WO2012102101A1 - Polycarbonate ayant une étonnante stabilité en termes de résistance à la chaleur et son procédé de production - Google Patents

Polycarbonate ayant une étonnante stabilité en termes de résistance à la chaleur et son procédé de production Download PDF

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WO2012102101A1
WO2012102101A1 PCT/JP2012/050621 JP2012050621W WO2012102101A1 WO 2012102101 A1 WO2012102101 A1 WO 2012102101A1 JP 2012050621 W JP2012050621 W JP 2012050621W WO 2012102101 A1 WO2012102101 A1 WO 2012102101A1
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polycarbonate
chain
repeating unit
asymmetric carbon
heat
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PCT/JP2012/050621
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English (en)
Japanese (ja)
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幸司 中野
京子 野崎
聖司 西岡
信貴 藤本
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国立大学法人東京大学
住友精化株式会社
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Priority to JP2012554721A priority Critical patent/JPWO2012102101A1/ja
Publication of WO2012102101A1 publication Critical patent/WO2012102101A1/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
    • C08G64/02—Aliphatic polycarbonates
    • C08G64/0208—Aliphatic polycarbonates saturated
    • 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
    • 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
    • C08G64/40—Post-polymerisation treatment
    • C08G64/403—Recovery of the polymer

Definitions

  • the present invention relates to a polycarbonate excellent in heat resistance and a method for producing the same.
  • Global warming is caused by the increase in greenhouse gases such as carbon dioxide, chlorofluorocarbons and methane in the atmosphere, so reducing the atmospheric concentration of carbon dioxide, which has a high contribution to global warming, It is extremely important, and various studies such as emission regulations and immobilization are being conducted on a global scale.
  • Non-patent Document 1 Non-patent Document 1
  • Polycarbonate is transparent and completely decomposes when heated to a predetermined temperature or higher, so it can be used for applications such as general moldings, films, and fibers, as well as optical materials such as optical fibers and optical disks, or ceramic binders. It can also be used as a thermally decomposable material such as lost foam casting.
  • polycarbonate is degradable in vivo, it can be applied as a medical material such as a sustained-release drug capsule, an additive of biodegradable resin, or a main component of biodegradable resin.
  • An object of the present invention is to provide a polycarbonate having excellent heat resistance stability and a method for producing the same.
  • the present inventors have obtained a polycarbonate having an optical isomer containing an asymmetric carbon as a repeating unit, and the absolute configuration of the asymmetric carbon center in one polymer chain.
  • the conceptual diagram which shows the representative example of the linear polycarbonate of this invention; (1) Stereoblock polymer and (2) Stereogradient polymer.
  • the thermogravimetric analysis curve of the polycarbonate obtained by the Example and the comparative example The thermogravimetric analysis curve of the polycarbonate obtained by the Example and the comparative example.
  • the thermogravimetric analysis curve of the polycarbonate obtained by the comparative example The thermogravimetric analysis curve of the polycarbonate obtained by the comparative example.
  • the heat-stable polycarbonate according to the present invention is a polycarbonate having an optical isomer containing an asymmetric carbon as a repeating unit, and among a plurality of types of repeating units having different absolute configurations of the asymmetric carbon center in one polymer chain.
  • a chain polycarbonate having a region containing a large amount of one type of repeating unit and a region containing a large amount of a repeating unit different from the one type of repeating unit hereinafter referred to as “asymmetric in the same polymer chain”. It is a polycarbonate that can be obtained by precipitation from a mixed solution of a solution in which a chain polycarbonate having regions having different absolute configurations at the carbon center is dissolved and a solvent that does not dissolve the chain polycarbonate.
  • the repeating unit of the chain polycarbonate used in the production of the heat-stable polycarbonate according to the present invention includes a plurality of types of repeating units having different asymmetric carbon center absolute configurations depending on the number of asymmetric carbons. For example, when the repeating unit contains one asymmetric carbon, there are two optical isomers of S-form and R-form in the repeat unit, and a region containing a large amount of repeat units of S-form in one polymer chain And a region containing a large amount of repeating units of the R isomer.
  • the chain polycarbonate used in the present invention has, for example, a region containing a large amount of repeating units of S form and a region containing a large amount of repeating units of R form.
  • a polycarbonate a copolymer having a block containing a large amount of repeating units of S isomer and a block containing a large amount of repeating units of R isomer (referred to as “stereo block polymer” in the present invention) and a polymer chain.
