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WO2014084558A1 - Procédé de préparation de polycarbonate - Google Patents

Procédé de préparation de polycarbonate Download PDF

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Publication number
WO2014084558A1
WO2014084558A1 PCT/KR2013/010742 KR2013010742W WO2014084558A1 WO 2014084558 A1 WO2014084558 A1 WO 2014084558A1 KR 2013010742 W KR2013010742 W KR 2013010742W WO 2014084558 A1 WO2014084558 A1 WO 2014084558A1
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Prior art keywords
atom
alkyl
aryl
halogen
chemical formula
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Inventor
Jin Su Ham
Yu Na Shim
Hyo Seung Park
Jong Ho Lim
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SK Innovation Co Ltd
SK Geo Centric Co Ltd
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SK Innovation Co Ltd
SK Global Chemical Co Ltd
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Priority claimed from KR1020130142607A external-priority patent/KR20140070392A/ko
Application filed by SK Innovation Co Ltd, SK Global Chemical Co Ltd filed Critical SK Innovation Co Ltd
Publication of WO2014084558A1 publication Critical patent/WO2014084558A1/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
    • C08G64/32—General preparatory processes using carbon dioxide
    • C08G64/34—General preparatory processes using carbon dioxide and cyclic ethers

Definitions

  • the present invention relates to a method for preparing polycarbonate, and more particularly, to a method for preparing polycarbonate in which polymerization of polycarbonate is performed via a one-pot process together with preparing an organic transition metal catalyst from a ligand.
  • polymers such as plastic contribute to convenience of our daily lives and development of various modern industries, but as an amount of the used polymer is increased, environmental contamination by waste polymers discarded after being used has also been significantly increased.
  • aliphatic polycarbonate which is a biodegradable polymer having excellent processability into a soft rubber phase plastic and an easily controlled degradation property by nature, is useful as a raw material for fabrics, packing materials, films, sheets, paints, adhesives, and the like.
  • the aliphatic polycarbonate is prepared from an epoxide compound and carbon dioxide or prepared through ring open polymerization of cyclic carbonate.
  • a method for preparing the aliphatic polycarbonate from the epoxide compound and carbon dioxide has eco-friendly high value in that phosgene, which is a toxic compound, is not used, and carbon dioxide may be cheaply obtained.
  • an additional oxidant or pure oxygen gas should be used, but in the case of using the oxidant, after a reaction is completed, a catalyst separating process is required, such that a process step may be increased, which is not economical. Further, in the case of using pure oxygen gas, a fire risk may be significantly high.
  • An object of the present invention is to provide a method for preparing polycarbonate.
  • a method for preparing polycarbonate includes: 1) putting epoxide compound, a salen ligand, a cobalt (II) source or chromium (II) source, and a chain transfer agent into a reactor and injecting air thereinto; and 2) injecting carbon dioxide into the reactor to polymerize the epoxide and carbon dioxide.
  • the epoxide compound may be at least one selected from a group consisting of (C2-C20)alkyleneoxide substituted or unsubstituted with halogen, (C1-C20)alkyloxy, (C6-C20)aryloxy, or (C6-C20)aryl(C1-C20)alkyloxy; (C4-C20)cycloalkyleneoxide substituted or unsubstituted with halogen, (C1-C20)alkyloxy, (C6-C20)aryloxy, or (C6-C20)aryl(C1-C20)alkyloxy; and (C8-C20)styreneoxide substituted or unsubstituted with halogen, (C1-C20)alkyloxy, (C6-C20)aryloxy, (C6-C20)aryl(C1-C20)alkyloxy, or (C1-C20)alkyl.
  • the chain transfer agent which is a compound having a plurality of sites capable of initiating polymerization of carbon dioxide and epoxide, may be represented by the following Chemical Formula 1.
  • LH may be -OH or -CO 2 H; and a may be an integer of 1 to 4.
  • the salen ligand may be represented by the following Chemical Formula 2.
