WO2014204279A1 - Method of separating aliphatic polycarbonate polymer and catalyst from preparing process of copolymer - Google Patents

Method of separating aliphatic polycarbonate polymer and catalyst from preparing process of copolymer Download PDF

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WO2014204279A1
WO2014204279A1 PCT/KR2014/005494 KR2014005494W WO2014204279A1 WO 2014204279 A1 WO2014204279 A1 WO 2014204279A1 KR 2014005494 W KR2014005494 W KR 2014005494W WO 2014204279 A1 WO2014204279 A1 WO 2014204279A1
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atom
halogen
alkyl
nitrogen
oxygen
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French (fr)
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Jun Hee Kim
Jin Su Ham
Jong Ho Lim
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Sk Innovation Co., Ltd.
Sk Global Chemical Co., Ltd.
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    • C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
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    • B01J2231/34—Other additions, e.g. Monsanto-type carbonylations, addition to 1,2-C=X or 1,2-C-X triplebonds, additions to 1,4-C=C-C=X or 1,4-C=-C-X triple bonds with X, e.g. O, S, NH/N
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    • B01J2231/34—Other additions, e.g. Monsanto-type carbonylations, addition to 1,2-C=X or 1,2-C-X triplebonds, additions to 1,4-C=C-C=X or 1,4-C=-C-X triple bonds with X, e.g. O, S, NH/N
    • B01J2231/349—1,2- or 1,4-additions in combination with further or prior reactions by the same catalyst, i.e. tandem or domino reactions, e.g. hydrogenation or further addition reactions
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Definitions

  • the present invention relates to a method of separating an aliphatic polycarbonate polymer and a catalyst from a preparing process of a copolymer, and more particularly, to a method of separating an aliphatic polycarbonate polymer and a catalyst from a reaction mixture obtained by copolymerizing an epoxide compound and carbon dioxide in the presence of the catalyst which is a complex compound containing an onium salt.
  • a method of preparing polycarbonate by copolymerizing epoxide and carbon dioxide using a complex compound containing an onium salt as a catalyst and a method of separatively collecting and regenerating a catalyst from a mixed solution of the catalyst and a copolymer as the product have been disclosed in Korean Patent Nos. 10-0853358 and 10-0981270 filed by the same applicant as the present invention.
  • a catalyst in the final step of preparing polycarbonate by copolymerization of epoxide and carbon dioxide using a complex compound containing an onium salt as the catalyst is disposed at an end group of a long polymer to have a direct chemical bond with a polymer chain.
  • the polymerized polymer is decomposed into carbon dioxide and cyclic propylene carbonate (CPC), thereby causing a decrease in a molecular weight of a copolymer and deterioration in all physical properties therefrom to reduce value as a product.
  • alumina, silica gel, ion exchange resin, and the like are generally utilized (Prog. Polym. Sci. 2004, 29, 1053) and a method of removing the catalyst by a direction function of the catalyst and functional groups such as OH, SH present on the surface of an absorbent is largely used.
  • general silica and alumina have a low catalyst removal rate, such that a large amount of them need to be used to sufficiently remove the catalyst, thereby increasing cost of materials and preparation cost (the use of solvent and loss in pressure, and the like), and the like.
  • An object of the present invention is to provide a method capable of obtaining aliphatic polycarbonate having high purity from a reaction mixture obtained by preparing a copolymer using a complex compound containing an onium salt as a catalyst, and effectively separating and removing the remaining catalyst and by-products from the reaction product.
  • the present invention provides a method of capable of obtaining an aliphatic polycarbonate polymer having high purity by more effectively and economically separating and removing a catalyst and by-products from a reaction mixture of an aliphatic polycarbonate polymerization reaction performed in the presence of the catalyst which is a complex compound containing an onium salt.
  • the present invention provides a method of separating an aliphatic polycarbonate polymer and a catalyst in a reaction mixture of an aliphatic polycarbonate polymerization reaction performed in the presence of the catalyst which is a complex compound containing an onium salt, using two kinds of solvents which are not mixed with each other in the reaction mixture.
  • the two kinds of solvents which are not mixed with each other may be an organic solvent and an aqueous solution.
  • the method may include:
  • the organic solvent may be at least one selected from toluene, benzene, xylene, tetrahydrofuran, dichloromethane, dichloroethane, ethyl acetate, propyl acetate, isopropyl acetate, and butyl acetate, and the aqueous solution may contain 0.1 to 10wt% of an inorganic salt.
  • the epoxide compound may be at least one selected from a group consisting of (C2-C20)alkylene oxide unsubstituted or substituted with halogen, (C1-C20)alkyloxy, (C6-C20)aryloxy or (C6-C20)ar(C1-C20)alkyl(aralkyl)oxy; (C4-C20) cycloalkylene oxide unsubstituted or substituted with halogen, (C1-C20)alkyloxy, (C6-C20)aryloxy or (C6-C20)ar(C1-C20)alkyl(aralkyl)oxy; and (C8-C20)styrene oxide unsubstituted or substituted with halogen, (C1-C20)alkyloxy, (C6-C20)aryloxy, (C6-C20)ar(C1-C20)alkyl(aralkyl)oxy or (C1-C20)
  • the complex compound containing an onium salt may be represented by the following Chemical Formula 1:
  • M is trivalent cobalt or trivalent chromium
  • A is an oxygen or sulfur atom
  • Q is a diradical connecting two nitrogen atoms
  • R 1 to R 10 are each independently hydrogen; halogen; (C1-C20)alkyl; (C1-C20)alkyl containing one or more of halogen, nitrogen, oxygen, silicon, sulfur and phosphorus; (C2-C20)alkenyl; (C2-C20)alkenyl containing one or more of halogen, nitrogen, oxygen, silicon, sulfur and phosphorus; (C1-C20)alkyl(C6-C20)aryl; (C1-C20)alkyl(C6-C20)aryl containing one or more of halogen, nitrogen, oxygen, silicon, sulfur and phosphorus; (C6-C20)aryl(C1-C20)alkyl; (C6-C20)aryl(C1-C20)alkyl containing one or more of halogen, nitrogen, oxygen, silicon, sulfur and phosphorus; (C1-C20)alkoxy; (C6-C30)aryloxy; formyl; (C1-C20
  • R 1 to R 10 may be linked with each other to form a ring
  • At least one hydrogen included in R 1 to R 10 and Q is a proton group selected from a group consisting of the following Chemical Formulas a, b, and c;
  • X - is each independently a halogen anion; HCO 3 - ; BF 4 - ; ClO 4 - ; NO 3 - ; PF 6 - ; a (C6-C20)aryloxy anion; a (C6-C20)aryloxy anion containing one or more of a halogen atom, a nitrogen atom, an oxygen atom, a silicon atom, a sulfur atom and a phosphorus atom; a (C1-C20)alkylcarboxyl anion; a (C1-C20)alkylcarboxyl anion containing one or more of a halogen atom, a nitrogen atom, an oxygen atom, a silicon atom, a sulfur atom and a phosphorus atom; a (C6-C20)arylcarboxyl anion; a (C6-C20)arylcarboxyl anion containing one or more of a halogen atom,
  • 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 one or more of halogen, nitrogen, oxygen, silicon, sulfur and phosphorus; (C2-C20) alkenyl; (C2-C20) alkenyl containing one or more of halogen, nitrogen, oxygen, silicon, sulfur and phosphorus; (C1-C20)alkyl(C6-C20)aryl; (C1-C20)alkyl(C6-C20)aryl containing one or more of halogen, nitrogen, oxygen, silicon, sulfur and phosphorus; (C6-C20)aryl(C1-C20)alkyl; (C6-C20)aryl(C1-C20)alkyl containing one or more of halogen, nitrogen, oxygen, silicon, sulfur and phosphorus; or a metalloid radical of Group 14 metal substituted with (
  • R 41 , R 42 and R 43 are each independently hydrogen; (C1-C20)alkyl; (C1-C20) alkyl containing one or more of halogen, nitrogen, oxygen, silicon, sulfur and phosphorus; (C2-C20) alkenyl; (C2-C20) alkenyl containing one or more of halogen, nitrogen, oxygen, silicon, sulfur and phosphorus; (C1-C20)alkyl(C6-C20)aryl; (C1-C20)alkyl(C6-C20)aryl containing one or more of halogen, nitrogen, oxygen, silicon, sulfur and phosphorus; (C6-C20)aryl(C1-C20)alkyl; (C6-C20)aryl(C1-C20)alkyl containing one or more of halogen, nitrogen, oxygen, silicon, sulfur and phosphorus; or a metalloid radical of Group 14 metal substituted with (C1-C20)alkyl or (C6-C20)ary
  • X' is an oxygen atom, a sulfur atom or N-R (wherein R is (C1-C20)alkyl);
  • n is an integer obtained by adding 1 to the total number of proton groups included in R 1 to R 10 and Q;
  • X - may be coordinated to M
  • a nitrogen atom of imine may be coordinated or decoordinated to M.
  • the present invention provides an apparatus of separating an aliphatic polycarbonate polymer and a catalyst in a reaction mixture of an aliphatic polycarbonate polymerization reaction performed in the presence of the catalyst which is a complex compound containing an onium salt, from the reaction mixture, the apparatus including:
  • a reactor 100 performing the aliphatic polycarbonate polymerization reaction catalyzed by the catalyst which is the complex compound containing an onium salt;
  • phase-separator 200 separating an organic layer and an aqueous solution layer by adding two kinds of solvents which are not mixed with each other to the reaction mixture of the polymerization reaction obtained by the reactor, and performing an extraction process;
  • a refiner 300 obtaining the aliphatic polycarbonate from the organic layer separated from the phase-separator.
  • a catalyst-collector (not-shown) collecting the catalyst from the aqueous solution layer separated from the phase-separator.
  • the method according to the present invention uses two kinds of solvents which are not mixed with each other in a reaction mixture of an aliphatic polycarbonate polymerization reaction performed in the presence of a catalyst which is a complex compound containing an onium salt to remove cyclic carbonate which is a by-product produced at the time of the polymerization reaction, thereby obtaining aliphatic polycarbonate having high purity and easily removing the catalyst used in the reaction.
  • the method according to the present invention removes the catalyst, using the two kinds of solvents which are not mixed with each other rather than using the existing silica or resin, in the reaction mixture of the aliphatic polycarbonate polymerization reaction performed in the presence of the catalyst which is the complex compound containing an onium salt, such that a back biting phenomenon of the previously prepared aliphatic polycarbonate polymer is not generated, whereby the cyclic carbonate may not be produced and cyclic carbonate produced at the time of time of the polymerization reaction may be removed.