  • stereo block polymer a copolymer having a block containing a large amount of repeating units of S isomer and a block containing a large amount of repeating units of R isomer
  • the “region containing a large amount” means a region where the molar ratio of one stereoisomer is 70% or more, preferably 78% based on the total number of repeating units contained in the region. It means the region having the above.
  • the abundance ratio of plural types of repeating units having different absolute configurations at the asymmetric carbon center may be the same mole number or different in one polymer chain and between each region. Good.
  • the chain polycarbonate used in the present invention can be produced, for example, by copolymerizing carbon dioxide and chiral epoxide in the presence of a catalyst.
  • a catalyst for example, by copolymerizing carbon dioxide and chiral epoxide in the presence of a catalyst.
  • the chiral epoxide is, for example, the following formula (1):
  • R 1 and R 2 may be the same or different, provided that they are not simultaneously hydrogen atoms, and R 1 and R 2 are independently of each other a hydrogen atom,
  • R 1 and R 2 together may form a saturated or unsaturated C 4 -C 8 alicyclic group; the aryl moiety in the aryl and arylalkyl and the alicyclic group, a halogen atom, a straight chain or C 1 ⁇ C 8 branched chain alkyl, C 2 ⁇ C 8 alkenyl, one or more selected from C 2 ⁇ C 8 alkynyl and C 4 ⁇ C 8 group consisting cycloalkyl May be substituted with substituents, or, forming
  • chiral epoxides include propylene oxide, 1-butene oxide, 2-butene oxide, 1-pentene oxide, 2-pentene oxide, cyclopentene oxide, 1-hexene oxide, cyclohexene oxide, 1-octene oxide, 1-dodecene oxide, styrene oxide, vinylcyclohexene oxide, 3-phenylpropylene oxide, 3,3,3-trifluoropropylene oxide, 3-naphthylpropylene oxide, butadiene monooxide, 3-trimethylsilyloxypropylene oxide, etc.
  • propylene oxide is particularly preferable from the viewpoint of high reactivity.
  • carbon dioxide to be copolymerized with the chiral epoxide is introduced into the reaction vessel as a gas and used for the reaction.
  • the pressure of carbon dioxide in the reaction vessel is preferably 0.01 to 6 MPa, more preferably 0.1 to 3.0 MPa.
  • the molar ratio of chiral epoxide to carbon dioxide used in the reaction is typically 1: 0.1 to 1:10, but is preferably 1: 0.5 to 1: 3.0, more preferably 1: 1.0 to 1: 2.0.
  • R 3 and R 4 may be the same or different and independently represent a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aromatic group, or a substituted or unsubstituted aromatic group.
  • R 5 independently represent 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 aromatic heterocyclic group, substituted or unsubstituted Unsubstituted alkoxy group, acyl group, substituted or unsubstituted alkoxycarbonyl dil group, substituted or unsubstituted aromatic oxycarbonyl group, substituted or unsubstituted aralkyloxycarbo Or a group, or an aliphatic ring or aromatic ring bonded to a substituted or unsubstituted and R 6 and R 7 together on adjacent carbon atoms may be formed.
  • R 3 , R 4 , R 5 , R 6 and R 7 are the same as defined above, and Z is F—, Cl—, Br—, I—, N 3 —, NO 3 —,
  • an anionic ligand selected from the group consisting of an aliphatic carboxylate, an aromatic carboxylate, an alkoxide and an aromatic oxide.
  • R 3 , R 4 and Z are as defined above, R 8 , R 9 , R 10 and R 11 are groups selected from the group consisting of W, X and Y; , R 8 , R 9 , R 10 , R 11 include at least one W and at least one X, Y may not be present, and at least one of R 8 , R 10 is a substituent W, W is a quaternary ammonium group represented by -CH 2 aminomethyl group represented by -NG 1 G 2, or -CH 2 -NG 1 G 2 ⁇ HT , R 9, At least one of R 11 is a substituent X, and X is selected from the group consisting of a C 4 to C 20 tertiary alkyl group, a C 3 to C 20 tertiary silyl group, and a C 6 to C 20 aromatic group.
  • Y is a hydrogen atom, a C 1 -C 20 alkyl group, C 1 Alkoxy group ⁇ C 20, C aromatic group 6 ⁇ C 20, carboxylic acid group of C 1 ⁇ C 20, acyl group of C 1 ⁇ C 20, a nitro group, a cyano group, is selected from the group consisting of halogen group
  • G 1 and G 2 may be the same or different, and are independently a C 1 -C 20 alkyl group, a C 1 -C 20 alkoxy group, and a C 6 -C 20 aromatic group.