  • A is an oxygen or sulfur atom
  • Q is a diradical linking two nitrogen atoms
  • R', R'' and R'' are each independently hydrogen; halogen; (C1-C20)alkyl; (C1-C20)alkyl containing at least one of a halogen atom, a nitrogen atom, an oxygen atom, a silicon atom, a sulfur atom, and a phosphorus atom; (C2-C20)alkenyl; (C2-C20)alkenyl containing at least one of a halogen atom, a nitrogen atom, an oxygen atom, a silicon atom, a sulfur atom, and a phosphorus atom; (C1-C20)alkyl(C6-C20)aryl; (C1-C20)alkyl(C6-C20)aryl containing at least one of a halogen atom, a nitrogen atom, an oxygen atom, a silicon atom, a sulfur atom, and a phosphorus atom; (C6-C20)aryl(C1-C20)
  • R', R'' and R''' may be linked to each other to form a ring, and the formed ring may be further substituted with at least one selected from a group consisting of halogen; cyano; nitro; (C1-C20)alkyl; (C1-C20)alkyl containing at least one of a halogen atom, a nitrogen atom, an oxygen atom, a silicon atom, a sulfur atom, and a phosphorus atom; (C2-C20)alkenyl; (C2-C20)alkenyl containing at least one of a halogen atom, a nitrogen atom, an oxygen atom, a silicon atom, a sulfur atom, and a phosphorus atom; (C1-C20)alkyl(C6-C20)aryl; (C1-C20)alkyl(C6-C20)aryl containing at least one of a halogen atom, a nitrogen atom, an oxygen atom
  • the salen ligand may be represented by the following Chemical Formula 3.
  • A is an oxygen or sulfur atom
  • Q is a diradical linking two nitrogen atoms
  • R 1 to R 10 are each independently hydrogen; halogen; (C1-C20)alkyl; (C1-C20)alkyl containing at least one of a halogen atom, a nitrogen atom, an oxygen atom, a silicon atom, a sulfur atom, and a phosphorus atom; (C2-C20)alkenyl; (C2-C20)alkenyl containing at least one of a halogen atom, a nitrogen atom, an oxygen atom, a silicon atom, a sulfur atom, and a phosphorus atom; (C1-C20)alkyl(C6-C20)aryl; (C1-C20)alkyl(C6-C20)aryl containing at least one of a halogen atom, a nitrogen atom, an oxygen atom, a silicon atom, a sulfur atom, and a phosphorus atom; (C6-C20)aryl(C1-C20)alkyl(C
  • R 1 to R 10 may be linked to each other to form a ring
  • At least one of the hydrogens contained in R 1 to R 10 and Q is substituted with a proton group selected from a group consisting of Chemical Formulas a, b, and c:
  • Z is a nitrogen or phosphorus atom
  • R 21 , R 22 , R 23 , R 31 , R 32 , R 33 , R 34 and R 35 are each independently (C1-C20)alkyl; (C1-C20)alkyl containing at least one of a halogen atom, a nitrogen atom, an oxygen atom, a silicon atom, a sulfur atom, and a phosphorus atom; (C2-C20)alkenyl; (C2-C20)alkenyl containing at least one of a halogen atom, a nitrogen atom, an oxygen atom, a silicon atom, a sulfur atom, and a phosphorus atom; (C1-C20)alkyl(C6-C20)aryl; (C1-C20)alkyl(C6-C20)aryl containing at least one of a halogen atom, a nitrogen atom, an oxygen atom, a silicon atom, a sulfur atom, and a phosphorus atom; (C6
  • R 41 , R 42 , and R 43 are each independently hydrogen; (C1-C20)alkyl; (C1-C20)alkyl containing at least one of a halogen atom, a nitrogen atom, an oxygen atom, a silicon atom, a sulfur atom, and a phosphorus atom; (C2-C20)alkenyl; (C2-C20)alkenyl containing at least one of a halogen atom, a nitrogen atom, an oxygen atom, a silicon atom, a sulfur atom, and a phosphorus atom; (C1-C20)alkyl(C6-C20)aryl; (C1-C20)alkyl(C6-C20)aryl containing at least one of a halogen atom, a nitrogen atom, an oxygen atom, a silicon atom, a sulfur atom, and a phosphorus atom; (C6-C20)aryl(C1-C20)alkyl
  • X' is an oxygen atom, a sulfur atom, or N-R (here, R is (C1-C20)alkyl).
