WO2009102078A1 - Procédé de production d'une résine de polycarbonate - Google Patents

Procédé de production d'une résine de polycarbonate Download PDF

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Publication number
WO2009102078A1
WO2009102078A1 PCT/JP2009/052827 JP2009052827W WO2009102078A1 WO 2009102078 A1 WO2009102078 A1 WO 2009102078A1 JP 2009052827 W JP2009052827 W JP 2009052827W WO 2009102078 A1 WO2009102078 A1 WO 2009102078A1
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group
substituted
unsubstituted
general formula
carbon dioxide
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PCT/JP2009/052827
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English (en)
Japanese (ja)
Inventor
Tohru Yamada
Satoshi Kikuchi
Yuudai Sugawara
Koji Nakano
Kyoko Nozaki
Kiyoshi Nishioka
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Keio University
The University Of Tokyo
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Publication of WO2009102078A1 publication Critical patent/WO2009102078A1/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 producing a polycarbonate resin, and more particularly to a method for producing a polycarbonate resin in which carbon dioxide and epoxide are alternately copolymerized in the presence of an optically active cobalt complex catalyst, optionally using a nucleophile. Background technology.
  • polystrengthen Ponate resin has excellent properties such as impact resistance, light weight, transparency, and heat resistance. Among them, aliphatic polycarbonate resin is biodegradable, so it has an environmental impact.
  • a method for producing a polycarbonate resin by a copolymerization reaction of carbon dioxide and an epoxide has been known.
  • the catalysts used for the copolymerization reaction of carbon dioxide and epoxide are mainly zinc complexes (G.-W. Coates et al., J. Am. Chem. Soc.
  • W Zinc complex has the problem that it is difficult to handle due to spontaneous ignition of the raw material, jetyl zinc, and is also expensive, and aluminum complex requires high temperature and high pressure as reaction conditions. There is a problem that the manufacturing cost is high.
  • porphyrin complexes have problems that they are relatively difficult to synthesize, and that when used as a catalyst, the complex is colored, so that the color remains in the product.
  • An object of the present invention is to provide a method for producing a polystrength Ponate resin that solves the above-mentioned problems in a conventional method for producing a polycarbonate resin.
  • Another object of the present invention is to provide a polycarbonate as a completely alternating copolymer that exhibits various unprecedented physical properties and contributes to the development of new applications.
  • R 1 and R 2 may be the same or different and are a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aromatic group, or R 1 and R 2 are They may combine with each other to form a substituted or unsubstituted ring)
  • R 3 and R 4 may be the same or different and independently of each other, a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aromatic group, or a substituted or An unsubstituted aromatic heterocyclic group, or two R 3 's or two R “ 1's may be bonded to each other to form a substituted or unsubstituted ring, and R 5 , R 6 and R 7 may be the same or different, and are a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted aromatic group, a substituted or unsubstituted group, An aromatic heterocyclic group, an acyl group, a substituted or unsubstituted alkoxycarbonyl group, a substituted or unsubstituted aromatic oxycarbonyl group, or a substituted or un unsub
  • the epoxide represented by the general formula (1) is the following:
  • R 3 and R 4 are hydrogen atoms or substituted or unsubstituted aromatic groups, or two R 3 or two R 4 May be bonded to each other to form a substituted or unsubstituted ring
  • R 5 , R 6 and R 7 are a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxycarbonyl group, Or a production method according to any one of 1 to 3 above, which is a substituted or unsubstituted aralkyloxycarbonyl group,
  • X is OB z F 5 —, 0 B z ⁇ , N ⁇ 3 —, ⁇ COCF 3 —, F or I — Described manufacturing method
  • Optically active cobalt complexes represented by general formula (2) and general formula (3) are as follows:
  • R 1 and R 2 may be the same or different and are a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aromatic group, or R 1 and R 2 are They may combine with each other to form a substituted or unsubstituted ring)
  • Polyethylene carbonate obtained by alternately bonding ethylene oxide and carbon dioxide, which does not contain an ether bond component detectable by 1 H-NMR analysis.
  • a polycarbonate resin can be produced in high yield by using carbon dioxide as a carbon source and using an inexpensive and easy-to-synthesize cobalt catalyst.
  • the activity and selectivity of the catalyst are high and the reaction conditions do not require high temperature and pressure, the production cost can be reduced.
  • the polycarbonate film according to the present invention is a completely alternating copolymer, and thus exhibits high unprecedented physical properties and contributes to the development of new applications.
  • Figure 1 is a polyethylene Gar Bonnet over preparative synthesized in Example 6 3 1 It is a graph which shows a H-NMR analysis result.
  • FIG. 2 is a graph showing the results of D SC analysis of the polyethylene carbonate synthesized in Example 63.