  • Represents a selected group, or G 1 , G 2 and N may be taken together to form a substituted or unsubstituted 3- to 8-membered cyclic amino group.
  • HT is an inorganic acid, aliphatic And a cobalt complex represented by a protonic acid selected from carboxylic acids, aromatic carboxylic acids, aliphatic sulfonic acids, and aromatic sulfonic acids.
  • the use ratio of the catalyst is preferably 0.05 mol or less, more preferably 0.01 mol or less, relative to 1 mol of the chiral epoxide. Moreover, since reaction time becomes long, it is preferable that it is 0.00001 mol or more, and it is more preferable that it is 0.00002 mol or more. In the copolymerization, a cocatalyst can be further used.
  • Co-catalysts include bis (triphenylphosphoranylidene) ammonium chloride (PPNCl), piperidine, bis (triphenylphosphoranylidene) ammonium fluoride (PPNF), bis (triphenylphosphoranylidene) ammonium pentafluoro Benzoate (PPNOBzF 5 ), tetra-n-butylammonium chloride (nBu 4 NCl), tetra-n-butylammonium bromide (nBu 4 NBr), tetra-n-butylammonium iodide (nBu 4 NI), tetra-n- butylammonium acetate (nBu 4 nOAc), such as triphenylphosphine (Ph 3 P) and the like, preferably PPNCl, PPNF, PPNOBzF 5 and nBu 4 NCl, more preferably A PPNCl and PPNF terms having high reaction activity.
  • the proportion of the cocatalyst used as necessary is preferably 0.1 to 10 mol, more preferably 0.3 to 5 mol, relative to 1 mol of the catalyst, Even more preferred is ⁇ 1.5 moles.
  • a solvent can be used as necessary.
  • the solvent used is not particularly limited as long as it does not react with the chiral epoxide, carbon dioxide, catalyst and cocatalyst used.
  • ethers and halogenated hydrocarbons are preferred because of their high solubility, and 1,2-dimethoxyethane and methylene chloride are particularly preferred.
  • These solvents may be used alone or in combination of two or more.
  • the amount used is preferably 50 to 10,000 parts by mass, more preferably 100 to 5000 parts by mass with respect to 100 parts by mass of the chiral epoxide.
  • the copolymerization can be carried out using a known polymerization reactor capable of being pressurized, for example, an autoclave.
  • the copolymerization is preferably carried out in an inert atmosphere in order to eliminate the influence of oxygen and the like.
  • the copolymerization reaction temperature is preferably 0 ° C. to 100 ° C. from the viewpoint of suppressing the formation reaction of the cyclic carbonate as a by-product and shortening the reaction time, and preferably 10 ° C. to 90 ° C. Is more preferable, and it is even more preferable that the temperature is 20 to 60 ° C.
  • the reaction time varies depending on the reaction conditions, but is usually 1 to 100 hours.
  • the chain polycarbonate thus obtained is a polycarbonate having an optical isomer containing an asymmetric carbon as a repeating unit, and is one of a plurality of types of repeating units having different absolute configurations of the asymmetric carbon center in one polymer chain. A region including a large amount of repeating units of a type and a region including a large amount of repeating units different from the one type of repeating unit.
  • This chain polycarbonate can be isolated by concentrating and drying by a conventional method after completion of the reaction. Further, the chain polycarbonate may be further purified using a known means such as column chromatography.
  • the molecular weight of the chain polycarbonate obtained by the copolymerization is, for example, 1000 or more, preferably 2,000 to 1,000, as a typical number average molecular weight (Mn) measured by gel permeation chromatography (GPC; converted to polystyrene). 1,000,000, more preferably 3,000 to 100,000.
  • the chain polycarbonate obtained by the copolymerization may have a relatively narrow molecular weight distribution (Mw / Mn). Specifically, for example, it is 4 or less, preferably 2.5 or less, and more preferably 1.0 to 1.6.
  • the catalyst or the like is appropriately selected, and after using only one of the optical isomers as a monomer raw material to completely react this, only the other optical isomer is further added.
  • a stereo block polymer having a region substantially composed only of one optical isomer monomer and a region composed only of the other optical isomer monomer by continuing the reaction Can be manufactured.
