WO2015072815A1 - Catalyseur organozincique, son procédé de préparation, et procédé pour la préparation d'une résine polyalkylène carbonate en faisant appel à celui-ci - Google Patents

Catalyseur organozincique, son procédé de préparation, et procédé pour la préparation d'une résine polyalkylène carbonate en faisant appel à celui-ci Download PDF

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Publication number
WO2015072815A1
WO2015072815A1 PCT/KR2014/011081 KR2014011081W WO2015072815A1 WO 2015072815 A1 WO2015072815 A1 WO 2015072815A1 KR 2014011081 W KR2014011081 W KR 2014011081W WO 2015072815 A1 WO2015072815 A1 WO 2015072815A1
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Prior art keywords
catalyst
zinc
acid
organic zinc
zinc catalyst
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PCT/KR2014/011081
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English (en)
Korean (ko)
Inventor
김성경
박승영
조현주
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주식회사 엘지화학
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Priority to EP14862667.4A priority Critical patent/EP3048129B1/fr
Priority to CN201480063125.7A priority patent/CN105764954B/zh
Priority to US15/034,696 priority patent/US10047196B2/en
Priority to JP2016526195A priority patent/JP6364076B2/ja
Priority claimed from KR1020140160747A external-priority patent/KR101650510B1/ko
Publication of WO2015072815A1 publication Critical patent/WO2015072815A1/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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/22—Organic complexes
    • B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
    • B01J31/2208—Oxygen, e.g. acetylacetonates
    • B01J31/2226—Anionic ligands, i.e. the overall ligand carries at least one formal negative charge
    • B01J31/223—At least two oxygen atoms present in one at least bidentate or bridging ligand
    • B01J31/2239—Bridging ligands, e.g. OAc in Cr2(OAc)4, Pt4(OAc)8 or dicarboxylate ligands
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
    • B01J2231/10—Polymerisation reactions involving at least dual use catalysts, e.g. for both oligomerisation and polymerisation
    • B01J2231/14—Other (co) polymerisation, e.g. of lactides, epoxides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/20—Complexes comprising metals of Group II (IIA or IIB) as the central metal
    • B01J2531/26—Zinc

Definitions

  • the present invention is an organic zinc catalyst that suppresses agglomeration between catalyst particles during the production process, has a more uniform and finer particle size, and thus exhibits an improved activity in the polymerization process for producing a polyalkylene carbonate resin, a method for preparing the same, and It relates to a method for producing a polyalkylene carbonate resin using the same.
  • such zinc dicarboxylate-based catalysts typically zinc glutarate catalysts, react with dicarboxylic acids such as zinc precursors and glutaric acid. It forms and takes the form of fine crystalline particles.
  • produces, and in many cases, it has a comparatively large particle size and a nonuniform particle shape. Due to such a large and nonuniform particle size, when the polymerization process for producing polyalkylene carbonate resin is performed using the zinc catalyst dicarocarboxylate-based catalyst, the contact area between the reactants and the catalyst is not secured and polymerization is performed. There was a drawback that the activity was not fully expressed
  • the present invention is suppressed and the aggregation between the particles during manufacture, more uniform and also the fine particle size to have, thereby producing a polyalkyl with an organic zinc catalyst showing an improved activity in the polymerization process for the production of alkylene carbonate resin, thereof in accordance with i To provide a way.
  • This invention also provides the manufacturing method of the polyalkylene carbonate resin using the said organic zinc catalyst.
  • the present invention is a zinc dicarboxylate organic zinc catalyst used in the reaction for producing a polyalkylene carbonate resin from carbon dioxide and epoxide,
  • an aliphatic hydrocarbon group having 3 to 15 carbon atoms (however, the aliphatic hydrocarbon group may or may not include one or more oxygen or carbonyl groups).
  • the present invention also provides a zinc precursor, a "dicarboxylic acid, monomethyl having an aliphatic hydrocarbon group having a carbon number of 3 to 15 (however, may not be included groups aliphatic hydrocarbons, include a one or more oxygen or carbonyl or.) It provides a method for producing the organic zinc catalyst comprising the step of reacting a carboxylic acid.
  • the present invention in the presence of the organic zinc catalyst, epoxide and It provides a method for producing a polyalkylene carbonate resin comprising the step of polymerizing a monomer including carbon dioxide.
  • an organic zinc catalyst according to an embodiment of the present invention a method for preparing the same, and a method for preparing a polyalkylene carbonate resin using the same will be described in detail.
  • the zinc dicarboxylate-based organic zinc catalyst used in the reaction for producing a polyalkylene carbonate resin from carbon dioxide and epoxide at least one side of the zinc dicarboxylate-based zinc catalyst
  • An organic zinc having a moiety derived from a monocarboxylic acid having an aliphatic hydrocarbon group having 3 to 15 carbon atoms (wherein the aliphatic hydrocarbon group may or may not include one or more oxygen or carbonyl groups) at the terminal of A catalyst is provided.