  • FIG. 3 is a graph showing the results of TGA analysis of the polyethylene carbonate synthesized in Example 63.
  • FIG. 4 is a graph showing the results of 1 H-NMR analysis of commercially available polyethylene carbonate.
  • Fig. 5 is a graph showing the results of DSC analysis of commercially available polyethylene carbonate.
  • Fig. 6 is a graph showing the results of TGA analysis of commercially available polyethylene carbonate. BEST MODE FOR CARRYING OUT THE INVENTION
  • R 1 and R 2 which may be the same or different, are a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aromatic group, or R 'And R 2 may be bonded to each other to form a substituted or unsubstituted ring.
  • alkyl group for R 1 and R 2 a linear or branched substituted or unsubstituted alkyl group having 1 to 10 carbon atoms is preferable, and examples thereof include a methyl group, an ethyl group, and an ⁇ -propyl group.
  • the alkyl group is substituted with one or more substituents selected from, for example, a hydroxyl group, an amino group, a carboxyl group, a sulfanyl group, a cyano group, a sulfo group, a formyl group, a halogen atom, and an aromatic group. It may be.
  • the substituted or unsubstituted aromatic group for R 1 and R 2 is preferably a substituted or unsubstituted aromatic group having 6 to 10 carbon atoms, such as a phenyl group, an indenyl group, a naphthyl group, Examples thereof include substituted or unsubstituted aromatic hydrocarbon groups such as a lahydronaphthyl group, and more preferably a phenyl group.
  • aromatic group examples include aromatic groups such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, and a tert-butyl group, a phenyl group, and a naphthyl group. It may be substituted with one or more substituents selected from a group and the like.
  • R 1 and R 2 may combine with each other to form a substituted or unsubstituted ring, and preferably form a substituted or unsubstituted aliphatic ring having 4 to 10 carbon atoms.
  • R when R) and are bonded to each other via — (CH 2 ) 4 —, a cyclohexane ring is formed.
  • the ring thus formed is, for example, a methyl group, an ethyl group, an n-propyl group, an isopyl pill group, an n-butyl group, a sec-butyl group, an alkyl group such as a tert-butyl group, a phenyl group, Select from aromatic groups such as naphthyl group May be substituted with one or more substituents.
  • Particular preferable epoxides represented by the general formula (1) include those represented by the following formulas (1 1 1) to (1 1 4).
  • optically active cobalt complex used as a catalyst has the general formula (2)
  • R 3 and R 4 which may be the same or different, are independently of each other a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aromatic group, or a substituted or unsubstituted group. Good It may be an aromatic heterocyclic group.
  • a linear or branched substituted or unsubstituted alkyl group of 1 to 10 is preferable, for example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert — And butyl group.
  • the alkyl group is, for example, one or two or more substituents selected from a hydroxy group, an amino group, a strong lpoxyl group, a sulfanyl group, a cyano group, a sulfo group, a formyl group, a halogen atom, an aromatic group and the like. May be substituted.
  • the substituted or unsubstituted aromatic group for R 3 and R 4 is preferably a substituted or unsubstituted aromatic group having 6 to 10 carbon atoms, for example, a substituted or unsubstituted group such as a phenyl group or a naphthyl group.
  • aromatic hydrocarbon groups examples include aromatic groups such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, and a tert-butyl group, a phenyl group, and a naphthyl group. It may be substituted with 1 or 2 or more substituents selected from a group or the like.
  • a substituted or unsubstituted aromatic heterocyclic group having 5 to 10 carbon atoms is preferable, for example, a furyl group, a chenyl group, a pyridyl group. , Pyrrolyl group, oxazolyl group, isoxazolyl group, thiazolyl group, isothiazolyl group, imidazolyl group, pyrazolyl group, pyrimidyl group, pyridazinyl group, bilaridinyl group, quinolyl group, isoquinolyl group, etc.
  • a cyclic group is mentioned.
  • the aromatic heterocyclic group includes, for example, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-propyl group, a sec-butyl group, an alkyl group such as a tert-butyl group, a phenyl group, and a naphthyl group. 1 or 2 or more selected from aromatic groups such as It may be substituted with the above substituents.
  • two R 3 s or two R 4 s may be bonded to each other to form a substituted or unsubstituted ring, and preferably a substituted or unsubstituted fatty acid having 4 to 10 carbon atoms.
  • a family ring may be formed. For example, when R 3 and R 4 are bonded to each other via — (CH 2 ) 4 —, a cyclohexane ring is formed.
  • the ring formed in this way is, for example, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec butyl group, an alkyl group such as a tert-butyl group, a phenyl group, a naphthyl group, etc. It may be substituted with 1 or 2 or more substituents selected from the following aromatic groups.