  • a may be 1, LH may be -OH or -CO 2 H; J may be -[CR 51 R 52 ] n -CR 53 R 54 R 55 , phenyl, or naphthyl; n may be an integer of 0 to 20; and R 51 to R 55 may be the same as or different from each other and is hydrogen, methyl, ethyl, propyl, or butyl.
  • a may be 2; LH(s) may be the same as or different from each other and be -OH or -CO 2 H; J may be -[CR 51 R 52 ] n -, para-phenylene, metha-phenylene, ortho-phenylene, 2,6-naphthalendiyl, -CH 2 CH 2 N(R 56 )CH 2 CH 2 -, or -[CH 2 CH(R 56 )O] m CH 2 CH(R)-; n may be an integer of 1 to 20; R 51 , R 52 , and R 56 may be the same as or different from each other and be hydrogen, methyl, ethyl, propyl, or butyl; and m may be an integer of 1 to 10.
  • a may be 3, LH may be -CO 2 H; and J may be 1,2,3-propanetriyl, 1,2,3-benzenetriyl, 1,2,4-benzenetriyl, or 1,3,5-benzenetriyl.
  • a may be 4, LH may be -CO 2 H; and J may be 1,2,3,4-butanetetrayl or 1,2,4,5-benzenetetrayl.
  • step 1) a solvent may be further injected into the reactor.
  • the solvent may be at least one selected from a group consisting of aromatic hydrocarbons, halogenated hydrocarbons, ethers, and esters.
  • the solvent may be at least one selected from a group consisting of toluene, dichloromethane, dichloroethane, tetrahydrofuran, and ethylacetate.
  • a molar ratio of the epoxide compound : the salen ligand may be 100:1 to 1,000,000:1.
  • a molar ratio of the cobalt source or chromium source : the salen ligand may be 1:0.9 to 1.1.
  • the method for preparing polycarbonate according to the exemplary embodiment of the present invention does not require a separate catalyst preparing step, such that simplicity of the entire process may be secured, and the catalyst loss generated during the manufacturing process may be decreased, thereby making it possible to decrease preparation cost of the catalyst and process cost.
  • the catalyst is partially reduced during storage and preservation of the catalyst, such that the catalytic activity may be deteriorated, but as in the present invention, in the case of preparing the catalyst from the ligand via the one-pot process, since there is no need to take care of storage and preservation of the catalyst and the activity due to reduction of the catalyst is not generated, such that stability may be secured.
  • an additional oxidant or pure oxygen gas should be used.
  • the oxidant after reaction, a catalyst separating process is required, and in the case of using pure oxygen gas, a fire risk may be significantly high, such that it may be difficult to secure stability.
  • the present invention since the organic metal catalyst in the high oxidation state is prepared via the one-pot process using air, which is a mixed gas having a low fire risk, to thereby be used in polymerization, the present invention is advantageous in view of safety.
  • the present invention provides a method for preparing polycarbonate. More particularly, the method for preparing polycarbonate includes:
  • the method for preparing polycarbonate according to the present invention which is to prepare polycarbonate having a high molecular weight and narrow molecular weight distribution simultaneously with preparing a catalyst from the salen ligand via a one-pot process, does not require a preparing process for a separate catalyst and may prevent a catalyst loss generated during a manufacturing process and an activity deterioration due to reduction during storage and preservation of the catalyst.
  • the present invention since the organic metal catalyst in a high oxidation state is prepared via the one-pot process using air, which is a mixed gas having a low fire risk, to thereby be used in polymerization, the present invention is advantageous in view of safety.
  • a pressure of the air injected in step 1) is not limited, but may be, preferably 1 to 30 atm.
  • cobalt (II) source or chromium (II) source any divalent cobalt or chromium source known in the art may be used, but preferably, cobalt acetate, cobalt acetylacetonate, cobalt benzoylacetonate, cobalt bromide, cobalt chloride, cobalt carbonate, cobalt cyanate, cobalt hydroxide, cobalt nitrate, cobalt sufate, cobalt thiocyanate, cobalt fluoroborate, cobalt oxalate, chromium acetate, chromium chloride, or the like, may be used.
  • any compound may be used as long as it has a plurality of sites at which copolymerization of carbon dioxide and epoxide may be initiated, but a compound represented by the following Chemical Formula 1 may be preferably used.
  • An example of the chain transfer agent of Chemical Formula 1 may include polyols, specifically, diol, triol, tetraol, or the like.