  • the method according to the present invention removes the catalyst with a simple process, using the two kinds of solvents which are not mixed with each other rather than using the existing silica, resin, and the like, to increase a removal rate of the catalyst and the by-products, which is significantly effective.
  • the method is significantly economical.
  • the removal rate of the cyclic carbonate produced at the time of polymerization with the catalyst is high, and the back biting phenomenon of the aliphatic polycarbonate polymer is not generated, such that the aliphatic polycarbonate polymer having high purity may be obtained, thereby improving quality of a product containing the same.
  • FIG. 1 is a schematic diagram showing a process of separating an aliphatic polycarbonate polymer and a catalyst from a reaction mixture of an aliphatic polycarbonate polymerization reaction according to an exemplary embodiment of the present invention.
  • REACTOR 200 PHASE-SEPARATOR
  • the present invention provides a method of separating an aliphatic polycarbonate polymer and a catalyst in a reaction mixture of an aliphatic polycarbonate polymerization reaction performed in the presence of the catalyst which is a complex compound containing an onium salt, using two kinds of solvents which are not mixed with each other in the reaction mixture.
  • the method according to the present invention may remove the catalyst used in the reaction and cyclic carbonate produced at the time of the polymerization reaction to obtain an aliphatic polycarbonate polymer having high purity.
  • the method according to the present invention does not need separate apparatuses required for the existing separation method or materials such as adsorbent, and the like, which is significantly economical, and has a high removal rate of cyclic carbonate produced at the time of polymerization reaction with the catalyst to deteriorate purity of the aliphatic polycarbonate polymer.
  • a back biting phenomenon of the aliphatic polycarbonate polymer produced at the time of separation using the existing silica, resin, and the like, is not generated, that is, the cyclic carbonate is not produced, such that the aliphatic polycarbonate polymer having high purity may be obtained at a high yield.
  • the reaction mixture which is a target of the present invention may be a solution obtained in the state in which epoxide and carbon dioxide are copolymerized using the catalyst with a polymerization reaction described in Korean Patent Laid-Open Publication No. 10-2009-0090154 and then the remaining carbon dioxide and epoxide which are not reacted are not removed, a solution obtained in the state in which after the polymerization, carbon dioxide is merely removed, or a solution obtained in the state in which after the polymerization, both of carbon dioxide and epoxide are removed, and other solvents are added again for a subsequent treatment.
  • Two kinds of solvents which are not mixed with each other according to an exemplary embodiment of the present invention may be an organic solvent and an aqueous solution.
  • the organic solvent according to an exemplary embodiment of the present invention may be at least one selected from toluene, benzene, xylene, tetrahydrofuran, dichloromethane, dichloroethane, ethyl acetate, propyl acetate, isopropyl acetate, butyl acetate, and in view of more effective separation, the organic solvent may be toluene, tetrahydrofuran or mixed solvents thereof.
  • the aqueous solution according to an exemplary embodiment of the present invention may contain 0.1 to 20wt% of an inorganic salt, preferably, 0.1 to 10wt%, and more preferably, 0.8 to 10wt% for more effective removal of the catalyst and the cyclic carbonate.
  • the inorganic salt according to an exemplary embodiment of the present invention is any inorganic salt as long as the salt is generally used; however, may be sodium chloride, ammonium chloride, sodium bicarbonate or mixtures thereof for increasing a removal rate of the catalyst and the reaction by-products.
  • the extraction process of step b) according to an exemplary embodiment of the present invention, that is, the extraction process in the separating of an organic layer and an aqueous solution layer including the adding of the two kinds of solvents which are not mixed with each other to the reaction mixture of the step a) and the performing of an extraction process may be performed once or more, preferably, three times or more to increase aliphatic polycarbonate having high purity and a removal rate of the catalyst and the by-products.
  • the organic solvent may be toluene, tetrahydrofuran or mixed solvents thereof, and the aqueous solution may contain 0.8 to 10wt% of an inorganic salt.
  • the aliphatic polycarbonate polymer according to an exemplary embodiment of the present invention which is polycarbonate prepared by polymerizing carbon dioxide and epoxide compound described below, may be polypropylene carbonate, polyethylene carbonate, polycyclohexene carbonate, polybutylene carbonate or polycyclopentene carbonate, preferably, polypropylene carbonate, polyethylene carbonate or polybutylene carbonate.
  • the epoxide compound according to an exemplary embodiment of the present invention may be at least one selected from a group consisting of (C2-C20)alkylene oxide unsubstituted or substituted with halogen, (C1-C20)alkyloxy, (C6-C20)aryloxy or (C6-C20)ar(C1-C20)alkyl(aralkyl)oxy; (C4-C20) cycloalkylene oxide unsubstituted or substituted with halogen, (C1-C20)alkyloxy, (C6-C20)aryloxy or (C6-C20)ar(C1-C20)alkyl(aralkyl)oxy; and (C8-C20)styrene oxide unsubstituted or substituted with halogen, (C1-C20)alkyloxy, (C6-C20)aryloxy, (C6-C20)ar(C1-C20)alkyl(aralkyl
  • the complex compound containing an onium salt may be represented by the following Chemical Formula 1:
  • M is trivalent cobalt or trivalent chromium
  • A is an oxygen or sulfur atom
  • Q is a diradical connecting two nitrogen atoms
  • R 1 to R 10 are each independently hydrogen; halogen; (C1-C20)alkyl; (C1-C20)alkyl containing one or more of halogen, nitrogen, oxygen, silicon, sulfur and phosphorus; (C2-C20)alkenyl; (C2-C20)alkenyl containing one or more of halogen, nitrogen, oxygen, silicon, sulfur and phosphorus; (C1-C20)alkyl(C6-C20)aryl; (C1-C20)alkyl(C6-C20)aryl containing one or more of halogen, nitrogen, oxygen, silicon, sulfur and phosphorus; (C6-C20)aryl(C1-C20)alkyl; (C6-C20)aryl(C1-C20)alkyl containing one or more of halogen, nitrogen, oxygen, silicon, sulfur and phosphorus; (C1-C20)alkoxy; (C6-C30)aryloxy; formyl; (C1-C20
  • R 1 to R 10 may be linked with each other to form a ring
  • At least one hydrogen included in R 1 to R 10 and Q is a proton group selected from a group consisting of the following Chemical Formulas a, b, and c;
  • X - is each independently a halogen anion; HCO 3 - ; BF 4 - ; ClO 4 - ; NO 3 - ; PF 6 - ; a (C6-C20)aryloxy anion; a (C6-C20)aryloxy anion containing one or more of a halogen atom, a nitrogen atom, an oxygen atom, a silicon atom, a sulfur atom and a phosphorus atom; a (C1-C20)alkylcarboxyl anion; a (C1-C20)alkylcarboxyl anion containing one or more of a halogen atom, a nitrogen atom, an oxygen atom, a silicon atom, a sulfur atom and a phosphorus atom; a (C6-C20)arylcarboxyl anion; a (C6-C20)arylcarboxyl anion containing one or more of a halogen atom,
  • 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 one or more of halogen, nitrogen, oxygen, silicon, sulfur and phosphorus; (C2-C20) alkenyl; (C2-C20) alkenyl containing one or more of halogen, nitrogen, oxygen, silicon, sulfur and phosphorus; (C1-C20)alkyl(C6-C20)aryl; (C1-C20)alkyl(C6-C20)aryl containing one or more of halogen, nitrogen, oxygen, silicon, sulfur and phosphorus; (C6-C20)aryl(C1-C20)alkyl; (C6-C20)aryl(C1-C20)alkyl containing one or more of halogen, nitrogen, oxygen, silicon, sulfur and phosphorus; or a metalloid radical of Group 14 metal substituted with (
  • R 41 , R 42 and R 43 are each independently hydrogen; (C1-C20)alkyl; (C1-C20) alkyl containing one or more of halogen, nitrogen, oxygen, silicon, sulfur and phosphorus; (C2-C20) alkenyl; (C2-C20) alkenyl containing one or more of halogen, nitrogen, oxygen, silicon, sulfur and phosphorus; (C1-C20)alkyl(C6-C20)aryl; (C1-C20)alkyl(C6-C20)aryl containing one or more of halogen, nitrogen, oxygen, silicon, sulfur and phosphorus; (C6-C20)aryl(C1-C20)alkyl; (C6-C20)aryl(C1-C20)alkyl containing one or more of halogen, nitrogen, oxygen, silicon, sulfur and phosphorus; or a metalloid radical of Group 14 metal substituted with (C1-C20)alkyl or (C6-C20)ary
  • X' is an oxygen atom, a sulfur atom or N-R (wherein R is (C1-C20)alkyl);
  • n is an integer obtained by adding 1 to the total number of proton groups included in R 1 to R 10 and Q;
  • X - may be coordinated to M
  • a nitrogen atom of imine may be coordinated or decoordinated to M.
  • M is trivalent cobalt
  • A is an oxygen
  • Q is a trans-1,2-cyclohexylene, phenylene or ethylene
  • R 1 and R 2 are the same or different primary (C1-C20)alkyl
  • R 3 to R 10 are each independently hydrogen or -[YR 51 3-a (CR 52 R 53 ) b N + R 54 R 55 R 56 a ];
  • Y is C or Si
  • R 51 , R 52 , R 53 , R 54 , R 55 and R 56 are each independently hydrogen; halogen; (C1-C20)alkyl; (C1-C20)alkyl containing one or more of halogen, nitrogen, oxygen, silicon, sulfur and phosphor; (C2-C20)alkenyl; (C2-C20)alkenyl containing one or more of halogen, nitrogen, oxygen, silicon, sulfur and phosphor; (C1-C20)alkyl(C6-C20)aryl; (C1-C20)alkyl(C6-C20)aryl containing one or more of halogen, nitrogen, oxygen, silicon, sulfur and phosphor; (C6-C20)aryl(C1-C20)alkyl; (C6-C20)aryl(C1-C20)alkyl containing one or more of halogen, nitrogen, oxygen, silicon, sulfur and phosphor; (C1-C30)
  • a is an integer of 1 to 3
  • b is an integer of 1 to 20;
  • n is an integer of 4 or more, obtained by adding 1 to the total number of a quaternary ammonium salt included in R 3 to R 10 ;
  • R 3 to R 10 when a is 1, at least three of R 3 to R 10 may be -[YR 51 3-a (CR 52 R 53 ) b N + R 54 R 55 R 56 a ], when a is 2, at least two of R 3 to R 10 may be -[YR 51 3-a (CR 52 R 53 ) b N + R 54 R 55 R 56 a ], and when a is 3, at least one of R 3 to R 10 may be -[YR 51 3-a (CR 52 R 53 ) b N + R 54 R 55 R 56 a ].