  • R 5 , R 6 and R 7 may be the same or different, and are a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted aromatic group, substituted or An unsubstituted aromatic heterocyclic group, an acyl group, a substituted or unsubstituted alkoxycarbonyl group, a substituted or unsubstituted aromatic oxycarbonyl group, or a substituted or unsubstituted aralkyloxycarbonyl group.
  • the substituted or unsubstituted alkyl group for R 5 , R 6 and R 7 is preferably a linear or branched substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, more preferably 1 carbon atom.
  • linear or branched substituted or unsubstituted alkyl groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, etc. Is mentioned.
  • the alkyl group is, for example, one or two or more substituents selected from a hydroxy group, an amino group, a strong lpoxyl group, a sulfanyl group, a cyano group, a sulfo group, a formyl group, a halogen atom, and an aromatic group. May be substituted.
  • alkenyl groups for R 5 , R 6 and R 7
  • a linear or branched alkenyl group having 2 to 10 carbon atoms is preferable, and a linear or branched alkenyl group having 2 to 6 carbon atoms, for example, a vinyl group or a 2-propenyl group.
  • the alkenyl group is, for example, one or two or more substituents selected from a hydroxy group, an amino group, a strong lpoxyl group, a sulfanyl group, a cyano group, a sulfo group, a formyl group, a halogen atom, and an aromatic group. It may be replaced.
  • a substituted or unsubstituted aromatic group having 6 to 10 carbon atoms is preferable, for example, a substituted or unsubstituted aromatic group such as a phenyl group or a naphthyl group.
  • a hydrocarbon group is mentioned.
  • the aromatic group includes, for example, a methyl group, an ethyl group, an n-propyl group, an isopyl pill group, an n-butyl group, a sec-butyl group, a tert-butyl group, an alkyl group, a phenyl group, a naphthyl group, etc. It may be substituted with 1 or 2 or more substituents selected from the following aromatic groups.
  • a substituted or unsubstituted aromatic heterocyclic group having 5 to 10 carbon atoms is preferable.
  • An unsubstituted aromatic heterocyclic group is mentioned.
  • the aromatic heterocyclic group is, for example, one or more selected from an alkyl group such as a methyl group or an ethyl group, an alkoxy group such as a methoxy group or an ethoxy group, a halogen atom group, a nitro group, or a cyan group. It may be substituted with a substituent.
  • an acyl group having 1 to 20 carbon atoms is preferable.
  • the substituted or unsubstituted alkoxycarbonyl group for R 5 , R 6 and R 7 is preferably a substituted or unsubstituted alkoxycarbonyl group having 2 to 20 carbon atoms, such as a methoxycarbonyl group or an ethoxycarbonyl group.
  • the alkoxy group is, for example, one or more substituents selected from a hydroxy group, an amino group, a carboxyl group, a sulfanyl group, a cyano group, a sulfo group, a formyl group, a halogen atom, an aromatic group and the like. May be substituted.
  • the substituted or unsubstituted aromatic oxyphenyl group of R 5 , R 6 and R 7 is preferably a substituted or unsubstituted aromatic oxycarbonyl group having 7 to 20 carbon atoms, such as phenoxy.
  • a carbonyl group is mentioned.
  • the aromatic oxycarbonyl group is selected from, for example, an alkyl group such as a methyl group or an ethyl group, an alkoxy group such as a methoxy group or an ethoxy group, a halogen atom group, a nitro group, or a cyan group. It may be substituted with 1 or 2 or more substituents.
  • an aralkyloxycarbonyl group having 7 to 20 carbon atoms is preferable, for example, a benzyloxycarbonyl group, Phenethyl Examples thereof include an oxy group and a sulfonyl group.
  • the aralkyloxycarbonyl group includes, for example, a hydroxy group, an amino group, a strong lpoxyl group, a sulfanyl group, a cyano group, a sulfo group, a formyl group, a halogen atom, an aromatic group, an alkoxyalkyleneoxy group. It may be substituted with a substituent on 1 or 2 selected from a group such as a methoxyethyleneoxy group.
  • R 6 and R 7 may be bonded to each other to form a ring, and may preferably form a substituted or unsubstituted aliphatic ring having 4 to 10 carbon atoms.
  • a cyclohexane ring is formed.
  • the ring thus formed can be, for example, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, an tert-butyl group or other alkyl group, a phenyl group, or a naphthyl group. It may be substituted with 1 or 2 or more substituents selected from aromatic groups and the like.
  • optically active cobalt complexes represented by the general formula (2) include those represented by the following formulas (2-1) to (2-11-1).
  • R 3 , R 4 , R 5 , and R 1 R 7 are defined with respect to the general formula (2).
