 16.
  • R 2 is a group represented by CX 2 Y 2 R 5 , that is, 2 Preferred is a tertiary or tertiary fluorine-containing alcohol
  • R 2 and R 3 are each a group represented by CX 2 Y 2 R 5 and a group represented by CX 3 Y 3 R 6 , that is, tertiary. More preferred is a fluorine-containing alcohol.
  • the carbon number of the fluorinated alcohol is preferably 2 to 10. If the fluorine-containing alcohol has 2 or more carbon atoms, a stable fluorine-containing alcohol in which a fluorine atom is not directly bonded to the ⁇ -position of the hydroxyl group can be selected. If the fluorine-containing alcohol has 10 or less carbon atoms, the boiling point of the fluorine-containing alcohol becomes a boiling point that can be easily removed under mild conditions when distilling off the fluorine-containing alcohol that dissociates during the ester exchange reaction. High quality polycarbonate can be produced without the need for high temperatures.
  • fluorine-containing alcohol examples include 2,2,2-trifluoroethanol, 2,2,3,3,3-pentafluoropropanol, 2,2,3,3-tetrafluoropropanol, 1,1,1 , 3,3,3-hexafluoro-2-propanol, 2-fluoropropanol, 2,2,3,4,4,4-hexafluorobutanol, 2,2,3,3,4,4,5,5 -Octafluoropentanol, perfluoro (t-butyl) alcohol, 2,2,3,3,4,4,5,5-octafluorocyclopentanol, 2,2,3,3,4,4,5 , 5,6,6-decafluorocyclohexanol and the like.
  • Specific methods for obtaining a fluorinated carbonate by a reaction using a fluorinated alcohol as a starting material include the following methods (a) to (c), and the yield can be obtained without using a toxic compound such as phosgene. From the viewpoint of high, the method (c) is preferable.
  • B A method of obtaining a fluorinated carbonate by a transesterification reaction between a dialkyl carbonate and a fluorinated alcohol.
  • C A method of obtaining a fluorinated carbonate by reacting the compound (6) with a fluorinated alcohol in the presence of a catalyst.
  • X 11 to X 13 are each independently a hydrogen atom or a halogen atom
  • at least one of X 11 to X 13 is a halogen atom
  • X 14 to X 16 are each independently a hydrogen atom or a halogen atom.
  • at least one of X 14 to X 16 is a halogen atom.
  • X 11 to X 16 are preferably all halogen atoms, more preferably fluorine atoms or chlorine atoms, and most preferably all chlorine atoms from the viewpoint that chloroform is obtained as a by-product.
  • the compound (6) include hexachloroacetone, pentachloroacetone, 1,1,3,3-tetrachloroacetone, 1,1,3-trichloroacetone, hexafluoroacetone, pentafluoroacetone, 1,1,3.
  • 3,3-tetrafluoroacetone 1,1,3-trifluoroacetone, 1,1,3,3-tetrachloro-1,3-difluoroacetone, 1,1,1-trichloro-3,3,3- Examples thereof include trifluoroacetone, 1,3-dichloro-1,1,3,3-tetrafluoroacetone, 1,1,3,3-tetrabromoacetone, pentabromoacetone, hexabromoacetone and the like. Hexachloroacetone is preferable because industrially useful chloroform can be produced in high yield.
  • chloroacetones can be easily produced by the method of chlorinating acetone described in Japanese Patent Publication No. 60-52741 and Japanese Patent Publication No. 61-16255.
  • a partially fluorinated compound can be easily produced by the method of fluorinating chloroacetones with hydrogen fluoride described in US Pat. No. 6,235,950.
  • the ratio between the number of moles of the first charge of the fluorinated alcohol and the number of moles of the first charge of the compound (6) (fluorinated alcohol / compound (6)) is from the point of improving the yield of the fluorinated carbonate, More than 2, preferably 2.5 or more, more preferably 3 or more.
  • the catalyst used in the method (c) includes alkali metal; alkaline earth metal; alkali metal hydride; alkaline earth metal hydride; alkali metal hydroxide; alkaline earth metal hydroxide; phase transfer catalyst; Alkali earth metal halide; Ammonia halide; Ion exchange resin; Compound or oxide of at least one metal selected from the group consisting of Sn, Ti, Al, W, Mo, Zr and Zn; Examples include a transesterification catalyst.