  • a specific example of the diol may include 1,2-ethanediol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 2,2-dimethylpropane-1,3-diol, 2-butyl-2-ethylpropane-1,3-diol, 1,5-hexanediol, 1,6-hexanediol, 1,8-octanediol, 1,10-decanediol, 1,12-dodecanediol, 2,2,4,4-tetramethylcyclobutane-1,3-diol, 1,3-cyclopentane
  • triol may include trimethylolethane; trimethylolpropane; glycerol; 1,2,4-butanetriol; 1,2,6-hexanetriol; tris(2-hydroxyethyl)isocyanurate; hexahydro-1,3,5-tris(hydroxyethyl)-s-triazine; 6-methylheptane-1,3,5-triol; polypropylene oxide triol; and aliphatic triols having a molecular weight smaller than 500 such as polyester triol, and the like.
  • tetraol may include erythritol, pentaerythritol, 2,2'-dihydroxymethyl-1,3-propandiol, 2,2'-(oxydimethylene)bis-(2-ethyl-1,3-propandiol), and the like.
  • an example of the chain transfer agent of Chemical Formula 1 may include diethylene glycol, triethylene glycol, tetraethylene glycol, higher poly(ethylene glycol) (preferably, having a number average molecular weight of 220 to about 2000g/mol), dipropylene glycol, tripropylene glycol, and higher poly(propylene glycol) (preferably, having a number average molecular weight of 234 to about 2000g/mol), and the like.
  • an example of the chain transfer agent of Chemical Formula 1 may include hydroxy acid, specifically, alpha-hydroxy acid or beta-hydroxy acid.
  • a specific example of the alpha-hydroxy acid may include glycolic acid, DL-lactic acid, D-lactic acid, L-lactic acid, citric acid, mandelic acid, and the like
  • a specific example of the beta-hydroxy acid may include 3-hydroxy propionic acid, DL-3-hydroxybutyric acid, D-3-hydroxybutyric acid, L-3-hydroxybutyric acid, DL-3-hydroxy valeric acid, D-3-hydroxy valeric acid, L-3-hydroxy valeric acid, salicylic acid and salicylic acid derivatives, and the like.
  • chain transfer agent of Chemical Formula 1 may include biacids, more specifically, phthalic acid, isophthalic acid, terephthalic acid, maleic acid, succinic acid, malonic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, and the like.
  • the chain transfer agent of Chemical Formula 1 may be preferably a compound in which LH is -OH or -CO 2 H; and a is an integer of 1 to 4.
  • a is 1; LH is -OH or -CO 2 H; J is -[CR 51 R 52 ] n -CR 53 R 54 R 55 , phenyl, or naphthyl; n is an integer of 0 to 20; and R 51 to R 55 may be the same as or different from each other and be hydrogen, methyl, ethyl, propyl, or butyl.
  • a is 2; LH(s) may be the same as or different from each other and be -OH or -CO 2 H; J is -[CR 51 R 52 ] n -, para-phenylene, metha-phenylene, ortho-phenylene, 2,6-naphthalendiyl, -CH 2 CH 2 N(R 56 )CH 2 CH 2 -, or -[CH 2 CH(R 56 )O] m CH 2 CH(R)-; n is an integer of 1 to 20; R 51 , R 52 , and R 56 may be the same as or different from each other and be hydrogen, methyl, ethyl, propyl, or butyl; and m is an integer of 1 to 10.
  • a is 3; LH is -CO 2 H; and J is 1,2,3-propanetriyl, 1,2,3-benzenetriyl, 1,2,4-benzenetriyl, or 1,3,5-benzenetriyl.
  • a is 4; LH is -CO 2 H; and J is 1,2,3,4-butanetetrayl or 1,2,4,5-benzenetetrayl.
  • chain transfer agent methanol, acetic acid, adipic acid, succinic acid, and phthalic acid may be used alone or mixed with another chain transfer agent to thereby be used in plural.
  • any salen ligand known in the art may be used, but a salen ligand represented by the following Chemical Formula 2 or 3, may be preferably used.