  • X— represents an anion pair that can form a salt.
  • Polycarbonate soot resin produced by the method of the present invention is generally (4): Where R 1 and R 2 are as described above.
  • the molecular weight of the polycarbonate resin represented by the general formula (4) is preferably about 1, 00 to: L 0 0, 0 00, more preferably about 2, 0 0 0 to 50 0, 0 0 0, particularly preferably in the range of about 2, 5 0 0 to 40, 0 0 0.
  • Particular preferred polycarbonate resins represented by the general formula (4) include those represented by the following formulas (4-1) to (4-14).
  • Nucleophiles can be used in the method of the present invention.
  • nucleophilic agent When no nucleophilic agent is used, it is considered that a trace amount of water acts as a polymerization initiator.
  • the nucleophiles include bis (triphenylphosphoranilidene) ammonium chloride (PPNC 1), piperidine, bis (triphenylphosphoranilidene) ammonium fluoride (PPNF), bi scan (Bok Li phenylpropyl phosphine Ola two isopropylidene) Anmoniumupen evening Furuo port Benzoe one preparative (PPN_ ⁇ B z F 5), n B u_
  • PPNC 1 bis (triphenylphosphoranilidene) ammonium chloride
  • PPNF bis (triphenylphosphoranilidene)
  • the amount of carbon dioxide used in the present invention is not particularly limited, but the reaction is usually carried out in a carbon dioxide atmosphere or under carbon dioxide pressure conditions.
  • a preferable carbon dioxide pressure is in the range of 0.1 IMpa to LOMpa, more preferably 0.1 MPa to 2 MPa.
  • the reaction can be performed in a mixed gas of an inert gas and carbon dioxide that does not significantly affect the reaction such as nitrogen or argon.
  • the reaction temperature is usually preferably from 40 to 50 ° C, more preferably from 0 to 30 ° C.
  • the reaction time varies depending on the reaction conditions, but is usually 1 to 100 hours.
  • a solvent can be used as necessary.
  • the solvent used is not particularly limited as long as it does not react with the used epoxide, carbon dioxide, optically active cobalt complex, or nucleophile.
  • hydrocarbons, ethers, esters, canes And octalogated hydrocarbons for example, hydrocarbons, ethers, esters, canes And octalogated hydrocarbons.
  • the amount of the solvent used it can be added in a mass ratio of 0.5 to 100, preferably 1 to 50 with respect to epoxide as a raw material.
  • the polycarbonate obtained by the process of the present invention is completely alternating It is thought that the unification of the various physical properties will contribute to the development of new applications.
  • the polycarbonate according to the present invention is thermally decomposed at a relatively low temperature and has almost no decomposition residue, as shown in an example described later (FIG. 3).
  • the polystrength Ponate according to the present invention which is excellent in heat decomposability, is useful as a binder resin for producing various molded bodies made of ceramic glass produced through, for example, degreasing and firing processes.
  • the polycarbonate according to the present invention is higher in quality than conventional polycarbonate in terms of various properties such as impact resistance, lightness, transparency, heat resistance, biodegradability, etc. It can be advantageously applied in various applications where polycarbonate is used.
  • ketoiminato cobalt pen fluorinated benzoate complex (3— 1) 0 0 1 4 3 mm o 1 and bis (triphenylphosphoranilidene) ammonium fluoride (P PNF ) 0. 0 1 4 3 mm o 1 and propylene oxide 2 8. 6 mm o 1 added, then carbon dioxide is injected under pressure so that the total pressure is 2.0 MPa. It was adjusted. After reacting at room temperature for 48 hours, carbon dioxide was removed, and this reaction mixture was analyzed by '-NMR. '--NMR analysis was carried out at a temperature of 22 ° C using deuterated form as a solvent and tetramethylsilane as an internal standard. Ma J 1 EL—EX 2 70 and GX—400 manufactured by JEOL Ltd. were used as the 1 H-NMR measuring apparatus.
  • the reaction was carried out in the same manner as in Example 1 except that P P N F was changed to bis (triphenylphosphoranylidene) ammonium chloride (P P N C 1).
  • the reaction mixture obtained at this time contained about 38% cyclic carbon dioxide. Yield was 54%, head-to-tail bond selectivity was 92%, Mn was 15570, MwZMrl.2 (standard polystyrene standard, THF).
  • the reaction was carried out in the same manner as in Example 1 except that PPNF was changed to bis (triphenylphosphoranylidene) ammonium pentafluobenzoate (PP NO B z F 5 ).
  • the reaction mixture obtained at this time was polycarbonate with a selectivity of 99% or more. Yield is 64%, head-to-tail bond selectivity is 9 2%, Mn is 2540, and MwZMn is 1.7 (standard polystyrene standard, THF). I got it.