  • the amount of the catalyst used in the method (c) is variously selected depending on the catalyst, but is preferably 0.01 to 30% by mass with respect to the substrate. 1 to 10% by mass is more preferable.
  • a solvent may be used for the purpose of promoting the reaction.
  • the reaction temperature in the method (c) is preferably 40 to 200 ° C.
  • the reaction pressure in the method (c) is usually atmospheric pressure.
  • diol examples include aliphatic diols and aromatic diols.
  • aliphatic diol examples include ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, 3-chloro-1,2-propanediol, 2-chloro-1,3-propanediol, and 1,4-cyclohexanediol.
  • an aliphatic diol having 2 to 10 carbon atoms is more preferable from the viewpoint of the usefulness of an aliphatic polycarbonate diol used as a raw material for polyurethane and the like, and 3-methyl-1,5-pentanediol, 1, Particularly preferred are aliphatic diols selected from 6-hexanediol, 1,3-propanediol and 1,4-butanediol.
  • aromatic diol examples include resorcinol, catechol, hydroquinone, 2,2-bis (4-hydroxyphenyl) propane [alias: bisphenol A], 2,2-bis (4-hydroxyphenyl) hexafluoropropane [alias] : Bisphenol AF], bis (4-hydroxyphenyl) methane, 4,4′-dihydroxybiphenyl, bis (4-hydroxybiphenyl) ether, dihydroxynaphthalene, phloroglicinol, and phenol condensates.
  • Bisphenol A is preferred from the viewpoint of availability and usefulness of polycarbonate.
  • the Lewis acid catalyst is a substance that increases the reactivity by accepting an electron pair of any raw material in the reaction system.
  • the Lewis acid catalyst at least one selected from the compound (7) or the following formula (8) is used because the effect of promoting the transesterification reactivity is great and the coloring of the synthesized polymer can be suppressed.
  • At least one selected from the compounds described above is preferred.
  • i j ⁇ m + k ⁇ n
  • i and j are each an integer of 1 or more
  • k is an integer of 2 or more
  • m and n are integers of 0 to 4, respectively.
  • M in the compound (7) and the compound (8) is a metal element or a metalloid element.
  • metal elements Li, Be, Na, Mg, Al, K, Ca, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga, Rb, Sr, Y, Zr, Nb , Mo, Ru, Rh, Pd, Ag, Cd, In, Sn, Cs, Ba, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Hf , Ta, W, Re, Os, Ir, Pt, Au, Hg, Tl, Pb, Bi, and the like.
  • the metalloid element include B, Si, Ge, As, Sb, Te, and Po.
  • X j- in the compound (7) and X q- in the compound (8) are conjugate bases of the organic acid group.
  • the conjugate base of the organic acid group COO ⁇ , SO 3 ⁇ , OSO 3 ⁇ , OPO 3 2 ⁇ , O ⁇ , CO ⁇ , SCO ⁇ , ONOO ⁇ , CONH ⁇ , CHNO ⁇ , SO ⁇ , NHCOO ⁇ , S -, NO -, and the like, thermal stability, in terms of reaction activity, COO -, SO 3 -, OSO 3 -, OPO 3 2-, or O - are preferred.
  • R 8 in the compound (7) and the compound (8) is a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms which may have a functional group, or a carbon group having 1 to 10 carbon atoms which may have a functional group. It is a polyfluoroalkyl group.
  • Y k- in the compound (7) and Y r- in the compound (8) are inorganic anions excluding halogen ions. Examples of Y k- and Y r- include O 2 ⁇ , S 2 ⁇ , N 3 ⁇ , P 3 ⁇ and the like.
  • a metal alkoxide compound, a metal triflate compound, or a metal oxide is preferable from the viewpoint of reaction activity and coloring degree of the synthetic polymer.
  • the metal alkoxide compound is preferably a metal alkoxide compound selected from Ti, Zr, Si and Sn from the viewpoint of reaction activity and low toxicity.