  • Chemical Formula 1 may be a complex compound represented by the following Chemical Formula 2:
  • R 61 and R 62 are each independently methyl or ethyl;
  • X - is each independently nitrate or acetate anion; nitrogen of imine may be coordinated or decoordinated to cobalt, and each anion may be coordinated to cobalt.
  • the present invention provides an aliphatic polycarbonate polymer containing the cyclic carbonate in a content of 2 to 7wt%, preferably, 2 to 5wt%, based on the obtained aliphatic polycarbonate polymer.
  • the present invention provides an aliphatic polycarbonate polymer containing the metal catalyst in a content of 10ppm or less, preferably, 5ppm, more preferably, 2ppm or less according to the method of the present invention.
  • M is trivalent cobalt
  • A is an oxygen
  • Q is a trans-1,2-cyclohexylene, phenylene or ethylene
  • R 1 and R 2 are the same or different primary (C1-C20)alkyl
  • R 3 to R 10 are each independently hydrogen or -[YR 51 3-a (CR 52 R 53 ) b N + R 54 R 55 R 56 a ];
  • Y is C or Si
  • R 51 , R 52 , R 53 , R 54 , R 55 and R 56 are each independently hydrogen; halogen; (C1-C20)alkyl; (C1-C20)alkyl containing one or more of halogen, nitrogen, oxygen, silicon, sulfur and phosphor; (C2-C20)alkenyl; (C2-C20)alkenyl containing one or more of halogen, nitrogen, oxygen, silicon, sulfur and phosphor; (C1-C20)alkyl(C6-C20)aryl; (C1-C20)alkyl(C6-C20)aryl containing one or more of halogen, nitrogen, oxygen, silicon, sulfur and phosphor; (C6-C20)aryl(C1-C20)alkyl; (C6-C20)aryl(C1-C20)alkyl containing one or more of halogen, nitrogen, oxygen, silicon, sulfur and phosphor; (C1-C30)
  • a is an integer of 1 to 3
  • b is an integer of 1 to 20;
  • n is an integer of 4 or more, obtained by adding 1 to the total number of a quaternary ammonium salt included in R 3 to R 10 ;
  • R 3 to R 10 may be -[YR 51 3-a (CR 52 R 53 ) b N + R 54 R 55 R 56 a ], when a is 2, at least two of R 3 to R 10 may be -[YR 51 3-a (CR 52 R 53 ) b N + R 54 R 55 R 56 a ], and when a is 3, at least one of R 3 to R 10 may be -[YR 51 3-a (CR 52 R 53 ) b N + R 54 R 55 R 56 a ], and the two kinds of solvents which are not mixed with each other may be a combination of the organic solvents such as toluene, tetrahydrofuran, or mixtures thereof, and the aqueous solution containing 0.5 to 10wt% of an inorganic salt, thereby providing the aliphatic polycarbonate polymer containing the cyclic carbonate in a content of 2 to 7wt%, preferably, 2 to 5wt%
  • Substituents including ⁇ alkyl ⁇ , ⁇ alkoxy ⁇ and other ⁇ alkyl ⁇ parts described in the present invention include both of linear type or branched type.
  • ⁇ aryl ⁇ described in the present invention which is an organic radical derived from aromatic hydrocarbon due to removal of one hydrogen, includes a single ring system or a fused ring system including 4 to 7 ring atoms, preferably, 5 or 6 ring atoms in each ring, and even includes a form in which a plurality of aryls are connected by a single bond.
  • alkenyl defined in the present invention means a linear-, branched-, or a cyclic hydrocarbon radical containing 2 to 20 carbon atoms and at least one carbon to carbon double bond.
  • ⁇ containing one or more of halogen, nitrogen, oxygen, silicon, sulfur and phosphorus ⁇ described in the present invention means substituent groups including one or more of halogen, nitrogen, oxygen, silicon, sulfur and phosphorus
  • ⁇ an alkyl containing one or more of halogen, nitrogen, oxygen, silicon, sulfur and phosphorus ⁇ means an alkyl including substituent groups including one or more of halogen, nitrogen, oxygen, silicon, sulfur and phosphorus.
  • haloalkyl, alkoxy and aminoalkyl may be included, but the present invention is not limited thereto.
  • (C1-C20)alkyl, (C1-C20)alkoxy, and (C3-C20)cycloalkyl may be preferably (C1-C10)alkyl, (C1-C10)alkoxy, (C3-C12)cycloalkyl;
  • (C6-C20)aryl may be preferably (C6-C12)aryl.
  • the present invention provides an apparatus of separating an aliphatic polycarbonate polymer and a catalyst in a reaction mixture of an aliphatic polycarbonate polymerization reaction performed in the presence of the catalyst which is a complex compound containing an onium salt, from the reaction mixture, the apparatus including:
  • a reactor 100 performing the aliphatic polycarbonate polymerization reaction catalyzed by the catalyst which is the complex compound containing an onium salt;
  • phase-separator 200 separating an organic layer and an aqueous solution layer by adding two kinds of solvents which are not mixed with each other to the reaction mixture of the polymerization reaction obtained by the reactor, and performing an extraction process;
  • a refiner 300 obtaining the aliphatic polycarbonate from the organic layer separated from the phase-separator.
  • a catalyst-collector (not-shown) collecting the catalyst from the aqueous solution layer separated from the phase-separator.
  • the reactor 100 is a place where the epoxide compound and carbon dioxide are reacted in the presence of the catalyst which is a complex compound containing an onium salt to perform the aliphatic polycarbonate polymerization reaction.
  • the reaction mixture may be moved to the phase-separator 200 and two kinds of solvents which are not mixed with each other may be put into the phase-separator to be separated into the organic layer and the aqueous solution layer, wherein the phase-separation may be performed by putting two kinds of solvents which are not mixed with each other into the reactor without moving the reaction mixture to the phase-separator, and thus, in this case, the reactor may be a phase-separator.
  • the reaction mixture prepared in the reactor of the present invention may be moved to the phase-separator 200 by a first pump 410, and the aqueous solution containing the inorganic salt may be supplied to the phase-separator 200 by a second pump 420.
  • the organic layer separated from the phase-separator may be moved to the refiner 300 by a third pump 430, the organic solvent may be discharged to an organic solvent discharging part 510 by distillation under reduced pressure and collected, and the aliphatic polycarbonate may be obtained by an aliphatic polycarbonate discharging part 520 and additional refinement may be performed to obtain an aliphatic polycarbonate having more high purity.
  • the aqueous solution layer separated from phase-separator may be moved to the catalyst-collector (not-shown) by a fourth pump 440, the catalyst and the reaction by-products may be removed, and the obtained catalyst may be collected so as to be reusable, by performing additional refinement.
  • Example 2 Method of Removing Catalyst by Extraction with 0.8 wt% Sodium Chloride Aqueous Solution
  • Example 5 Method of Removing Catalyst by Extraction with 5.0 wt% Sodium Chloride Aqueous Solution Three Times
  • Example 8 Method of Removing Catalyst by Extraction with Acetonitrile - 5.0 wt% Sodium Chloride Aqueous Solution Three Times
  • a tube having a diameter of 4.0 cm and a length of 30.0 cm was filled with an ion-exchange resin (Amberlyst 15) and a sufficient amount of dichloromethane was allowed to flow thereinto.
  • 30 g of polypropylenecarbonate diol (cyclopropylene carbonate: 12%) of which the reaction was completed under the polymerization conditions was diluted with 100 mL of dichloromethane in a tube filled with an ion-exchange resin or silica gel and then was allowed to flow into a tube filled with an adsorbent at a flow velocity of 3.0 mL/min. The organic solvent was removed by distillation under reduced pressure and 30 g of polypropylenecarbonate diol was obtained.
  • a tube having a diameter of 4.0 cm and a length of 30.0 cm was filled with 20g of a silica gel and a sufficient amount of dichloromethane was allowed to flow thereinto.
  • 30 g of polypropylenecarbonate diol (cyclopropylene carbonate: 12%) of which the reaction was completed under the polymerization conditions was diluted with 100 mL of dichloromethane in a tube filled with an ion-exchange resin or silica gel and then was allowed to flow into a tube filled with an adsorbent at a flow velocity of 3.0 mL/min. The organic solvent was removed by and 30 g of polypropylenecarbonate diol was obtained.
  • the separation method according to the present invention is remarkably effective process in which an aliphatic polycarbonate polymer having high purity may be effectively and economically obtained by a simple process.

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Abstract

Provided is a method of separating a catalyst from a solution containing a copolymer and the catalyst dissolved therein, after a polymerization reaction is performed using the catalyst, and more specifically, selection and utilization of an adsorbent used for separation.

Description

METHOD OF SEPARATING ALIPHATIC POLYCARBONATE POLYMER AND CATALYST FROM PREPARING PROCESS OF COPOLYMER
The present invention relates to a method of separating an aliphatic polycarbonate polymer and a catalyst from a preparing process of a copolymer, and more particularly, to a method of separating an aliphatic polycarbonate polymer and a catalyst from a reaction mixture obtained by copolymerizing an epoxide compound and carbon dioxide in the presence of the catalyst which is a complex compound containing an onium salt.
A method of preparing polycarbonate by copolymerizing epoxide and carbon dioxide using a complex compound containing an onium salt as a catalyst and a method of separatively collecting and regenerating a catalyst from a mixed solution of the catalyst and a copolymer as the product have been disclosed in Korean Patent Nos. 10-0853358 and 10-0981270 filed by the same applicant as the present invention.
There is a case in which a metal catalyst for polymer polymerization is not separated from the final product, such as a Ziegler Natta catalyst; however, this case is extremely rare and catalysts should be necessarily removed or collected by the following reasons.
A catalyst in the final step of preparing polycarbonate by copolymerization of epoxide and carbon dioxide using a complex compound containing an onium salt as the catalyst is disposed at an end group of a long polymer to have a direct chemical bond with a polymer chain. When time elapses in the state in which the catalyst is not separate, the polymerized polymer is decomposed into carbon dioxide and cyclic propylene carbonate (CPC), thereby causing a decrease in a molecular weight of a copolymer and deterioration in all physical properties therefrom to reduce value as a product.