  • the reaction was carried out in the same manner as in Example 1 except that PPNF was changed to tetra-n-butylammonium chloride.
  • the reaction mixture obtained at this time contained about 4% of cyclic carbonate.
  • the yield was 43%, the head-to-head binding selectivity was 91%, the Mn was 1790, and the Mw Mn was 1, 0 (standard polystyrene standard, THF).
  • the reaction was conducted in the same manner as in Example 1 except that P P N F was changed to triphenylphosphine.
  • the reaction mixture obtained at this time was polycarbonate with a selectivity of 99% or more. Yield was 10%, head-to-head binding selectivity was 85%, M r i 4 400, Mw / M n was 1.1 (standard polystyrene standard, THF).
  • Example 1 the reaction was carried out in the same manner unless otherwise specified except that the nucleophile was changed.
  • the results are shown in the table below (standard polystyrene standard, Kuguchiguchi Holm).
  • the reaction was carried out in the same manner as in Example 1 except that the ketoiminato cobalt pen fluorate benzoate complex was changed to the ketoiminato cobalt benzoate complex (3 — 2).
  • the reaction mixture obtained at this time was polyponeate with a selectivity of 99% or more.
  • the yield was 85%, the head-to-tail selectivity was 91%, Mn was 2 6400, and MwMn was 1.7 (standard polystyrene standard, THF).
  • the reaction was conducted in the same manner as in Example 1 except that the ketoiminato cobalt pen fluorobenzoate complex was changed to the ketoiminato cobalt nitrate complex (3-3).
  • the reaction mixture obtained at this time was a poly force mononate with a selectivity of 99% or more. Yield 8 1%, head-to-head binding selectivity 9 1%, Mn 1 6 90 0, Mw / M n was 1.2 (standard polystyrene standard, THF).
  • the reaction was carried out in the same manner as in Example 1 except that the ketoiminato cobalt pen fluorate benzoate complex was changed to the cheminatocobalt trifluoroacetate complex (3-4).
  • the reaction mixture obtained at this time was a polystrength with a selectivity of 99% or more. Yield was 82%, head-to-head binding selectivity was 91%, Mn was 265500, MwZMn was 1.7 (standard polystyrene standard, THF).
  • the reaction was conducted in the same manner as in Example 1 except that the ketoiminatocobalt pentafluorene benzoate complex was changed to the ketoiminatocobaltate complex (3-5).
  • the reaction mixture obtained at this time contained about 36% cyclic carbonate. Yield was 50%, head-to-head binding selectivity was 77%, M i 4 2 0 0, w / M n was 1.0 (standard polystyrene standard, T H F).
  • the reaction was conducted in the same manner as in Example 1 except that the ketoiminato cobalt pentafluoride complex was changed to the ketoiminato cobalt iodide complex (3-6).
  • the reaction mixture obtained at this time contained about 43% cyclic carbonate. Yield was 41%, head-to-head binding selectivity was 76%, Mn was 8200, and Mw / n was 1.4 (standard polystyrene standard, black mouth form).
  • the reaction was conducted in the same manner as in Example 1 except that the ketoiminato cobalt pen fluorobenzoate complex was changed to the ketoiminatocobalt (II) complex (2-1).
  • the reaction mixture obtained at this time The compound contained about 3% cyclic carbonate. Yield was 57%, head-to-tail selectivity was 92%, Mn was 2070, and Mw / Mn was 1.4 (standard polystyrene standard, THF).
  • Example 1 the reaction was carried out in the same manner unless otherwise specified except that the complex was changed and P P N F was changed to P P N C 1.
  • the results are shown in the table below (standard polystyrene standards, black mouth form).
  • Example 1 except that the anion pair of the ketoiminato cobalt pen fluorobenzoate complex (3-1) was changed and PPNF was changed to PPNC 1, the same applies. A response was made. The results are shown in the table below (standard polystyrene standards, chloroform). Table 3
  • the reaction was carried out in the same manner as in Example 1 except that the solvent-free place was changed to 2 mL of the tetrahydrofuran solvent.
  • the reaction mixture obtained at this time contained about 7% cyclic carbonate. Yield was 52%, head-to-head binding selectivity was 88%, Mn was 1370, and MwZMn was 1.2 (standard polystyrene standard, THF).
  • Example 44 The reaction was conducted in the same manner as in Example 1 except that the solvent-free place was changed to 2 mL of methylene chloride solvent.
  • the reaction mixture obtained at this time contained about 4% of a ring carbon nanotube. Yield was 28%, head-to-head binding selectivity was 89%, Mr9200, MwZMn was 1.5 (standard polystyrene standard, THF).