  • A is an oxygen or sulfur atom
  • Q is a diradical linking two nitrogen atoms
  • R', R'' and R'' are each independently hydrogen; halogen; (C1-C20)alkyl; (C1-C20)alkyl containing at least one of a halogen atom, a nitrogen atom, an oxygen atom, a silicon atom, a sulfur atom, and a phosphorus atom; (C2-C20)alkenyl; (C2-C20)alkenyl containing at least one of a halogen atom, a nitrogen atom, an oxygen atom, a silicon atom, a sulfur atom, and a phosphorus atom; (C1-C20)alkyl(C6-C20)aryl; (C1-C20)alkyl(C6-C20)aryl containing at least one of a halogen atom, a nitrogen atom, an oxygen atom, a silicon atom, a sulfur atom, and a phosphorus atom; (C6-C20)aryl(C1-C20)
  • R', R'' and R''' may be linked to each other to form a ring, and the formed ring may be further substituted with at least one selected from a group consisting of halogen; cyano; nitro; (C1-C20)alkyl; (C1-C20)alkyl containing at least one of a halogen atom, a nitrogen atom, an oxygen atom, a silicon atom, a sulfur atom, and a phosphorus atom; (C2-C20)alkenyl; (C2-C20)alkenyl containing at least one of a halogen atom, a nitrogen atom, an oxygen atom, a silicon atom, a sulfur atom, and a phosphorus atom; (C1-C20)alkyl(C6-C20)aryl; (C1-C20)alkyl(C6-C20)aryl containing at least one of a halogen atom, a nitrogen atom, an oxygen atom
  • A is an oxygen or sulfur atom
  • Q is a diradical linking two nitrogen atoms
  • R 1 to R 10 are each independently hydrogen; halogen; (C1-C20)alkyl; (C1-C20)alkyl containing at least one of a halogen atom, a nitrogen atom, an oxygen atom, a silicon atom, a sulfur atom, and a phosphorus atom; (C2-C20)alkenyl; (C2-C20)alkenyl containing at least one of a halogen atom, a nitrogen atom, an oxygen atom, a silicon atom, a sulfur atom, and a phosphorus atom; (C1-C20)alkyl(C6-C20)aryl; (C1-C20)alkyl(C6-C20)aryl containing at least one of a halogen atom, a nitrogen atom, an oxygen atom, a silicon atom, a sulfur atom, and a phosphorus atom; (C6-C20)aryl(C1-C20)alkyl(C
  • R 1 to R 10 may be linked to each other to form a ring
  • At least one of the hydrogens contained in R 1 to R 10 and Q is substituted with a proton group selected from a group consisting of Chemical Formulas a, b, and c:
  • Z is a nitrogen or phosphorus atom
  • R 21 , R 22 , R 23 , R 31 , R 32 , R 33 , R 34 and R 35 are each independently (C1-C20)alkyl; (C1-C20)alkyl containing at least one of a halogen atom, a nitrogen atom, an oxygen atom, a silicon atom, a sulfur atom, and a phosphorus atom; (C2-C20)alkenyl; (C2-C20)alkenyl containing at least one of a halogen atom, a nitrogen atom, an oxygen atom, a silicon atom, a sulfur atom, and a phosphorus atom; (C1-C20)alkyl(C6-C20)aryl; (C1-C20)alkyl(C6-C20)aryl containing at least one of a halogen atom, a nitrogen atom, an oxygen atom, a silicon atom, a sulfur atom, and a phosphorus atom; (C6
  • R 41 , R 42 , and R 43 are each independently hydrogen; (C1-C20)alkyl; (C1-C20)alkyl containing at least one of a halogen atom, a nitrogen atom, an oxygen atom, a silicon atom, a sulfur atom, and a phosphorus atom; (C2-C20)alkenyl; (C2-C20)alkenyl containing at least one of a halogen atom, a nitrogen atom, an oxygen atom, a silicon atom, a sulfur atom, and a phosphorus atom; (C1-C20)alkyl(C6-C20)aryl; (C1-C20)alkyl(C6-C20)aryl containing at least one of a halogen atom, a nitrogen atom, an oxygen atom, a silicon atom, a sulfur atom, and a phosphorus atom; (C6-C20)aryl(C1-C20)alkyl
  • X' is an oxygen atom, a sulfur atom, or N-R (here, R is (C1-C20)alkyl).