  • relatively hydrophobic end capping structures can suppress aggregation between catalyst particles from each other. Therefore, the organozinc catalyst is suppressed between the catalyst particles during the manufacturing process, it can exhibit a more uniform and fine particle size.
  • the organic zinc catalyst of the embodiment has a more uniform and fine particle diameter by suppressing aggregation between catalyst particles during the manufacturing process, and shows an improved activity in the polymerization process for producing polyalkylene carbonate resin, such a polymerization process Very preferably.
  • Such organic zinc catalysts may basically comprise a chain structure equivalent to previously known zinc dicarboxylate-based catalysts. That is, the organic zinc catalyst may have a structure in which zinc, a dicarboxylate, for example, an aliphatic dicarboxylate having 3 to 20 carbon atoms or an aromatic dicarboxylate having 8 to 40 carbon atoms is bonded. , The monocarboxylic acid-derived residue may be bonded to the terminal.
  • the organic zinc catalyst may have a chemical structure of Formula 1:
  • R1 and R3 are each independently an aliphatic hydrocarbon group having 3 to 15 carbon atoms derived from a monocarboxylic acid (however, the aliphatic hydrocarbon group may or may not include one or more oxygen or carbonyl groups).
  • R2 may represent an aliphatic hydrocarbon group having 1 to 20 carbon atoms or an aromatic hydrocarbon group having 6 to 40 carbon atoms derived from dicarboxylic acid or dicarboxylate.
  • the dicarboxylate is an aliphatic dicarboxylate having 3 to 20 carbon atoms, such as glutarate, malonate, succinate, or adipate, terephthalate, isophthalate, homo It may be any of aromatic dicarboxylates having 8 to 40 carbon atoms, such as phthalate or phenylglutarate.
  • the dicarboxylate is glutarate in view of the activity of the organic zinc catalyst.
  • the zinc dicarboxylate-based organic zinc catalyst is preferably a zinc glutarate-based catalyst.
  • Such dicarboxylates are aliphatic dicarboxylic acids having 3 to 20 carbon atoms, such as dicarboxylic acids such as glutaric acid, malonic acid, succinic acid or adipic acid, and terephthalic acid, isophthalic acid and homo. It is derived from aromatic dicarboxylic acids having 8 to 40 carbon atoms such as phthalic acid or phenyl glutaric acid, and can be formed by reaction of these dicarboxylic acids with zinc.
  • the moiety bonded and capped to at least one end of the organic zinc catalyst may include 3 to 15 carbon atoms, or 4 to 15 carbon atoms, or an aliphatic carbon of 6 to 15 carbon atoms, with or without one or more oxygen or carbonyl groups.
  • a monocarboxylic acid having a hydrocarbon group representative examples of such a monocarboxylic acid, valeric acid; Lauric acid; 3,5-dioxonucleosanic acid; 3,5,7-trioxo-dodecanoic acid; Keto acids such as acetoacetic acid or levulinic acid; Black is 4-oxo-4H-1-benzopyran-2-carboxylic acid (4-oxo-4H-1 -benzopyran-2-carboxycarboxylic acid) or 5-hydroxy-4-oxo-4H-pyran- Oxo carboxylic acids such as 2-carboxylic acid (5-Hydroxy-4-oxo-4H-pyran-2-carboxylic acid), and two or more kinds of mixtures selected for these cases may be used.
  • the organic zinc catalyst may be end capped with a monocarboxylic acid-derived residue through reaction with various monocarboxylic acids.
  • an organic zinc catalyst end-capped with a monocarboxylic acid having an aliphatic hydrocarbon group having less than 3 carbon atoms for example, propionic acid, etc.
  • a monocarboxylic acid having an aliphatic hydrocarbon group having less than 3 carbon atoms for example, propionic acid, etc.
  • the monocarboxylic acid-derived residues are more capped at both ends of the zinc dicarboxylate-based organic zinc catalyst in order to more effectively suppress aggregation during the catalyst preparation process.
  • the monocarboxylic acid-derived moiety is about 0.1 to 0.5 moles, or about 0.2 to 0.5 moles, and black is about 1 mole of the dicarboxylate-derived moiety bound to the organic zinc catalyst. It is appropriate that they are bonded in a ratio of 0.2 to 0.4 mol.
  • the organic zinc catalyst of the above-described embodiment is about 0.2 to 0.9 / ffli, or about 0.3 to 0.8 ⁇ , as the aggregation between the catalyst particles is suppressed during the manufacturing process Or in the form of uniform particles having an average particle diameter of about 0.5 to 0.7 and a standard deviation of about 0.05 to 0.3 ⁇ , or about 0.05 to Q.2, or about 0.05 to 0.1 ⁇ .
  • the organic zinc catalyst is used as a catalyst in the production of polyalkylene carbonate resin by copolymerization of carbon dioxide and epoxide, the contact area between the catalyst particles and the reactant may be increased, thereby improving activity.