In addition, when a ligand containing a chromophore and a transition metal complex salt are not completely removed in the product, final product has a color to have a problem in quality and commercial value, and due to toxicity of the transition metal, an application field as the polymer may be limited.
In particular, in a case of a copolymerization catalyst of carbon dioxide/epoxide which is an inventive subject of the present invention, since the metal itself is expensive and the catalyst contains many high priced ligands, the catalyst used in order to secure economical efficiency should be necessarily removed and collected.
In order to separate or remove the catalyst used in the polymer polymerization, alumina, silica gel, ion exchange resin, and the like, are generally utilized (Prog. Polym. Sci. 2004, 29, 1053) and a method of removing the catalyst by a direction function of the catalyst and functional groups such as OH, SH present on the surface of an absorbent is largely used. However, general silica and alumina have a low catalyst removal rate, such that a large amount of them need to be used to sufficiently remove the catalyst, thereby increasing cost of materials and preparation cost (the use of solvent and loss in pressure, and the like), and the like.
Therefore, an effective and economical method capable of obtaining an aliphatic polycarbonate polymer having high purity from a preparing process of a copolymer and separating and removing a catalyst and reaction by-products has been required.
An object of the present invention is to provide a method capable of obtaining aliphatic polycarbonate having high purity from a reaction mixture obtained by preparing a copolymer using a complex compound containing an onium salt as a catalyst, and effectively separating and removing the remaining catalyst and by-products from the reaction product.
The present invention provides a method of capable of obtaining an aliphatic polycarbonate polymer having high purity by more effectively and economically separating and removing a catalyst and by-products from a reaction mixture of an aliphatic polycarbonate polymerization reaction performed in the presence of the catalyst which is a complex compound containing an onium salt.
In one general aspect, the present invention provides a method of separating an aliphatic polycarbonate polymer and a catalyst in a reaction mixture of an aliphatic polycarbonate polymerization reaction performed in the presence of the catalyst which is a complex compound containing an onium salt, using two kinds of solvents which are not mixed with each other in the reaction mixture.
The two kinds of solvents which are not mixed with each other may be an organic solvent and an aqueous solution.
The method may include:
a) polymerizing carbon dioxide and an epoxide compound in the presence of the catalyst which is the complex compound containing an onium salt;
b) separating an organic layer and an aqueous solution layer by adding the two kinds of solvents which are not mixed with each other to the reaction mixture of the step a) and performing an extraction process;
c) obtaining aliphatic polycarbonate from the separated organic layer; and
d) collecting the catalyst from the separated aqueous solution layer.
The organic solvent may be at least one selected from toluene, benzene, xylene, tetrahydrofuran, dichloromethane, dichloroethane, ethyl acetate, propyl acetate, isopropyl acetate, and butyl acetate, and the aqueous solution may contain 0.1 to 10wt% of an inorganic salt.
The epoxide compound may be at least one selected from a group consisting of (C2-C20)alkylene oxide unsubstituted or substituted with halogen, (C1-C20)alkyloxy, (C6-C20)aryloxy or (C6-C20)ar(C1-C20)alkyl(aralkyl)oxy; (C4-C20) cycloalkylene oxide unsubstituted or substituted with halogen, (C1-C20)alkyloxy, (C6-C20)aryloxy or (C6-C20)ar(C1-C20)alkyl(aralkyl)oxy; and (C8-C20)styrene oxide unsubstituted or substituted with halogen, (C1-C20)alkyloxy, (C6-C20)aryloxy, (C6-C20)ar(C1-C20)alkyl(aralkyl)oxy or (C1-C20)alkyl. The aliphatic polycarbonate polymer may be polypropylene carbonate, polyethylene carbonate, polycyclohexene carbonate, polybutylene carbonate, polycyclopentene carbonate, polycyclooctene carbonate.
The complex compound containing an onium salt may be represented by the following Chemical Formula 1:
[Chemical Formula 1]
[Rectified under Rule 91, 05.08.2014]
Figure WO-DOC-FIGURE-22
in Chemical Formula 1 above,
M is trivalent cobalt or trivalent chromium;
A is an oxygen or sulfur atom;
Q is a diradical connecting two nitrogen atoms;
R1 to R10 are each independently hydrogen; halogen; (C1-C20)alkyl; (C1-C20)alkyl containing one or more of halogen, nitrogen, oxygen, silicon, sulfur and phosphorus; (C2-C20)alkenyl; (C2-C20)alkenyl containing one or more of halogen, nitrogen, oxygen, silicon, sulfur and phosphorus; (C1-C20)alkyl(C6-C20)aryl; (C1-C20)alkyl(C6-C20)aryl containing one or more of halogen, nitrogen, oxygen, silicon, sulfur and phosphorus; (C6-C20)aryl(C1-C20)alkyl; (C6-C20)aryl(C1-C20)alkyl containing one or more of halogen, nitrogen, oxygen, silicon, sulfur and phosphorus; (C1-C20)alkoxy; (C6-C30)aryloxy; formyl; (C1-C20)alkylcarbonyl; or (C6-C20)arylcarbonyl; or a metalloid radical of Group 14 metal substituted with (C1-C20)alkyl or (C6-C20)aryl;
two of R1 to R10 may be linked with each other to form a ring;
at least one hydrogen included in R1 to R10 and Q is a proton group selected from a group consisting of the following Chemical Formulas a, b, and c;
[Chemical Formula a] [Chemical Formula b] [Chemical Formula c]
Figure PCTKR2014005494-appb-I000002
Figure PCTKR2014005494-appb-I000003
Figure PCTKR2014005494-appb-I000004
X- is each independently a halogen anion; HCO3 -; BF4 -; ClO4 -; NO3 -; PF6 -; a (C6-C20)aryloxy anion; a (C6-C20)aryloxy anion containing one or more of a halogen atom, a nitrogen atom, an oxygen atom, a silicon atom, a sulfur atom and a phosphorus atom; a (C1-C20)alkylcarboxyl anion; a (C1-C20)alkylcarboxyl anion containing one or more of a halogen atom, a nitrogen atom, an oxygen atom, a silicon atom, a sulfur atom and a phosphorus atom; a (C6-C20)arylcarboxyl anion; a (C6-C20)arylcarboxyl anion containing one or more of a halogen atom, a nitrogen atom, an oxygen atom, a silicon atom, a sulfur atom and a phosphorus atom; a (C1-C20)alkoxy anion; a (C1-C20)alkoxy anion containing one or more of a halogen atom, a nitrogen atom, an oxygen atom, a silicon atom, a sulfur atom and a phosphorus atom; a (C1-C20)alkylcarbonate anion; a (C1-C20)alkylcarbonate anion containing one or more of a halogen atom, a nitrogen atom, an oxygen atom, a silicon atom, a sulfur atom and a phosphorus atom; a (C6-C20)arylcarbonate anion; a (C6-C20)arylcarbonate anion containing one or more of a halogen atom, a nitrogen atom, an oxygen atom, a silicon atom, a sulfur atom and a phosphorus atom; a (C1-C20)alkylsulfonate anion; a (C1-C20)alkylsulfonate anion containing one or more of a halogen atom, a nitrogen atom, an oxygen atom, a silicon atom, a sulfur atom and a phosphorus atom; a (C1-C20)alkylamido anion; a (C1-C20)alkylamido anion containing one or more of a halogen atom, a nitrogen atom, an oxygen atom, a silicon atom, a sulfur atom and a phosphorus atom; a (C6-C20)arylamido anion; a (C6-C20)arylamido anion containing one or more of a halogen atom, a nitrogen atom, an oxygen atom, a silicon atom, a sulfur atom and a phosphorus atom; a (C1-C20)alkylcarbamate anion; a (C1-C20)alkylcarbamate anion containing one or more of a halogen atom, a nitrogen atom, an oxygen atom, a silicon atom, a sulfur atom and a phosphorus atom; a (C6-C20)arylcarbamate anion; or a (C6-C20)arylcarbamate anion containing one or more of a halogen atom, a nitrogen atom, an oxygen atom, a silicon atom, a sulfur atom and a phosphorus atom;
Z is a nitrogen or phosphorus atom;
R21, R22, R23, R31, R32, R33, R34 and R35 are each independently (C1-C20)alkyl; (C1-C20) alkyl containing one or more of halogen, nitrogen, oxygen, silicon, sulfur and phosphorus; (C2-C20) alkenyl; (C2-C20) alkenyl containing one or more of halogen, nitrogen, oxygen, silicon, sulfur and phosphorus; (C1-C20)alkyl(C6-C20)aryl; (C1-C20)alkyl(C6-C20)aryl containing one or more of halogen, nitrogen, oxygen, silicon, sulfur and phosphorus; (C6-C20)aryl(C1-C20)alkyl; (C6-C20)aryl(C1-C20)alkyl containing one or more of halogen, nitrogen, oxygen, silicon, sulfur and phosphorus; or a metalloid radical of Group 14 metal substituted with (C1-C20)alkyl or (C6-C20)aryl; two of R21, R22 and R23 or two of R31, R32, R33, R34 and R35 may be linked with each other to form a ring;
R41, R42 and R43 are each independently hydrogen; (C1-C20)alkyl; (C1-C20) alkyl containing one or more of halogen, nitrogen, oxygen, silicon, sulfur and phosphorus; (C2-C20) alkenyl; (C2-C20) alkenyl containing one or more of halogen, nitrogen, oxygen, silicon, sulfur and phosphorus; (C1-C20)alkyl(C6-C20)aryl; (C1-C20)alkyl(C6-C20)aryl containing one or more of halogen, nitrogen, oxygen, silicon, sulfur and phosphorus; (C6-C20)aryl(C1-C20)alkyl; (C6-C20)aryl(C1-C20)alkyl containing one or more of halogen, nitrogen, oxygen, silicon, sulfur and phosphorus; or a metalloid radical of Group 14 metal substituted with (C1-C20)alkyl or (C6-C20)aryl; two of R41, R42 and R43 may be linked with each other to form a ring;
X' is an oxygen atom, a sulfur atom or N-R (wherein R is (C1-C20)alkyl);
n is an integer obtained by adding 1 to the total number of proton groups included in R1 to R10 and Q;
X- may be coordinated to M; and
a nitrogen atom of imine may be coordinated or decoordinated to M.