  • Q is a divalent group capable of having two radicals to thereby be bonded to two nitrogen atoms and any divalent group may be used without limitation as long as it has a structure capable of linking two nitrogen atoms to each other.
  • Q may be a (C1-C30)hydrocarbon diradical with or without at least one of a halogen atom, a nitrogen atom, an oxygen atom, a silicon atom, a sulfur atom, and a phosphorus atom, more specifically, (C1-C20)alkylene, (C2-C20)alkenylene, (C2-C20)alkinylene, (C3-C20)cycloalkylene, or (C6-C30)arylene, wherein the alkylene, alkenylene, cycloalkylene, and arylene may include or not include at least one of a halogen atom, a nitrogen atom, an oxygen atom, a silicon atom, a sulfur atom, and a phosphorus atom. More preferably, Q is trans-1,2-cyclohexylene, phenylene, or ethylene.
  • R'' and R''' may be linked to each other to form an aromatic ring, and the formed aromatic ring may be further substituted with at least one selected from a group consisting of halogen; cyano; nitro; (C1-C20)alkyl; (C1-C20)alkyl substituted with a halogen atom; (C1-C20)alkyl(C6-C20)aryl; (C6-C20)aryl(C1-C20)alkyl; (C1-C20)alkoxy; (C6-C30)aryloxy; formyl; (C1-C20)alkylcarbonyl; and (C6-C20)arylcarbonyl.
  • R 1 to R 10 are each independently hydrogen, halogen, (C1-C20)alkyl, (C2-C20)alkenyl, (C1-C20)alkyl(C6-C20)aryl, (C6-C20)aryl(C1-C20)alkyl, (C1-C20)alkoxy, (C6-C30)aryloxy, formyl, (C1-C20)alkylcarbonyl, (C6-C20)arylcarbonyl, or a metalloid radical of Group 14 metal substituted with (C1-C20)alkyl or (C6-C20)aryl, at least one of R 1 to R 8 is -[YR 44 3-a ⁇ (CR 45 R 46 ) b N + R 21 R 22 R 23 ⁇ a ], Y is C or Si, R 44 , R 45 , R 46 , R 21 , R 22 , and R 23 are each
  • the epoxide compound may be at least one selected from a group consisting of (C2-C20)alkyleneoxide substituted or unsubstituted with halogen, (C1-C20)alkyloxy, (C6-C20)aryloxy, or (C6-C20)aryl(C1-C20)alkyloxy; (C4-C20)cycloalkyleneoxide substituted or unsubstituted with halogen, (C1-C20)alkyloxy, (C6-C20)aryloxy, or (C6-C20)aryl(C1-C20)alkyloxy; and (C8-C20)styreneoxide substituted or unsubstituted with halogen, (C1-C20)alkyloxy, (C6-C20)aryloxy, (C6-C20)aryl(C1-C20)alkyloxy
  • a specific example of the epoxide compound may include ethylene oxide, propylene oxide, butene oxide, pentene oxide, hexene oxide, octene oxide, decene oxide, dodecene oxide, tetradecene oxide, hexadecene oxide, octadecene oxide, butadiene monoxide, 1,2-epoxide-7-octene, epifluorohydrin, epichlorohydrin, epibromohydrin, isopropyl glycidyl ether, butyl glycidyl ether, t-butyl glycidyl ether, 2-ethylhexyl glycidyl ether, allyl glycidyl ether, cyclopentene oxide, cyclohexene oxide, cyclooctene oxide, cyclododec
  • step 1 bulk polymerization may be performed using the epoxide compound itself as a solvent, or a solvent may be further included as a reaction medium to thereby be used in polymerization. That is, in step 1), the solvent may be further put into the reactor. In this case, activity deterioration according to viscosity at the time of polymerization reaction may be suppressed by putting the solvent thereinto, and it may be easy to control a catalyst quenching and separation process after the reaction is completed.
  • the solvent may be at least one selected from a group consisting of aromatic hydrocarbons, halogenated hydrocarbons, ethers, and esters.