  • Example 4 5 The reaction was carried out in the same manner as in Example 1 except that the solvent-free place was changed to 2 mL of chloroform-form solvent.
  • the reaction mixture obtained at this time contained about 6% cyclic carbonate.
  • the yield was 86%
  • the head-to-head binding selectivity was 82%
  • the Mn was 1230
  • the wZMn was 1.3 (standard polystyrene standard, THF).
  • the reaction was conducted in the same manner as in Example 1 except that the reaction time was changed to 5 hours.
  • the reaction mixture obtained at this time contained about 10% cyclic carbonate.
  • the yield was 6%
  • head-to-head binding selectivity was 91%
  • Mn was 44 61
  • MwZMn was 1.2 (standard polystyrene standard, THF).
  • the reaction was conducted in the same manner as in Example 1 except that the reaction time was changed to 10 hours.
  • the reaction mixture obtained at this time was polyponicate with a selectivity of more than 99%.
  • the yield was 29%, head-to-head binding selectivity was 91%, Mn was 1560,00 and w / Mn was 1.1 (standard polystyrene standard, THF). .
  • the reaction was conducted in the same manner as in Example 1 except that the reaction time was changed to 15 hours.
  • the reaction mixture obtained at this time was polycarbonate with a selectivity of 99% or more. Yield was 34%, head-to-head binding selectivity was 91%, Mn was 1730, and MwZMn was 1.0 (standard polystyrene standard, THF).
  • the reaction was conducted in the same manner as in Example 1 except that the reaction time was changed to 24 hours.
  • the reaction mixture obtained at this time was 99% or more.
  • the reaction was performed in the same manner as in Example 1 except that the reaction time was changed to 72 hours.
  • the reaction mixture obtained at this time was polyponicate with a selectivity of more than 99%. Yield was 69%, head-to-head binding selectivity was 92%, Mn was 335,000 and MwZMn was 1.7 (standard polystyrene standard, THF).
  • Example 1 the reaction was carried out in the same manner except that the pressure vessel was previously dried under reduced pressure.
  • the reaction mixture obtained at this time was polycarbonate with a selectivity of 99% or more. Yield was 83%, head-to-head binding selectivity was 93%, Mn was 3100, and Mw / Mn was 1.6 (standard polystyrene standard, THF).
  • Example 10 the reaction was carried out in the same manner except that the pressure vessel was previously dried under reduced pressure.
  • the reaction mixture obtained at this time contained about 2% cyclic carbonate.
  • the yield was 69%, head-to-head binding selectivity was 92%, Mn was 1720, and MwZMn was 1.0 (standard polystyrene standard, THF).
  • Example 1 the reaction was carried out in the same manner except that the ketoiminato cobalt pen fluor benzene complex was not used, but the reaction did not proceed at all.
  • Example 5 2 In a stainless steel pressure vessel, ketoiminato cobalt pen fluorinated benzoate complex (3 — 1) 0.0 1 4 3 mm o 1 and bis (triphenylphosphoranilidene) ammonium fluoride (PPNF) After adding 0.01 4 3 mmol and adding cyclohexenoxide 14.8 mmol, carbon dioxide was injected under pressure to adjust the total pressure to 2.0 MPa. After reacting at 30 ° C. for 48 hours, carbon dioxide was removed, and the reaction mixture was analyzed by —NMR.
  • the resulting reaction mixture contains 99% or more of poly force monoponate in which carbon dioxide and cyclohexenoxide react alternately, and cyclic force in which carbon dioxide and cyclohexene oxide react one molecule at a time. Almost no ponate was produced. Furthermore, according to 'H-NMR, the proportion of carbonate bonds contained in the polycarbonate chain was 99% or more, that is, the product was a complete alternating copolymer. The yield of the obtained polycarbonate was 58%. In addition, when the obtained polyforce was analyzed by GPC, the number average molecular weight ⁇ ⁇ was 6 00 0 and the molecular weight distribution ⁇ / ⁇ 11 was 1.4 (standard polystyrene standard, THF). .
  • Example 52 except that PPNF was changed to bis (triphenylphosphranylidene) ammonium chloride (PPNC 1) and the reaction time was changed from 48 hours to 65 hours, the reaction was conducted in the same manner. went.
  • the yield was 57%, MrW3 ⁇ 45 100, and the molecular weight distribution Mw / Mn was 1.1 (standard polystyrene standard, THF).
  • Example 52 the reaction was performed in the same manner except that 0.5 mL of toluene was added as a solvent. Yield is 69%, ⁇ [11 is 6 0 0 0 The molecular weight distribution MwZM n was 1.1 (standard polystyrene standard, TH F).