  • one optical isomer monomer is converted to the other.
  • a stereogradient polymer having a region configured to be contained in a larger amount than the optical isomer monomer and a region in which the quantitative relationship of the optical isomer monomer is reversed can be produced.
  • the polycarbonate having excellent heat stability according to the present invention includes a solution in which a chain polycarbonate having a plurality of regions having different asymmetric carbon center absolute configurations in the same polymer chain, a solvent that does not dissolve the chain polycarbonate, It can be obtained by precipitation from a mixed solution.
  • dissolution with respect to polycarbonate means that the polycarbonate is completely dissolved, the polycarbonate is not completely dissolved but partially dissolved, and the polycarbonate is swollen.
  • “precipitation” of the polycarbonate means that the polycarbonate appears completely or partially from a solution in which the polycarbonate is completely or partially dissolved, and that the swollen polycarbonate is immersed in the solvent. It means that the solvent is removed by filtration or the like, and the swollen polycarbonate is exposed.
  • Examples of the solvent for dissolving the chain polycarbonate used in the present invention include aromatic hydrocarbons, ethers, esters, ketones, halogenated hydrocarbons and the like. Specifically, benzene, toluene, xylene, dibutyl ether, tetrahydrofuran, 1,4-dioxane, methyl acetate, ethyl acetate, propyl acetate, methyl ethyl ketone, methyl isobutyl ketone, diethyl ketone, methylene chloride, chloroform, dichloroethane, trichloroethane, chlorobenzene Etc.
  • esters are preferable from the viewpoint of high solubility, and methyl lactate, ethyl lactate, methyl acetate, and ethyl acetate are particularly preferably used.
  • These solvents for dissolving the polycarbonate may be used alone or in combination of two or more.
  • the amount of the solvent used is preferably 50 to 10,000 parts by mass, more preferably 100 to 5000 parts by mass with respect to 100 parts by mass of the polycarbonate.
  • Examples of the solvent that does not dissolve the polycarbonate include alcohol solvents such as methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, sec-butyl alcohol, tert-butyl alcohol, isobutyl alcohol, pentane, Examples thereof include aliphatic hydrocarbon solvents such as hexane, octane, decane, and cyclohexane, and water.
  • alcohol-based solvents are preferable from the viewpoint of improving the heat resistance stability of the obtained polycarbonate, and methyl alcohol, ethyl alcohol, and isopropyl alcohol are particularly preferably used.
  • These solvents that do not dissolve the polycarbonate may be used alone or in combination of two or more.
  • the amount of the solvent that does not dissolve the polycarbonate is preferably 50 to 100,000 parts by mass, more preferably 100 to 50,000 parts by mass with respect to 100 parts by mass of the polycarbonate.
  • a specific method for precipitating a polycarbonate having excellent heat resistance stability by mixing a solution in which the chain polycarbonate used in the present invention is dissolved with a solvent that does not dissolve the chain polycarbonate is, for example, the chain polycarbonate.
  • a method in which the solution in which the solution is dissolved is added to a solvent that does not dissolve the chain polycarbonate to precipitate the polycarbonate, followed by decantation, filtration, and drying by a known method.
  • the obtained polycarbonate may be washed with water or methyl alcohol and then dried by a known method.
  • the number average molecular weight (Mn) and molecular weight distribution (Mw / Mn) of the polycarbonate obtained in this example and the like are determined by gel permeation chromatography (High Performance Liquid Chromatography System DG660B / PU713 / UV702 / RI631A manufactured by GL Sciences Inc.). ) And measured at 40 ° C. in THF, and calculated based on standard polystyrene.
  • the 1 H NMR spectrum of the polycarbonate obtained in this example was measured using JNM-ECP500 (500 MHz) manufactured by JEOL.
  • the measurement of the heat resistance stability of the polycarbonate obtained in this example and the like was performed using a TG / DTA6200 manufactured by SII Nanotechnology, Inc., from room temperature to 350 ° C. at a temperature rising rate of 20 ° C./min. This was done by raising the temperature.
  • Example 1 To a 5 mL eggplant flask, 100 mg of the polycarbonate obtained in Synthesis Example 2 and 0.5 mL of ethyl acetate were added and stirred to completely dissolve. Thereafter, the total amount of the solution was added to 50 mL of methyl alcohol to precipitate a polymer. The precipitated polymer was filtered, washed with 10 mL of methyl alcohol, and dried under reduced pressure at 25 ° C. for 24 hours to obtain 85 mg of a polycarbonate which is a stereogradient polymer. (Sample 1).