  • aromatic hydrocarbons such as benzene, toluene, xylene, and the like
  • the halogenated hydrocarbons such as chloromethane, methylenechloride, chloroform, carbon tetrachloride, 1,1-dichloroethane, 1,2-dichloroethane, ethylchloride, trichloroethane, 1-chloropropane, 2-chloropropane, 1-chlorobutane, 2-chlorobutane, 1-chloro-2-methylpropane, chlorobenzene, bromobenze, and the like
  • the ethers such as tetrahydrofuran, diethylether, di
  • the solvent may be at least one selected from a group consisting of toluene, dichloromethane, dichloroethane, tetrahydrofuran, and ethylacetate.
  • pressure of carbon dioxide in step 2) may be atmospheric pressure to 100 atm.
  • the pressure may be 5 to 30 atm.
  • An internal temperature of the reactor after injecting carbon dioxide, that is, a polymerization temperature may be 100°C or less, preferably 20 to 100°C, more preferably 20 to 60°C, and the polymerization may be performed for 5 to 20 hours.
  • a molar ratio of the epoxide compound : the salen ligand may be 100:1 to 1,000,000:1, preferably 100:1 to 50,000:1.
  • the epoxide compound may be used as the solvent simultaneously with a polymerization reactant, but in the case in which the molar ratio of the epoxide compound to the salen ligand is out of the above-mentioned range, a concentration of the reactant is significantly diluted, such that a polymerization activity of the catalyst may be deteriorated.
  • a molar ratio of the cobalt or chromium source : the salen ligand may be 1:0.9 to 1.1.
  • the molar ratio is out of the above-mentioned range, a significant difference in the ratio between the cobalt or chromium source and the salen ligand may be generated, such that a production amount of propylene carbonate may be increased, which may decrease polymerization selectivity.
  • a ligand 1 was prepared according to a method described in J. Am. Chem. Soc. 2002, 124, 1307 and used.
  • a ligand 2 was prepared according to Korean Patent B1 0853358 and used.
  • Propylene oxide (10mL), a ligand 1 (39mg), Co(OAc) 2 (13mg), bis(triphenylphospho-ranylidene)ammonium chloride (PPNCl, 41mg), and adipic acid (104mg) as a chain transfer agent were put into a 50mL reactor (stainless bomb reactor), and then the reactor was assembled. After injecting air having a pressure of 10 bar, the mixture was stirred at room temperature for 3 hours. Carbon dioxide having a pressure of 20 bar was additionally injected at room temperature and stirred for 6 hours. In this case, a total pressure of the reactor was 30 bar. After the reaction was finished, the reactor was cooled, and the reaction was terminated by removing gas pressure of carbon dioxide and air.
  • the prepared catalyst had the following structure.
  • Propylene oxide (10mL), a ligand 2 (111mg), Co(OAc) 2 (10mg), adipic acid (626mg) as a chain transfer agent, and toluene (10mL) as a solvent were put into a 50mL reactor (stainless bomb reactor), and then the reactor was assembled. After injecting air at 10 bar, the mixture was stirred at room temperature for 2 hours. Carbon dioxide having a pressure of 20 bar was additionally injected at room temperature and stirred for 15 hours while maintaining a temperature in the reactor at 50°C. In this case, a total pressure of the reactor was 30 bar. After the reaction was finished, the reactor was cooled, and the reaction was terminated by removing gas pressure of carbon dioxide and air.
  • the prepared catalyst had the following structure.
  • Example 1 Example Ligand PO/ligand Chain transfer agent Reaction PO conversion rate/selectivity Mn PDI Temperature(°C) time
  • Example 1 2000:1 Adipic acid (10eq) RT 6h 28%/91% 1335 1.05
  • Example 2 1 2000:1 AcOH (2eq) RT 16h 91%/33% 4251 1.31
  • Example 3 1 2000:1 MeOH (100eq) RT 15h 53%/95% 1826 1.06
  • Example 4 2 2000:1 Adipic acid(60eq) 50 15h 98%/95% 2136 1.08
  • Example 5 2 5000:1 Adipic acid(120eq) 50 15h 93%/97% 2247 1.08
  • the desired polycarbonate may be prepared by performing the putting of a metal source and a chain transfer agent into the reactor and injecting air and the injecting of carbon dioxide to polymerize epoxide and carbon dioxide regardless of the kind of ligand. It may be appreciated that in the case of Comparative Example 1, polymerization was attempted by the same method as in Examples 4 and 5 except that the chain transfer agent was not used, but the catalyst was not prepared from the ligand, such that the polymerization was not carried out. Therefore, it may be appreciated that in order to perform the polymerization simultaneously with preparing the catalyst from the ligand, the chain transfer agent was necessarily injected.