  • the reaction was carried out in the same manner as in Example 52 except that the ketoiminatocobalt pentafluorobenzoate complex (3-1) was changed to the ketoiminatocobalt iodide complex (3-5).
  • the yield was 29%, M n was 45 500, and the molecular weight distribution MwZM n was 1.1 (standard polystyrene standard, THF).
  • Example 52 except that the ketoiminato cobalt pen fluorobenzoate complex (3—1) was changed to the ketoiminatocobalt complex complex (3—5) and PPNF was changed to PPNC 1 Reaction was performed.
  • the yield was 5%
  • M n was 190,000
  • the molecular weight distribution Mw / M n was 1.1 (standard polystyrene standard, THF).
  • Example 52 the ketoiminato cobalt pen fluorobenzoate complex (3 — 1) was changed to the ketiminatocobalt iodide complex (3 — 5), PPNF was changed to PPNC 1, and toluene was used as the solvent.
  • the reaction was performed in the same manner except that 0.5 mL was added.
  • the yield was 70%, Mn was 4300, and the molecular weight distribution MwZMn was 1.1 (standard polystyrene standard, THF).
  • Example 52 except that the ketoiminato cobalt pen fluorobenzoate complex (3-1) was changed to the ketoiminato cobalt iodide complex (3-5), and 0.5 mL of toluene was added as a solvent. The reaction was carried out. Yield 39%, Mn 1 5 0 0, The molecular weight distribution MwZM n was 1.2 (standard polystyrene standard, THF).
  • Ketominato cobalt iodide complex (3 — 5) 5.8 mg (1 0 ⁇ ⁇ 1), PPNF 5.4 mg (l O mol), methylene chloride 1.
  • O mL Ethylene oxide (1.56 g, 35 mm o 1) was charged, charged with carbon dioxide (2.0 Pa), and reacted at 25 ° C. for 48 hours. Thereafter, the pressure was released, and dilute hydrochloric acid and methanol were added to stop the reaction. The contents were washed with dilute hydrochloric acid and poured into methanol to obtain a white precipitate. This was filtered and dried under reduced pressure to obtain 1.94 g of polyethylene carbonate.
  • Ketominato cobalt iodide complex (3-5) 5.8 mg (1 0 mo 1), PPNC 1 5. 7 mg (l O mol), methylene chloride in a 5 O mL autoclave mL, 1.50 g (3 4 mm o 1) of ethylene oxide were charged, charged with carbon dioxide (2.0 MPa), and reacted at 25 for 48 hours. Thereafter, the pressure was released and dilute hydrochloric acid and methanol were added to stop the reaction. The contents were washed with dilute hydrochloric acid and poured into methanol to obtain a white precipitate. This was filtered and dried under reduced pressure to obtain 0.86 g of polyethylene carbonate.
  • Ketominatocobalt tetrafluoroporate complex (3-1 3) 5.4 mg (1 0 / imol), PPNC 1 5.
  • 7 mg (1 0 ⁇ mol), methylene chloride in a 5 O mL autoclave O mL and 1.16 g (26 mm o 1) of ethylene oxide were charged, charged with carbon dioxide (2.0 MPa), and reacted at 25 ° C. for 48 hours. Thereafter, the pressure was released, and dilute hydrochloric acid and methanol were added to stop the reaction. The contents were washed with dilute hydrochloric acid and poured into methanol to obtain a white precipitate. This was filtered and dried under reduced pressure to obtain 0.08 g of polyethylene carbonate.
  • Ketominatocobalt fluoride complex (3 — 1 4) 4.7 mg (l O ⁇ mol) PPNC 1 5.7 mg (1 0 mol), methylene chloride 1.
  • O mL in an autoclave with an internal volume of 5 O mL
  • ethylene oxide (1.02 g, 23 mmol) was charged, charged with carbon dioxide (2.0 MPa), and reacted at 25 ° C for 48 hours. Thereafter, the pressure was released, and dilute hydrochloric acid and methanol were added to stop the reaction. The contents were washed with dilute hydrochloric acid and poured into methanol to obtain a white precipitate. This was filtered and dried under reduced pressure to obtain 1.04 g of polyethylene carbonate.
  • Ketominato cobalt iodide complex (3 — 5) 5.8 mg (1 0 mo 1), PPNF 5.4 mg (l O mol), methylene chloride 1, O mL, ethylene Oxide 10 0.37 g (2500 mmol) was charged, charged with carbon dioxide (2.0 MPa), and reacted at 25 for 48 hours. Then, the pressure was released and dilute hydrochloric acid and methanol were added to stop the reaction. The contents were washed with dilute hydrochloric acid and poured into methanol to obtain a white precipitate. This is filtered After drying under reduced pressure, 2.45 g of polyethylene carbonate was obtained.