In another general aspect, the present invention provides an apparatus of separating an aliphatic polycarbonate polymer and a catalyst in a reaction mixture of an aliphatic polycarbonate polymerization reaction performed in the presence of the catalyst which is a complex compound containing an onium salt, from the reaction mixture, the apparatus including:
a reactor 100 performing the aliphatic polycarbonate polymerization reaction catalyzed by the catalyst which is the complex compound containing an onium salt;
a phase-separator 200 separating an organic layer and an aqueous solution layer by adding two kinds of solvents which are not mixed with each other to the reaction mixture of the polymerization reaction obtained by the reactor, and performing an extraction process;
a refiner 300 obtaining the aliphatic polycarbonate from the organic layer separated from the phase-separator; and
a catalyst-collector (not-shown) collecting the catalyst from the aqueous solution layer separated from the phase-separator.
The method according to the present invention uses two kinds of solvents which are not mixed with each other in a reaction mixture of an aliphatic polycarbonate polymerization reaction performed in the presence of a catalyst which is a complex compound containing an onium salt to remove cyclic carbonate which is a by-product produced at the time of the polymerization reaction, thereby obtaining aliphatic polycarbonate having high purity and easily removing the catalyst used in the reaction.
In addition, the method according to the present invention removes the catalyst, using the two kinds of solvents which are not mixed with each other rather than using the existing silica or resin, in the reaction mixture of the aliphatic polycarbonate polymerization reaction performed in the presence of the catalyst which is the complex compound containing an onium salt, such that a back biting phenomenon of the previously prepared aliphatic polycarbonate polymer is not generated, whereby the cyclic carbonate may not be produced and cyclic carbonate produced at the time of time of the polymerization reaction may be removed.
Further, the method according to the present invention removes the catalyst with a simple process, using the two kinds of solvents which are not mixed with each other rather than using the existing silica, resin, and the like, to increase a removal rate of the catalyst and the by-products, which is significantly effective. In addition, since other apparatuses are not needed, the method is significantly economical.
Further, with the method according to the present invention, the removal rate of the cyclic carbonate produced at the time of polymerization with the catalyst is high, and the back biting phenomenon of the aliphatic polycarbonate polymer is not generated, such that the aliphatic polycarbonate polymer having high purity may be obtained, thereby improving quality of a product containing the same.
The above and other objects, features and advantages of the present invention will become apparent from the following description of preferred embodiments given in conjunction with the accompanying drawings, in which:
FIG. 1 is a schematic diagram showing a process of separating an aliphatic polycarbonate polymer and a catalyst from a reaction mixture of an aliphatic polycarbonate polymerization reaction according to an exemplary embodiment of the present invention.
[Detailed Description of Main Elements]
100 : REACTOR 200 : PHASE-SEPARATOR
300 : REFINER 410 : FIRST PUMP
420 : SECOND PUMP 430 : THIRD PUMP
440 : FOURTH PUMP
510 : ORGANIC SOLVENT DISCHARGING PART
520 : POLYCARBONATE DISCHARGING PART
The present invention provides a method of separating an aliphatic polycarbonate polymer and a catalyst in a reaction mixture of an aliphatic polycarbonate polymerization reaction performed in the presence of the catalyst which is a complex compound containing an onium salt, using two kinds of solvents which are not mixed with each other in the reaction mixture.
The method according to the present invention, which is simple and effective, may remove the catalyst used in the reaction and cyclic carbonate produced at the time of the polymerization reaction to obtain an aliphatic polycarbonate polymer having high purity.
In addition, the method according to the present invention does not need separate apparatuses required for the existing separation method or materials such as adsorbent, and the like, which is significantly economical, and has a high removal rate of cyclic carbonate produced at the time of polymerization reaction with the catalyst to deteriorate purity of the aliphatic polycarbonate polymer.
Further, a back biting phenomenon of the aliphatic polycarbonate polymer produced at the time of separation using the existing silica, resin, and the like, is not generated, that is, the cyclic carbonate is not produced, such that the aliphatic polycarbonate polymer having high purity may be obtained at a high yield.
The reaction mixture which is a target of the present invention may be a solution obtained in the state in which epoxide and carbon dioxide are copolymerized using the catalyst with a polymerization reaction described in Korean Patent Laid-Open Publication No. 10-2009-0090154 and then the remaining carbon dioxide and epoxide which are not reacted are not removed, a solution obtained in the state in which after the polymerization, carbon dioxide is merely removed, or a solution obtained in the state in which after the polymerization, both of carbon dioxide and epoxide are removed, and other solvents are added again for a subsequent treatment.
Two kinds of solvents which are not mixed with each other according to an exemplary embodiment of the present invention may be an organic solvent and an aqueous solution.
The method of separating the aliphatic polycarbonate polymer and the catalyst in the reaction mixture of the aliphatic polycarbonate polymerization reaction performed in the presence of the catalyst which is a complex compound containing an onium salt from the reaction mixture according to an exemplary embodiment of the present invention includes:
a) polymerizing carbon dioxide and an epoxide compound in the presence of the catalyst which is the complex compound containing an onium salt;
b) separating an organic layer and an aqueous solution layer by adding the two kinds of solvents which are not mixed with each other to the reaction mixture of the step a) and performing an extraction process;
c) obtaining aliphatic polycarbonate from the separated organic layer; and
d) collecting the catalyst from the separated aqueous solution layer.
The organic solvent according to an exemplary embodiment of the present invention may be at least one selected from toluene, benzene, xylene, tetrahydrofuran, dichloromethane, dichloroethane, ethyl acetate, propyl acetate, isopropyl acetate, butyl acetate, and in view of more effective separation, the organic solvent may be toluene, tetrahydrofuran or mixed solvents thereof.
The aqueous solution according to an exemplary embodiment of the present invention may contain 0.1 to 20wt% of an inorganic salt, preferably, 0.1 to 10wt%, and more preferably, 0.8 to 10wt% for more effective removal of the catalyst and the cyclic carbonate.
The inorganic salt according to an exemplary embodiment of the present invention is any inorganic salt as long as the salt is generally used; however, may be sodium chloride, ammonium chloride, sodium bicarbonate or mixtures thereof for increasing a removal rate of the catalyst and the reaction by-products.
The extraction process of step b) according to an exemplary embodiment of the present invention, that is, the extraction process in the separating of an organic layer and an aqueous solution layer including the adding of the two kinds of solvents which are not mixed with each other to the reaction mixture of the step a) and the performing of an extraction process may be performed once or more, preferably, three times or more to increase aliphatic polycarbonate having high purity and a removal rate of the catalyst and the by-products.
More preferably, in order to increase aliphatic polycarbonate polymer having high purity and a removal efficiency of the catalyst and the by-products, the organic solvent may be toluene, tetrahydrofuran or mixed solvents thereof, and the aqueous solution may contain 0.8 to 10wt% of an inorganic salt.
The aliphatic polycarbonate polymer according to an exemplary embodiment of the present invention, which is polycarbonate prepared by polymerizing carbon dioxide and epoxide compound described below, may be polypropylene carbonate, polyethylene carbonate, polycyclohexene carbonate, polybutylene carbonate or polycyclopentene carbonate, preferably, polypropylene carbonate, polyethylene carbonate or polybutylene carbonate.
The epoxide compound according to an exemplary embodiment of the present invention may be at least one selected from a group consisting of (C2-C20)alkylene oxide unsubstituted or substituted with halogen, (C1-C20)alkyloxy, (C6-C20)aryloxy or (C6-C20)ar(C1-C20)alkyl(aralkyl)oxy; (C4-C20) cycloalkylene oxide unsubstituted or substituted with halogen, (C1-C20)alkyloxy, (C6-C20)aryloxy or (C6-C20)ar(C1-C20)alkyl(aralkyl)oxy; and (C8-C20)styrene oxide unsubstituted or substituted with halogen, (C1-C20)alkyloxy, (C6-C20)aryloxy, (C6-C20)ar(C1-C20)alkyl(aralkyl)oxy or (C1-C20)alkyl.