  • the catalytic activity was more excellent as compared to the ligand 1, which is a simple salen ligand in Examples 1 to 3.
  • polycarbonate was prepared with high yield and selectivity, and polycarbonate having narrow molecular distribution near a number average molecular weight of 2000 was obtained by using the chain transfer agent.
  • the method for preparing polycarbonate according to the exemplary embodiment of the present invention does not require a separate catalyst preparing step, such that simplicity of the entire process may be secured, and the catalyst loss generated during the manufacturing process may be decreased, thereby making it possible to decrease preparation cost of the catalyst and process cost.
  • the catalyst is partially reduced during storage and preservation of the catalyst, such that the catalytic activity may be deteriorated, but as in the present invention, in the case of preparing the catalyst from the ligand via the one-pot process, since there is no need to take care of storage and preservation of the catalyst and the activity due to reduction of the catalyst is not generated, such that stability may be secured.
  • an additional oxidant or pure oxygen gas should be used.
  • the oxidant after reaction, a catalyst separating process is required, and in the case of using pure oxygen gas, a fire risk may be significantly high, such that it may be difficult to secure stability.
  • the present invention since the organic metal catalyst in the high oxidation state is prepared via the one-pot process using air, which is a mixed gas having a low fire risk, to thereby be used in polymerization, the present invention is advantageous in view of safety.

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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 de préparation de polycarbonate, et plus particulièrement, un procédé de préparation de polycarbonate dans lequel la polymérisation de polycarbonate est effectuée par un procédé en enceinte unique conjointement avec la préparation d'un catalyseur de métal de transition organique. La présente invention concerne un procédé de préparation de polycarbonate, et plus particulièrement, un procédé de préparation de polycarbonate dans lequel la polymérisation de polycarbonate est effectuée par un procédé en enceinte unique conjointement avec la préparation d'un catalyseur de métal de transition organique à partir d'un ligand.
PCT/KR2013/010742 2012-11-29 2013-11-25 Procédé de préparation de polycarbonate Ceased WO2014084558A1 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
KR10-2012-0137394 2012-11-29
KR20120137394 2012-11-29
KR1020130142607A KR20140070392A (ko) 2012-11-29 2013-11-22 폴리 카보네이트의 신규한 제조방법
KR10-2013-0142607 2013-11-22

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WO2014084558A1 true WO2014084558A1 (fr) 2014-06-05

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20100136310A (ko) * 2009-06-18 2010-12-28 에스케이에너지 주식회사 이산화탄소/에폭사이드 공중합 촉매 시스템
WO2011028056A2 (fr) * 2009-09-03 2011-03-10 Sk Innovation Co., Ltd. Procédé continu pour la fabrication de polycarbonate aliphatique à partir de dioxyde de carbone et de composés époxydes
US20110207899A1 (en) * 2008-09-17 2011-08-25 Novomer, Inc. Aliphatic polycarbonate quench method
US20110230580A1 (en) * 2008-09-08 2011-09-22 Novomer, Inc Polycarbonate polyol compositions and methods
US20120226016A1 (en) * 2007-05-04 2012-09-06 Sk Innovation Co., Ltd. Process for producing polycarbonates and a coordination complex used therefor

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20120226016A1 (en) * 2007-05-04 2012-09-06 Sk Innovation Co., Ltd. Process for producing polycarbonates and a coordination complex used therefor
US20110230580A1 (en) * 2008-09-08 2011-09-22 Novomer, Inc Polycarbonate polyol compositions and methods
US20110207899A1 (en) * 2008-09-17 2011-08-25 Novomer, Inc. Aliphatic polycarbonate quench method
KR20100136310A (ko) * 2009-06-18 2010-12-28 에스케이에너지 주식회사 이산화탄소/에폭사이드 공중합 촉매 시스템
WO2011028056A2 (fr) * 2009-09-03 2011-03-10 Sk Innovation Co., Ltd. Procédé continu pour la fabrication de polycarbonate aliphatique à partir de dioxyde de carbone et de composés époxydes

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