  • Ketominato cobalt iodide complex (3 — 5) 5.8 mg (l O ⁇ mol) PPNF 5.4 mg (l O mol), methylene chloride 1.
  • O mL Ethylene oxide (9.97 g, 230 mm o 1) was charged, charged with carbon dioxide (2.0 Pa), and reacted at 40 ° C. for 48 hours. Thereafter, the pressure was released and dilute hydrochloric acid and methanol were added to stop the reaction. The contents were washed with dilute hydrochloric acid and poured into methanol to obtain a white precipitate. This was filtered and dried under reduced pressure to obtain 3.45 g of polyethylene strength.
  • the polyethylene strength monoponate obtained in Example 63 is substantially free of peaks derived from ether linkages (around 3.6 ppm) in the NMR analysis (Fig. 1).
  • the peak (less than 1%) that appears only around 3.7 ppm is a peak derived from the proton of the terminal methylene group of polyethylene saponate. Therefore, it can be said that this polyethylene carbonate is a completely alternating copolymer in which ethylene oxide and carbon dioxide are alternately polymerized one by one (even if an ether bond is present, the detection limit of 1 H-NMR analysis is exceeded). Is the amount below).
  • the commercially available polyethylene strength “QPAC 2 5” has the following characteristics: — In the NMR analysis, in addition to the peak derived from the terminal proton (around 3.7 ppm), the peak derived from the ether bond (3.6) about 3 to 5%) (Fig. 4). In other words, the polyethylene carbonate includes a portion where ethylene oxides are bonded to each other.
  • the polyethylene carbonate obtained in Example 63 had a glass transition temperature Tg of 17.5 ° C. in DSC analysis (FIG. 2).
  • the commercially available polyethylene carbonate “QP AC 25” had a glass transition temperature Tg of 15.7 ° C. in DSC analysis (FIG. 5).
  • the polyethylene carbonate obtained in Example 63 was shown to be substantially entirely decomposed at around 2500 ° C. by TGA analysis (FIG. 3).
  • TGA analysis showed that about 3% was not decomposed even if it exceeded 300, and complete decomposition requires more than 3500 ( Figure 6).
  • the polyethylene carbonate according to the present invention is a completely alternating copolymer, it can be seen that it has remarkably different thermal characteristics from the existing polyethylene carbonate. Industrial applicability
  • the method according to the present invention is useful for the industrialization of the production of polystrengthen resin using carbon dioxide as a carbon source. Further, the polycarbonate according to the present invention is a completely alternating copolymer, and thus exhibits various unprecedented physical properties and contributes to the development of new applications.

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

Abstract

Cette invention concerne un procédé de production d'une résine de polycarbonate qui utilise du dioxyde de carbone comme source de carbone et qui prend ainsi en compte l'utilisation des ressources et le respect de l'environnement. Le procédé de production d'une résine de polycarbonate se caractérise par l'exécution d'une copolymérisation alternée de dioxyde de carbone et d'époxyde en présence d'un catalyseur de complexe de cobalt optiquement actif utilisant éventuellement un agent nucléophile. La résine de polycarbonate produite par le procédé est un copolymère entièrement alterné.
PCT/JP2009/052827 2008-02-14 2009-02-12 Procédé de production d'une résine de polycarbonate WO2009102078A1 (fr)

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JP2011153186A (ja) * 2010-01-26 2011-08-11 Univ Of Tokyo コバルト−ケトイミナト錯体、および当該錯体を用いたポリカルボナートの製造方法
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PL2321364T3 (pl) * 2008-08-22 2016-01-29 Novomer Inc Sposoby syntezy polimerów
CN111848940B (zh) * 2008-09-08 2024-09-06 沙特阿美技术公司 聚碳酸酯多元醇组合物和方法
JP2011153181A (ja) * 2010-01-26 2011-08-11 Keio Gijuku コバルト−ケトイミナト錯体、および当該錯体を用いたポリカルボナートの製造方法
JP2011191687A (ja) * 2010-03-16 2011-09-29 Univ Of Tokyo 光弾性を有する光学素子
JP2011195637A (ja) * 2010-03-17 2011-10-06 Univ Of Tokyo ポリカルボナート組成物
JP2011195635A (ja) * 2010-03-17 2011-10-06 Univ Of Tokyo 二核金属錯体、および当該二核金属錯体を用いたポリカルボナートの製造方法
JPWO2012102101A1 (ja) * 2011-01-28 2014-06-30 国立大学法人 東京大学 耐熱安定性に優れたポリカーボネートおよびその製造方法
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JP2011153186A (ja) * 2010-01-26 2011-08-11 Univ Of Tokyo コバルト−ケトイミナト錯体、および当該錯体を用いたポリカルボナートの製造方法

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