The complex compound containing an onium salt may be represented by the following Chemical Formula 1:
[Chemical Formula 1]
[Rectified under Rule 91, 05.08.2014]
Figure WO-DOC-FIGURE-78
in Chemical Formula 1 above,
M is trivalent cobalt or trivalent chromium;
A is an oxygen or sulfur atom;
Q is a diradical connecting two nitrogen atoms;
R1 to R10 are each independently hydrogen; halogen; (C1-C20)alkyl; (C1-C20)alkyl containing one or more of halogen, nitrogen, oxygen, silicon, sulfur and phosphorus; (C2-C20)alkenyl; (C2-C20)alkenyl containing one or more of halogen, nitrogen, oxygen, silicon, sulfur and phosphorus; (C1-C20)alkyl(C6-C20)aryl; (C1-C20)alkyl(C6-C20)aryl containing one or more of halogen, nitrogen, oxygen, silicon, sulfur and phosphorus; (C6-C20)aryl(C1-C20)alkyl; (C6-C20)aryl(C1-C20)alkyl containing one or more of halogen, nitrogen, oxygen, silicon, sulfur and phosphorus; (C1-C20)alkoxy; (C6-C30)aryloxy; formyl; (C1-C20)alkylcarbonyl; or (C6-C20)arylcarbonyl; or a metalloid radical of Group 14 metal substituted with (C1-C20)alkyl or (C6-C20)aryl;
two of R1 to R10 may be linked with each other to form a ring;
at least one hydrogen included in R1 to R10 and Q is a proton group selected from a group consisting of the following Chemical Formulas a, b, and c;
[Chemical Formula a] [Chemical Formula b] [Chemical Formula c]
[Rectified under Rule 91, 05.08.2014]
Figure WO-DOC-FIGURE-87a
X- is each independently a halogen anion; HCO3 -; BF4 -; ClO4 -; NO3 -; PF6 -; a (C6-C20)aryloxy anion; a (C6-C20)aryloxy anion containing one or more of a halogen atom, a nitrogen atom, an oxygen atom, a silicon atom, a sulfur atom and a phosphorus atom; a (C1-C20)alkylcarboxyl anion; a (C1-C20)alkylcarboxyl anion containing one or more of a halogen atom, a nitrogen atom, an oxygen atom, a silicon atom, a sulfur atom and a phosphorus atom; a (C6-C20)arylcarboxyl anion; a (C6-C20)arylcarboxyl anion containing one or more of a halogen atom, a nitrogen atom, an oxygen atom, a silicon atom, a sulfur atom and a phosphorus atom; a (C1-C20)alkoxy anion; a (C1-C20)alkoxy anion containing one or more of a halogen atom, a nitrogen atom, an oxygen atom, a silicon atom, a sulfur atom and a phosphorus atom; a (C1-C20)alkylcarbonate anion; a (C1-C20)alkylcarbonate anion containing one or more of a halogen atom, a nitrogen atom, an oxygen atom, a silicon atom, a sulfur atom and a phosphorus atom; a (C6-C20)arylcarbonate anion; a (C6-C20)arylcarbonate anion containing one or more of a halogen atom, a nitrogen atom, an oxygen atom, a silicon atom, a sulfur atom and a phosphorus atom; a (C1-C20)alkylsulfonate anion; a (C1-C20)alkylsulfonate anion containing one or more of a halogen atom, a nitrogen atom, an oxygen atom, a silicon atom, a sulfur atom and a phosphorus atom; a (C1-C20)alkylamido anion; a (C1-C20)alkylamido anion containing one or more of a halogen atom, a nitrogen atom, an oxygen atom, a silicon atom, a sulfur atom and a phosphorus atom; a (C6-C20)arylamido anion; a (C6-C20)arylamido anion containing one or more of a halogen atom, a nitrogen atom, an oxygen atom, a silicon atom, a sulfur atom and a phosphorus atom; a (C1-C20)alkylcarbamate anion; a (C1-C20)alkylcarbamate anion containing one or more of a halogen atom, a nitrogen atom, an oxygen atom, a silicon atom, a sulfur atom and a phosphorus atom; a (C6-C20)arylcarbamate anion; or a (C6-C20)arylcarbamate anion containing one or more of a halogen atom, a nitrogen atom, an oxygen atom, a silicon atom, a sulfur atom and a phosphorus atom;
Z is a nitrogen or phosphorus atom;
R21, R22, R23, R31, R32, R33, R34 and R35 are each independently (C1-C20)alkyl; (C1-C20) alkyl containing one or more of halogen, nitrogen, oxygen, silicon, sulfur and phosphorus; (C2-C20) alkenyl; (C2-C20) alkenyl containing one or more of halogen, nitrogen, oxygen, silicon, sulfur and phosphorus; (C1-C20)alkyl(C6-C20)aryl; (C1-C20)alkyl(C6-C20)aryl containing one or more of halogen, nitrogen, oxygen, silicon, sulfur and phosphorus; (C6-C20)aryl(C1-C20)alkyl; (C6-C20)aryl(C1-C20)alkyl containing one or more of halogen, nitrogen, oxygen, silicon, sulfur and phosphorus; or a metalloid radical of Group 14 metal substituted with (C1-C20)alkyl or (C6-C20)aryl; two of R21, R22 and R23 or two of R31, R32, R33, R34 and R35 may be linked with each other to form a ring;
R41, R42 and R43 are each independently hydrogen; (C1-C20)alkyl; (C1-C20) alkyl containing one or more of halogen, nitrogen, oxygen, silicon, sulfur and phosphorus; (C2-C20) alkenyl; (C2-C20) alkenyl containing one or more of halogen, nitrogen, oxygen, silicon, sulfur and phosphorus; (C1-C20)alkyl(C6-C20)aryl; (C1-C20)alkyl(C6-C20)aryl containing one or more of halogen, nitrogen, oxygen, silicon, sulfur and phosphorus; (C6-C20)aryl(C1-C20)alkyl; (C6-C20)aryl(C1-C20)alkyl containing one or more of halogen, nitrogen, oxygen, silicon, sulfur and phosphorus; or a metalloid radical of Group 14 metal substituted with (C1-C20)alkyl or (C6-C20)aryl; two of R41, R42 and R43 may be linked with each other to form a ring;
X' is an oxygen atom, a sulfur atom or N-R (wherein R is (C1-C20)alkyl);
n is an integer obtained by adding 1 to the total number of proton groups included in R1 to R10 and Q;
X- may be coordinated to M; and
a nitrogen atom of imine may be coordinated or decoordinated to M.
Preferably, in the Chemical Formula 1 above representing the complex compound catalyst containing an onium salt of the present invention,
M is trivalent cobalt;
A is an oxygen;
Q is a trans-1,2-cyclohexylene, phenylene or ethylene;
R1 and R2 are the same or different primary (C1-C20)alkyl;
R3 to R10 are each independently hydrogen or -[YR51 3-a(CR52R53)bN+R54R55R56 a];
Y is C or Si;
R51, R52, R53, R54, R55 and R56 are each independently hydrogen; halogen; (C1-C20)alkyl; (C1-C20)alkyl containing one or more of halogen, nitrogen, oxygen, silicon, sulfur and phosphor; (C2-C20)alkenyl; (C2-C20)alkenyl containing one or more of halogen, nitrogen, oxygen, silicon, sulfur and phosphor; (C1-C20)alkyl(C6-C20)aryl; (C1-C20)alkyl(C6-C20)aryl containing one or more of halogen, nitrogen, oxygen, silicon, sulfur and phosphor; (C6-C20)aryl(C1-C20)alkyl; (C6-C20)aryl(C1-C20)alkyl containing one or more of halogen, nitrogen, oxygen, silicon, sulfur and phosphor; (C1-C20)alkoxy; (C6-C30)aryloxy; formyl; (C1-C20)alkylcarbonyl; (C6-C20)arylcarbonyl; or a metalloid radical of Group 14 metal substituted with hydrocarbyl, and two of R54, R55 and R56 may be linked with each other to form a ring;
a is an integer of 1 to 3, and b is an integer of 1 to 20;
n is an integer of 4 or more, obtained by adding 1 to the total number of a quaternary ammonium salt included in R3 to R10; and
provided that when a is 1, at least three of R3 to R10 may be -[YR51 3-a(CR52R53)bN+R54R55R56 a], when a is 2, at least two of R3 to R10 may be -[YR51 3-a(CR52R53)bN+R54R55R56 a], and when a is 3, at least one of R3 to R10 may be -[YR51 3-a(CR52R53)bN+R54R55R56 a].
More preferably, the Chemical Formula 1 above may be a complex compound represented by the following Chemical Formula 2:
[Chemical Formula 2]
Figure PCTKR2014005494-appb-I000009
in Chemical Formula 2 above, R61 and R62 are each independently methyl or ethyl; X- is each independently nitrate or acetate anion; nitrogen of imine may be coordinated or decoordinated to cobalt, and each anion may be coordinated to cobalt.
In addition, the present invention provides an aliphatic polycarbonate polymer containing the cyclic carbonate in a content of 2 to 7wt%, preferably, 2 to 5wt%, based on the obtained aliphatic polycarbonate polymer.
Further, the present invention provides an aliphatic polycarbonate polymer containing the metal catalyst in a content of 10ppm or less, preferably, 5ppm, more preferably, 2ppm or less according to the method of the present invention.
For effective separation in the method according to an exemplary embodiment of the present invention, preferably, in the complex compound catalyst represented by the Chemical Formula 1 above,
M is trivalent cobalt;
A is an oxygen;
Q is a trans-1,2-cyclohexylene, phenylene or ethylene;
R1 and R2 are the same or different primary (C1-C20)alkyl;
R3 to R10 are each independently hydrogen or -[YR51 3-a(CR52R53)bN+R54R55R56 a];
Y is C or Si;
R51, R52, R53, R54, R55 and R56 are each independently hydrogen; halogen; (C1-C20)alkyl; (C1-C20)alkyl containing one or more of halogen, nitrogen, oxygen, silicon, sulfur and phosphor; (C2-C20)alkenyl; (C2-C20)alkenyl containing one or more of halogen, nitrogen, oxygen, silicon, sulfur and phosphor; (C1-C20)alkyl(C6-C20)aryl; (C1-C20)alkyl(C6-C20)aryl containing one or more of halogen, nitrogen, oxygen, silicon, sulfur and phosphor; (C6-C20)aryl(C1-C20)alkyl; (C6-C20)aryl(C1-C20)alkyl containing one or more of halogen, nitrogen, oxygen, silicon, sulfur and phosphor; (C1-C20)alkoxy; (C6-C30)aryloxy; formyl; (C1-C20)alkylcarbonyl; (C6-C20)arylcarbonyl; or a metalloid radical of Group 14 metal substituted with hydrocarbyl, and two of R54, R55 and R56 may be linked with each other to form a ring;
a is an integer of 1 to 3, and b is an integer of 1 to 20;
n is an integer of 4 or more, obtained by adding 1 to the total number of a quaternary ammonium salt included in R3 to R10; and
provided that in the complex compound catalyst that when a is 1, at least three of R3 to R10 may be -[YR51 3-a(CR52R53)bN+R54R55R56 a], when a is 2, at least two of R3 to R10 may be -[YR51 3-a(CR52R53)bN+R54R55R56 a], and when a is 3, at least one of R3 to R10 may be -[YR51 3-a(CR52R53)bN+R54R55R56 a], and the two kinds of solvents which are not mixed with each other may be a combination of the organic solvents such as toluene, tetrahydrofuran, or mixtures thereof, and the aqueous solution containing 0.5 to 10wt% of an inorganic salt, thereby providing the aliphatic polycarbonate polymer containing the cyclic carbonate in a content of 2 to 7wt%, preferably, 2 to 5wt%, based on the obtained aliphatic polycarbonate polymer.
Substituents including 「alkyl」, 「alkoxy」 and other 「alkyl」 parts described in the present invention include both of linear type or branched type. In addition, 「aryl」 described in the present invention, which is an organic radical derived from aromatic hydrocarbon due to removal of one hydrogen, includes a single ring system or a fused ring system including 4 to 7 ring atoms, preferably, 5 or 6 ring atoms in each ring, and even includes a form in which a plurality of aryls are connected by a single bond. Specific examples of the aryl include phenyl, naphthyl, biphenyl, anthryl, indenyl, fluorenyl, and the like, but the present invention is not limited thereto. alkenyl defined in the present invention means a linear-, branched-, or a cyclic hydrocarbon radical containing 2 to 20 carbon atoms and at least one carbon to carbon double bond.