  • Specific examples of the metal alkoxide compound include tetramethoxy titanium, tetraethoxy titanium, tetrapropoxy titanium, tetraisopropoxy titanium, tetra n-butoxy titanium, tetra tert-butoxy titanium, tetra sec-butoxy titanium, tetrapentoxy titanium, tetra Hexoxytitanium, tetraheptoxytitanium, tetraoctoxytitanium, tetranoninoxytitanium, tetradecyloxytitanium, tetraundecyloxytitanium, tetralauryloxytitanium, tetramyristoxytitanium, tetrapalmitoxytitanium, tetrastearoxytitan
  • the metal triflate compound is preferably a metal triflate compound selected from Ce, Hf, La, Nd, Sc, Tm, Yb and Y from the viewpoint of reaction activity.
  • Specific examples of the metal triflate compound include cerium (III) trifluoromethanesulfonate, copper (I) trifluoromethanesulfonate, copper (II) trifluoromethanesulfonate, hafnium (IV) trifluoromethanesulfonate, and trifluoromethanesulfonic acid.
  • the metal oxide is preferably a metal oxide selected from Al, Zn, Sn, and Pb from the viewpoint of reactivity.
  • a specific method for obtaining a polycarbonate by transesterification of a fluorine-containing carbonate and a diol in the presence of a Lewis acid catalyst includes the following method (A) or (B). From the viewpoint of production, the method (A) is preferable.
  • B A method of subjecting a fluorine-containing carbonate and a diol to solution polycondensation in the presence of a Lewis acid catalyst.
  • the reaction temperature in the method (A) is preferably not less than the melting point of the diol at the beginning of the reaction, and preferably not less than the melting point of the polycarbonate in the later stage of the reaction.
  • the reaction temperature in the method (A) is preferably 300 ° C. or lower from the viewpoint of suppressing the coloring of the polycarbonate.
  • the ratio between the number of moles of the initial charge of the fluorinated carbonate and the number of moles of the first charge of the diol may be appropriately selected according to the target molecular weight of the polycarbonate.
  • the fluorine-containing carbonate / diol ratio (molar ratio) in the case of obtaining an aliphatic or aromatic polycarbonate diol is 0.90 to 1.1 because an aliphatic or aromatic polycarbonate diol having a molecular weight of about 1000 to 100,000 is obtained. 30 is preferred.
  • the fluorine-containing carbonate compound in the present invention has a high degree of dissociation of the ester site due to the effect of electron withdrawing by fluorine atoms, and is easily transesterified with an aromatic diol or an aliphatic diol.
  • the method for producing a polycarbonate of the present invention using a compound is an excellent production method that can solve problems such as coloring caused by a long-time reaction at a high temperature, which was a problem of a conventional method for producing a polycarbonate by a transesterification method.
  • GC analysis was performed using an Agilent 6890 series.
  • Example 1 Synthesis of polycarbonate 1 (tetra n-butoxy titanium catalyst): In a reactor of a 300 mL melt polymerization apparatus, 87.3 g (0.30 mol) of bisphenol A (compound (12)), 75.4 g (0.33 mol) of compound (11), 1 of tetra-n-butoxytitanium 0.02 g (3.0 mmol) was charged. The following deoxygenation step was repeated three times. Deoxygenation step: After exhausting oxygen at 0 ° C. until the pressure in the reactor is about 1 Torr, the reactor is again filled with nitrogen.
  • the reactor was immersed in an oil bath preheated to 180 ° C. Stirring was performed at an oil bath temperature of 180 ° C. and a stirring speed of 200 rpm. After 10 minutes, the mixture was thermally equilibrated and the solids were completely melted to form a colorless and uniform liquid. Thereafter, when the reaction was continued for 5 minutes while maintaining the pressure in the reactor at 740 torr and the temperature in the reactor at 180 ° C., 2,2,3,3-tetrafluoropropanol was evacuated from the reaction vessel, and the receiving flask I started distilling inside. After 30 minutes, the temperature in the reactor was raised to 200 ° C. and the pressure in the reactor was maintained at 740 torr.
  • the pressure in the reactor was reduced to 500 torr while maintaining the temperature in the reactor at 200 ° C. and maintained for another 30 minutes.
  • 2,2,3,3-Tetrafluoropropanol continued to distill into the receiving flask.
  • the temperature in the reactor was raised to 250 ° C. and the pressure in the reactor was reduced to 100 torr, and then this condition was maintained for 30 minutes. Thereafter, when the temperature in the reactor was raised to 290 ° C. and lowered to 1 torr in the reactor, the viscosity of the molten material began to rise.