  • Example 2 In Example 1, except that 100 mg of the polycarbonate obtained in Synthesis Example 3 was used in place of 100 mg of the polycarbonate obtained in Synthesis Example 2, 87 mg of a polycarbonate which is a stereo block polymer was obtained in the same manner as in Example 1 ( Sample 2).
  • Comparative Example 2 100 mg of a polycarbonate, which is a stereoblock polymer, was obtained in the same manner as in Comparative Example 1, except that 100 mg of the polycarbonate obtained in Synthesis Example 3 was used instead of 100 mg of the polycarbonate obtained in Synthesis Example 2. Sample 4).
  • the polycarbonate of Sample 1 obtained in Example 1 showed a greatly improved thermal decomposition temperature as compared with the polycarbonate of Sample 3 obtained in Comparative Example 1.
  • the polycarbonate of Sample 2 obtained in Example 2 also showed a greatly improved thermal decomposition temperature compared to the polycarbonate of Sample 4 obtained in Comparative Example 2.
  • the polycarbonates of Samples 5 and 6 obtained in Comparative Example 3 and Comparative Example 4 showed a lower thermal decomposition temperature than the polycarbonates of Samples 1 to 4, and even if the precipitation treatment was performed, No change was seen. That is, it can be understood that the thermal decomposition temperature is improved by the precipitation treatment, which is a phenomenon peculiar to the chain polycarbonate having regions having different absolute configurations of asymmetric carbon centers in the same polymer chain.
  • heat resistance stability can be imparted to a polycarbonate that is transparent and completely decomposes when heated to a predetermined temperature or higher.

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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 polycarbonate ayant une étonnante stabilité en termes de résistance à la chaleur et son procédé de production. Plus spécifiquement, cette invention concerne un polycarbonate doué de stabilité en termes de résistance à la chaleur qui est un polycarbonate contenant un motif répétitif de type isomère optique qui contient un atome de carbone asymétrique, et cette invention concerne également un procédé de production dudit polycarbonate doué de stabilité en termes de résistance à la chaleur. Le polycarbonate peut être obtenu par précipitation à partir d'un mélange constitué comme suit : une solution contenant à l'état dissous un polycarbonate monocaténaire ayant, dans une chaîne polymère unique, une région riche en un type de motif répétitif parmi une pluralité de types de motifs répétitifs qui diffèrent en position absolue du centre carbone asymétrique, et une région riche en un motif répétitif différent du type de motif répétitif précité ; et un solvant qui ne dissout pas le polycarbonate monocaténaire.
PCT/JP2012/050621 2011-01-28 2012-01-13 Polycarbonate ayant une étonnante stabilité en termes de résistance à la chaleur et son procédé de production WO2012102101A1 (fr)

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH07268092A (ja) * 1994-03-31 1995-10-17 Mitsui Toatsu Chem Inc ポリカーボネートの製造法
JPH09291143A (ja) * 1996-04-25 1997-11-11 Idemitsu Petrochem Co Ltd ポリカーボネート粉粒体の製造方法
WO2008150033A1 (fr) * 2007-06-08 2008-12-11 The University Of Tokyo Copolymère alterné stéréosélectif époxy-dioxyde de carbone
JP2009215529A (ja) * 2008-02-14 2009-09-24 Keio Gijuku ポリカーボネート樹脂の製造方法
JP2010001443A (ja) * 2008-06-23 2010-01-07 Univ Of Tokyo エポキシドと二酸化炭素との立体選択的交互共重合

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH07268092A (ja) * 1994-03-31 1995-10-17 Mitsui Toatsu Chem Inc ポリカーボネートの製造法
JPH09291143A (ja) * 1996-04-25 1997-11-11 Idemitsu Petrochem Co Ltd ポリカーボネート粉粒体の製造方法
WO2008150033A1 (fr) * 2007-06-08 2008-12-11 The University Of Tokyo Copolymère alterné stéréosélectif époxy-dioxyde de carbone
JP2009215529A (ja) * 2008-02-14 2009-09-24 Keio Gijuku ポリカーボネート樹脂の製造方法
JP2010001443A (ja) * 2008-06-23 2010-01-07 Univ Of Tokyo エポキシドと二酸化炭素との立体選択的交互共重合

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