The phrase: 「containing one or more of halogen, nitrogen, oxygen, silicon, sulfur and phosphorus」 described in the present invention means substituent groups including one or more of halogen, nitrogen, oxygen, silicon, sulfur and phosphorus, and as an example thereof, 「an alkyl containing one or more of halogen, nitrogen, oxygen, silicon, sulfur and phosphorus」 means an alkyl including substituent groups including one or more of halogen, nitrogen, oxygen, silicon, sulfur and phosphorus. Specifically, haloalkyl, alkoxy and aminoalkyl may be included, but the present invention is not limited thereto.
(C1-C20)alkyl, (C1-C20)alkoxy, and (C3-C20)cycloalkyl according to an exemplary embodiment of the present invention may be preferably (C1-C10)alkyl, (C1-C10)alkoxy, (C3-C12)cycloalkyl; (C6-C20)aryl may be preferably (C6-C12)aryl.
In addition, the present invention provides an apparatus of separating an aliphatic polycarbonate polymer and a catalyst in a reaction mixture of an aliphatic polycarbonate polymerization reaction performed in the presence of the catalyst which is a complex compound containing an onium salt, from the reaction mixture, the apparatus including:
a reactor 100 performing the aliphatic polycarbonate polymerization reaction catalyzed by the catalyst which is the complex compound containing an onium salt;
a phase-separator 200 separating an organic layer and an aqueous solution layer by adding two kinds of solvents which are not mixed with each other to the reaction mixture of the polymerization reaction obtained by the reactor, and performing an extraction process;
a refiner 300 obtaining the aliphatic polycarbonate from the organic layer separated from the phase-separator; and
a catalyst-collector (not-shown) collecting the catalyst from the aqueous solution layer separated from the phase-separator.
The reactor 100 according to the apparatus of the present invention is a place where the epoxide compound and carbon dioxide are reacted in the presence of the catalyst which is a complex compound containing an onium salt to perform the aliphatic polycarbonate polymerization reaction. When the polymerization reaction is completed in the reactor, the reaction mixture may be moved to the phase-separator 200 and two kinds of solvents which are not mixed with each other may be put into the phase-separator to be separated into the organic layer and the aqueous solution layer, wherein the phase-separation may be performed by putting two kinds of solvents which are not mixed with each other into the reactor without moving the reaction mixture to the phase-separator, and thus, in this case, the reactor may be a phase-separator.
The reaction mixture prepared in the reactor of the present invention may be moved to the phase-separator 200 by a first pump 410, and the aqueous solution containing the inorganic salt may be supplied to the phase-separator 200 by a second pump 420.
The organic layer separated from the phase-separator may be moved to the refiner 300 by a third pump 430, the organic solvent may be discharged to an organic solvent discharging part 510 by distillation under reduced pressure and collected, and the aliphatic polycarbonate may be obtained by an aliphatic polycarbonate discharging part 520 and additional refinement may be performed to obtain an aliphatic polycarbonate having more high purity.
The aqueous solution layer separated from phase-separator may be moved to the catalyst-collector (not-shown) by a fourth pump 440, the catalyst and the reaction by-products may be removed, and the obtained catalyst may be collected so as to be reusable, by performing additional refinement.
The present invention will be described in detail with reference to Examples and Comparative Examples. However, Examples below are not intended to limit the scope of the present invention but only for exemplifying the present invention.
[Example 1] Preparation of Polypropylenecarbonate Diol Solution
100.0 mL of propylene oxide, 50.0 mL of toluene were put into a 500 mL high pressure reactor, and 6.3 g of an adipic acid and 0.5 g of a catalyst having a structure of the following structural formula 1 were put thereinto. The reactor was completely sealed, and reacted while maintaining the condition of 20 bar of carbon dioxide, 50 to 55℃ of a reaction inner temperature and 500 rpm of a stirring rate. After 15 hours, the reactor was cooled to room temperature, the pressure of carbon dioxide was reduced to atmospheric pressure and 0.5 g of a malonic acid was put thereinto, thereby completing the reaction.
[Structural Formula 1]
Figure PCTKR2014005494-appb-I000010
[Example 2] Method of Removing Catalyst by Extraction with 0.8 wt% Sodium Chloride Aqueous Solution Once
500 mL of toluene was put into the polypropylenecarbonate diol solution (cyclopropylene carbonate: 9%) of which the reaction was completed under the polymerization conditions of the Example 1 above and stirred. 400 mL of 0.8 wt% sodium chloride aqueous solution was put thereinto and stirred for 30 minutes, and an aqueous solution layer was removed. The extracted toluene layer was distilled under reduced pressure to remove toluene and 141 g of polypropylenecarbonate diol was obtained. (cyclopropylene carbonate: 6 %, cobalt: 1.6 ppm, molecular weight: 1,626 g/mol)
[Example 3] Method of Removing Catalyst by Extraction with 0.8 wt% Sodium Chloride Aqueous Solution Three Times
500 mL of toluene was put into the polypropylenecarbonate diol solution (9% cyclopropylene carbonate) of which the reaction was completed under the polymerization conditions of the Example 1 above and stirred. 400 mL of 0.8 wt% sodium chloride aqueous solution was put thereinto and stirred for 30 minutes, and an aqueous solution layer was removed. 400 mL of 0.8 % sodium chloride aqueous solution was put into the separated toluene layer and further extracted twice. The extracted toluene layer was distilled under reduced pressure to remove toluene and 137 g of polypropylenecarbonate diol was obtained. (cyclopropylene carbonate: 3 %, cobalt: 0 ppm, molecular weight: 2,339 g/mol)
[Example 4] Method of Removing Catalyst by Extraction with 0.1 wt% Sodium Chloride Aqueous Solution Three Times
500 mL of toluene was put into the polypropylenecarbonate diol solution (cyclopropylene carbonate: 9%) of which the reaction was completed under the polymerization conditions of the Example 1 above and stirred. 400 mL of 0.1 wt% sodium chloride aqueous solution was put thereinto and stirred for 30 minutes, and an aqueous solution layer was removed. The extracted toluene layer was distilled under reduced pressure to remove toluene and 120 g of polypropylenecarbonate diol was obtained. (cyclopropylene carbonate: 3 %, cobalt: 18 ppm, molecular weight: 2,322 g/mol)
[Example 5] Method of Removing Catalyst by Extraction with 5.0 wt% Sodium Chloride Aqueous Solution Three Times
500 mL of toluene was put into the polypropylenecarbonate diol solution (cyclopropylene carbonate: 16 %) of which the reaction was completed under the polymerization conditions of the Example 1 above and stirred. 400 mL of 5.0 wt% sodium chloride aqueous solution was put thereinto and stirred for 30 minutes, and an aqueous solution layer was removed. 400 mL of 5.0 % sodium chloride aqueous solution was put into the separated toluene layer and further extracted twice. The extracted toluene layer was distilled under reduced pressure to remove toluene and 139 g of polypropylenecarbonate diol was obtained. (cyclopropylene carbonate: 2 %, cobalt: 0 ppm)
[Example 6] Method of Removing Catalyst by Extraction with 11.0 wt% Sodium Chloride Aqueous Solution Three Times
500 mL of toluene was put into the polypropylenecarbonate diol solution (cyclopropylene carbonate: 16 %) of which the reaction was completed under the polymerization conditions of the Example 1 above and stirred. 400 mL of 11.0 wt% sodium chloride aqueous solution was put thereinto and stirred for 30 minutes, and an aqueous solution layer was removed. 400 mL of 11.0 % sodium chloride aqueous solution was put into the separated toluene layer and further extracted twice. The extracted toluene layer was distilled under reduced pressure to remove toluene and 135 g of polypropylenecarbonate diol was obtained. (cyclopropylene carbonate: 6 %, cobalt: 12 ppm)
[Example 7] Method of Removing Catalyst by Extraction with Mixture of Tetrahydrofuran-Water Three Times
400 mL of toluene and 100 mL of tetrahydrofuran were put into the polypropylenecarbonate diol solution (cyclopropylene carbonate: 6 %) of which the reaction was completed under the polymerization conditions of the Example 1 above. 400 mL of water was put thereinto and stirred for 30 minutes, and an aqueous solution layer was removed. 400 mL of water was put into the separated toluene layer and further extracted twice. The extracted toluene layer was distilled under reduced pressure to remove an organic solvent and 136 g of polypropylenecarbonate diol was obtained. (cyclopropylene carbonate: 2 %, cobalt: 15 ppm, molecular weight: 1536 g/mol)
[Example 8] Method of Removing Catalyst by Extraction with Acetonitrile - 5.0 wt% Sodium Chloride Aqueous Solution Three Times
500 mL of acetonitrile was put into the polypropylenecarbonate diol (cyclopropylene carbonate: 6 %) of which the reaction was completed under the polymerization conditions of the Example 1 above.. 400 mL of 5.0 wt% sodium chloride aqueous solution was put thereinto and stirred for 30 minutes, and an aqueous solution layer was removed. 400 mL of water was put into the separated toluene layer and further extracted twice. The extracted toluene layer was distilled under reduced pressure to remove an organic solvent and 105 g of polypropylenecarbonate diol was obtained. (cyclopropylene carbonate: 5%, cobalt: 7 ppm, molecular weight: 2115 g/mol)
[Comparative Example 1] Method of Removing Catalyst By Ion-Exchange Resin
A tube having a diameter of 4.0 cm and a length of 30.0 cm was filled with an ion-exchange resin (Amberlyst 15) and a sufficient amount of dichloromethane was allowed to flow thereinto. 30 g of polypropylenecarbonate diol (cyclopropylene carbonate: 12%) of which the reaction was completed under the polymerization conditions was diluted with 100 mL of dichloromethane in a tube filled with an ion-exchange resin or silica gel and then was allowed to flow into a tube filled with an adsorbent at a flow velocity of 3.0 mL/min. The organic solvent was removed by distillation under reduced pressure and 30 g of polypropylenecarbonate diol was obtained. (cyclopropylene carbonate: 12%, cobalt: 60 ppm, molecular weight: 1,870 g/mol)
[Comparative Example 2] Method of Removing Catalyst by Silica Gel
A tube having a diameter of 4.0 cm and a length of 30.0 cm was filled with 20g of a silica gel and a sufficient amount of dichloromethane was allowed to flow thereinto. 30 g of polypropylenecarbonate diol (cyclopropylene carbonate: 12%) of which the reaction was completed under the polymerization conditions was diluted with 100 mL of dichloromethane in a tube filled with an ion-exchange resin or silica gel and then was allowed to flow into a tube filled with an adsorbent at a flow velocity of 3.0 mL/min. The organic solvent was removed by and 30 g of polypropylenecarbonate diol was obtained. (cyclopropylene carbonate: 12%, cobalt: 49 ppm, molecular weight: 1,870 g/mol)
It could be appreciated from the result of Examples that since the aliphatic polycarbonate polymer obtained by the separation method according to the present invention had a high removal rate of a cyclic carbonate which is a by-product at the time of polymerization reaction, the cyclic carbonate in the aliphatic polycarbonate polymer had a significantly low content and cobalt which is a metal caused from the catalyst also had a significantly low content, such that a removal rate of the catalyst was high.