  • the polymerization was terminated by cooling at room temperature to obtain a polycarbonate represented by the following formula (13).
  • the mass average molecular weight (Mw) by GPC analysis of the obtained polycarbonate was 25,000, the number average molecular weight (Mn) was 13,200, and the dispersity (Mw / Mn) was 1.89.
  • the polycarbonate was not colored and was found to be of high purity.
  • Example 2 Synthesis of polycarbonate 2 (scandium (III) trifluoromethanesulfonate catalyst): A polycarbonate was obtained in the same manner as in Example 1 except that 1.48 g (3.0 mmol) of scandium (III) trifluoromethanesulfonate was used instead of tetra n-butoxytitanium as a catalyst.
  • the mass average molecular weight (Mw) by GPC analysis of the obtained polycarbonate was 14,900, the number average molecular weight (Mn) was 7,487, and the dispersity (Mw / Mn) was 1.99.
  • the polycarbonate was not colored and was found to be of high purity.
  • the aromatic polycarbonate obtained by the production method of the present invention is useful as engineering plastics.
  • the aliphatic polycarbonate obtained by the production method of the present invention is useful as a raw material for polyurethane, polyol, polyester and the like.

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  • Health & Medical Sciences (AREA)
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Abstract

La présente invention concerne un procédé permettant de produire un polycarbonate de grande qualité, non décoloré et présentant une grande pureté, de façon relativement rapide, par un procédé simple et sans avoir à recourir à un composé toxique tel que le phosgène. L'invention concerne, plus précisément, un procédé de production de polycarbonate par transestérification d'un carbonate contenant du fluor, choisi parmi les composés (1) à (3), par un diol en présence d'un catalyseur de type acide de Lewis. Dans les formules générales (1) à (3), R1 représente CX1Y1R4 ; R2 représente H ou CX2Y2R5 ; R3 représente H ou CX3Y3R6 ; R7 représente un perfluoroalkylène en C1-C5 ; X1 à X3 représentent H, F ou Rf ; Y1 à Y3 représentent F ou Rf ; R4 à R6 représentent F, Rf, ORf ou équivalent ; et Rf représente un fluoroalkyle en C1-C4.
PCT/JP2010/064118 2009-08-28 2010-08-20 Procédé de production de polycarbonate Ceased WO2011024732A1 (fr)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2014027586A1 (fr) * 2012-08-15 2014-02-20 旭硝子株式会社 Procédé de production d'un carbonate de polyester
WO2014171367A1 (fr) * 2013-04-16 2014-10-23 旭硝子株式会社 Procédé de fabrication d'un polycarbonate et polycarbonate correspondant
JP2023061092A (ja) * 2021-10-19 2023-05-01 Ａｇｃ株式会社 ポリカーボネートポリオールの製造方法

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JPH1077340A (ja) * 1996-08-02 1998-03-24 Ausimont Spa ポリカーボネート構造を有するパーフルオロエーテル化合物
JPH10158380A (ja) * 1996-11-27 1998-06-16 Fuji Electric Co Ltd 新規ポリカーボネート樹脂およびこれを用いた電子写真用感光体
JP2005060261A (ja) * 2003-08-08 2005-03-10 Asahi Glass Co Ltd ビス（２，２，３，４，４，４−ヘキサフルオロブチル）カーボネートおよびその製造方法、および非水系電解液
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Publication number Priority date Publication date Assignee Title
WO2014027586A1 (fr) * 2012-08-15 2014-02-20 旭硝子株式会社 Procédé de production d'un carbonate de polyester
WO2014171367A1 (fr) * 2013-04-16 2014-10-23 旭硝子株式会社 Procédé de fabrication d'un polycarbonate et polycarbonate correspondant
US9447235B2 (en) 2013-04-16 2016-09-20 Asahi Glass Company, Limited Polycarbonate manufacturing method and polycarbonate
JPWO2014171367A1 (ja) * 2013-04-16 2017-02-23 旭硝子株式会社 ポリカーボネートの製造方法およびポリカーボネート
JP2023061092A (ja) * 2021-10-19 2023-05-01 Ａｇｃ株式会社 ポリカーボネートポリオールの製造方法

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