In addition, it could be appreciated that cyclic carbonate produced at the time of separation according to the existing separation method was not produced, and thus, the separation method according to the present invention is remarkably effective process in which an aliphatic polycarbonate polymer having high purity may be effectively and economically obtained by a simple process.

Claims (8)

  1. A method of separating an aliphatic polycarbonate polymer and a catalyst in a reaction mixture of an aliphatic polycarbonate polymerization reaction performed in the presence of a catalyst which is a complex compound containing an onium salt, using two kinds of solvents which are not mixed with each other in the reaction mixture.
  2. The method of claim 1, wherein the two kinds of solvents which are not mixed with each other are an organic solvent and an aqueous solution.
  3. The method of claim 1, comprising:
    a) polymerizing carbon dioxide and an epoxide compound in the presence of the catalyst which is the complex compound containing an onium salt;
    b) separating an organic layer and an aqueous solution layer by adding the two kinds of solvents which are not mixed with each other to the reaction mixture of the step a) and performing an extraction process;
    c) obtaining aliphatic polycarbonate from the separated organic layer; and
    d) collecting the catalyst from the separated aqueous solution layer.
  4. The method of claim 2 or 3, wherein the organic solvent is at least one selected from toluene, benzene, tetrahydrofuran and (dichloromethane, ethyl acetate), and the aqueous solution contains 0.1 to 10wt% of an inorganic salt.
  5. The method of claim 1 or 3, wherein the aliphatic polycarbonate polymer is polypropylene carbonate, polyethylene carbonate, polycyclohexene carbonate, polybutylene carbonate, or polycyclopentene carbonate.
  6. The method of claim 3, wherein the epoxide compound is at least one selected from a group consisting of (C2-C20)alkylene oxide unsubstituted or substituted with halogen, (C1-C20)alkyloxy, (C6-C20)aryloxy or (C6-C20)ar(C1-C20)alkyl(aralkyl)oxy; (C4-C20) cycloalkylene oxide unsubstituted or substituted with halogen, (C1-C20)alkyloxy, (C6-C20)aryloxy or (C6-C20)ar(C1-C20)alkyl(aralkyl)oxy; and (C8-C20)styrene oxide unsubstituted or substituted with halogen, (C1-C20)alkyloxy, (C6-C20)aryloxy, (C6-C20)ar(C1-C20)alkyl(aralkyl)oxy or (C1-C20)alkyl.
  7. [Rectified under Rule 91, 05.08.2014]
    The method of claim 1 or 3, wherein the complex compound containing an onium salt is represented by the following Chemical Formula 1:
    [Chemical Formula 1]
    Figure WO-DOC-FIGURE-7A

    in Chemical Formula 1 above,
    M is trivalent cobalt or trivalent chromium;
    A is an oxygen or sulfur atom;
    Q is a diradical connecting two nitrogen atoms;
    R1 to R10 are each independently hydrogen; halogen; (C1-C20)alkyl; (C1-C20)alkyl containing one or more of halogen, nitrogen, oxygen, silicon, sulfur and phosphorus; (C2-C20)alkenyl; (C2-C20)alkenyl containing one or more of halogen, nitrogen, oxygen, silicon, sulfur and phosphorus; (C1-C20)alkyl(C6-C20)aryl; (C1-C20)alkyl(C6-C20)aryl containing one or more of halogen, nitrogen, oxygen, silicon, sulfur and phosphorus; (C6-C20)aryl(C1-C20)alkyl; (C6-C20)aryl(C1-C20)alkyl containing one or more of halogen, nitrogen, oxygen, silicon, sulfur and phosphorus; (C1-C20)alkoxy; (C6-C30)aryloxy; formyl; (C1-C20)alkylcarbonyl; or (C6-C20)arylcarbonyl; or a metalloid radical of Group 14 metal substituted with (C1-C20)alkyl or (C6-C20)aryl;
    two of R1 to R10 may be linked with each other to form a ring;
    at least one hydrogen included in R1 to R10 and Q is a proton group selected from a group consisting of the following Chemical Formulas a, b, and c;
    [Chemical Formula a] [Chemical Formula b] [Chemical Formula c]
    Figure WO-DOC-FIGURE-7B

    X- is each independently a halogen anion; HCO3 -; BF4 -; ClO4 -; NO3 -; PF6 -; a (C6-C20)aryloxy anion; a (C6-C20)aryloxy anion containing one or more of a halogen atom, a nitrogen atom, an oxygen atom, a silicon atom, a sulfur atom and a phosphorus atom; a (C1-C20)alkylcarboxyl anion; a (C1-C20)alkylcarboxyl anion containing one or more of a halogen atom, a nitrogen atom, an oxygen atom, a silicon atom, a sulfur atom and a phosphorus atom; a (C6-C20)arylcarboxyl anion; a (C6-C20)arylcarboxyl anion containing one or more of a halogen atom, a nitrogen atom, an oxygen atom, a silicon atom, a sulfur atom and a phosphorus atom; a (C1-C20)alkoxy anion; a (C1-C20)alkoxy anion containing one or more of a halogen atom, a nitrogen atom, an oxygen atom, a silicon atom, a sulfur atom and a phosphorus atom; a (C1-C20)alkylcarbonate anion; a (C1-C20)alkylcarbonate anion containing one or more of a halogen atom, a nitrogen atom, an oxygen atom, a silicon atom, a sulfur atom and a phosphorus atom; a (C6-C20)arylcarbonate anion; a (C6-C20)arylcarbonate anion containing one or more of a halogen atom, a nitrogen atom, an oxygen atom, a silicon atom, a sulfur atom and a phosphorus atom; a (C1-C20)alkylsulfonate anion; a (C1-C20)alkylsulfonate anion containing one or more of a halogen atom, a nitrogen atom, an oxygen atom, a silicon atom, a sulfur atom and a phosphorus atom; a (C1-C20)alkylamido anion; a (C1-C20)alkylamido anion containing one or more of a halogen atom, a nitrogen atom, an oxygen atom, a silicon atom, a sulfur atom and a phosphorus atom; a (C6-C20)arylamido anion; a (C6-C20)arylamido anion containing one or more of a halogen atom, a nitrogen atom, an oxygen atom, a silicon atom, a sulfur atom and a phosphorus atom; a (C1-C20)alkylcarbamate anion; a (C1-C20)alkylcarbamate anion containing one or more of a halogen atom, a nitrogen atom, an oxygen atom, a silicon atom, a sulfur atom and a phosphorus atom; a (C6-C20)arylcarbamate anion; or a (C6-C20)arylcarbamate anion containing one or more of a halogen atom, a nitrogen atom, an oxygen atom, a silicon atom, a sulfur atom and a phosphorus atom;
    Z is a nitrogen or phosphorus atom;
    R21, R22, R23, R31, R32, R33, R34 and R35 are each independently (C1-C20)alkyl; (C1-C20) alkyl containing one or more of halogen, nitrogen, oxygen, silicon, sulfur and phosphorus; (C2-C20) alkenyl; (C2-C20) alkenyl containing one or more of halogen, nitrogen, oxygen, silicon, sulfur and phosphorus; (C1-C20)alkyl(C6-C20)aryl; (C1-C20)alkyl(C6-C20)aryl containing one or more of halogen, nitrogen, oxygen, silicon, sulfur and phosphorus; (C6-C20)aryl(C1-C20)alkyl; (C6-C20)aryl(C1-C20)alkyl containing one or more of halogen, nitrogen, oxygen, silicon, sulfur and phosphorus; or a metalloid radical of Group 14 metal substituted with (C1-C20)alkyl or (C6-C20)aryl; two of R21, R22 and R23 or two of R31, R32, R33, R34 and R35 may be linked with each other to form a ring;
    R41, R42 and R43 are each independently hydrogen; (C1-C20)alkyl; (C1-C20) alkyl containing one or more of halogen, nitrogen, oxygen, silicon, sulfur and phosphorus; (C2-C20) alkenyl; (C2-C20) alkenyl containing one or more of halogen, nitrogen, oxygen, silicon, sulfur and phosphorus; (C1-C20)alkyl(C6-C20)aryl; (C1-C20)alkyl(C6-C20)aryl containing one or more of halogen, nitrogen, oxygen, silicon, sulfur and phosphorus; (C6-C20)aryl(C1-C20)alkyl; (C6-C20)aryl(C1-C20)alkyl containing one or more of halogen, nitrogen, oxygen, silicon, sulfur and phosphorus; or a metalloid radical of Group 14 metal substituted with (C1-C20)alkyl or (C6-C20)aryl; two of R41, R42 and R43 may be linked with each other to form a ring;
    X' is an oxygen atom, a sulfur atom or N-R (wherein R is (C1-C20)alkyl);
    n is an integer obtained by adding 1 to the total number of proton groups included in R1 toR10 and Q;
    X- may be coordinated to M; and
    a nitrogen atom of imine may be coordinated or decoordinated to M.
  8. An apparatus of separating an aliphatic polycarbonate polymer and a catalyst in a reaction mixture of an aliphatic polycarbonate polymerization reaction performed in the presence of the catalyst which is a complex compound containing an onium salt, from the reaction mixture, the apparatus comprising:
    a reactor performing the aliphatic polycarbonate polymerization reaction catalyzed by the catalyst which is the complex compound containing an onium salt;
    a phase-separator separating an organic layer and an aqueous solution layer by adding two kinds of solvents which are not mixed with each other to the reaction mixture of the polymerization reaction obtained by the reactor, and performing an extraction process;
    a refiner obtaining the aliphatic polycarbonate from the organic layer separated from the phase-separator; and
    a catalyst-collector collecting the catalyst from the aqueous solution layer separated from the phase-separator.
PCT/KR2014/005494 2013-06-21 2014-06-20 Method of separating aliphatic polycarbonate polymer and catalyst from preparing process of copolymer WO2014204279A1 (en)

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