  • Such a production method may include, for example, a zinc precursor, a dicarboxylic acid, and an aliphatic hydrocarbon group having 3 to 15 carbon atoms (however, the aliphatic hydrocarbon group may or may not include one or more oxygen or carbonyl groups). Reacting a monocarboxylic acid having a may be included.
  • the reaction step may include reacting the zinc precursor, the dicarboxylic acid, and further adding the monocarboxylic acid to react.
  • an organic zinc catalyst may be prepared.
  • an organic zinc catalyst of one embodiment which exhibits a more uniform and finer particle size and improved activity, can be prepared.
  • the zinc precursor may be zinc oxide or zinc hydroxide, or zinc such as zinc acetate (Zn (0 2 CCH 3 ) 2 ), zinc nitrate (Zn (N0 3 ) 2 ) or zinc sulfate (ZnS0 4 ). Salts may be used, and any zinc precursors previously used in the preparation of zinc dicarboxylate catalysts may be 'used' without any limitation.
  • any zinc precursors previously used in the preparation of zinc dicarboxylate catalysts may be 'used' without any limitation.
  • the reaction step of the dicarboxylic acid is about
  • the reaction may be performed for about 0.5 to 10 hours at a silver degree of 40 to 90 ° C., and the reaction of the monocarboxylic acid may be performed for about 1 to 20 hours at a temperature of about 80 to 150 ° C.
  • agglomeration between the catalyst particles during the catalyst preparation process can be effectively suppressed while ensuring the proper production of the zinc dicarboxylate-based catalyst, so that a catalyst having a more uniform and finer particle size and excellent activity can be produced properly.
  • the monocarboxylic acid in the preparation of the catalyst, may be used in a ratio of about 0.1 to 0.5 moles per 1 mole of the dicarboxylic acid, the dicarboxylic acid is about 1.0 to 1 mole of the zinc precursor To 1.5 mol.
  • agglomeration between the catalyst particles during the catalyst preparation process is more effectively suppressed while ensuring proper production of the zinc dicarboxylate-based catalyst having excellent activity, so that a catalyst having a more uniform and finer particle size and excellent activity can be produced properly.
  • a method for producing a polyalkylene carbonate resin comprising the step of polymerizing a monomer comprising epoxide and carbon dioxide ⁇ in the presence of the above-described organic zinc catalyst.
  • the organic zinc catalyst may be used in the form of a heterogeneous catalyst, and the polymerization step may proceed to solution polymerization in an organic solvent.
  • the heat of reaction can be appropriately controlled, and the molecular weight or viscosity of the polyalkylene carbonate resin to be obtained can be easily controlled.
  • solvents include methylene chloride, ethylene dichloride, trichloroethane, tetrachloroethane, chloroform, acetonitrile propionitrile, dimethylformamide, ⁇ -methyl-2-pyridoneone dimethyl sulfoxide, Nitromethane, 1,4-dioxane, nucleic acid, toluene, tetrahydrofuran, methyl ethyl ketone, methyl amine ketone, methyl isobutyl ketone, acetone, cyclonuclear xanone, trichloroethylene, methyl acetate, vinyl acetate, ethyl acetate It may be used propyl acetate, butyl lactone, caprolactone, nitropropane, at least one selected from benzene, styrene, xylene, and the group consisting of methyl Pro pajol (me thyl)
  • the solvent may be used in a weight ratio of about 1: 0.5 to 1: 100 relative to the epoxide, and may be suitably used in a weight ratio of about 1: 1 to 1:10. At this time, if the ratio is too small, less than about 1: 0.5, the solvent may not function properly as a reaction medium and it may be difficult to take advantage of the above-described solution polymerization. In addition, when the ratio exceeds about 1: 100, the concentration of epoxide and the like may be relatively lowered, which may lower productivity, and may lower the molecular weight of the finally formed resin or increase side reactions.
  • the .organic zinc catalyst may be added in a molar ratio of about 1:50 to 1: 1000 relative to the epoxide. More preferably, the organic zinc catalyst may be added in a molar ratio of about 1:70 to 1: 600, or about 1:80 to 1: 300 relative to the epoxide. If the ratio is too small, it is difficult to show a catalytic catalytic activity during solution polymerization. On the contrary, if the ratio is too large, an excessive amount of catalyst is used to produce inefficient and by-products, or back-biting of the resin due to heating in the presence of a catalyst. ) May occur.
  • examples of the epoxide include an alkylene oxide having 2 to 20 carbon atoms unsubstituted or substituted with halogen or an alkyl group having 1 to 5 carbon atoms; Cycloalkylene oxide having 4 to 20 carbon atoms unsubstituted or substituted with halogen or alkyl group having 1 to 5 carbon atoms; And a styrene oxide having 8 to 20 carbon atoms substituted or unsubstituted with halogen or an alkyl group having 1 to 5 carbon atoms.
  • the epoxide may be an alkylene oxide having 2 to 20 carbon atoms unsubstituted or substituted with halogen or an alkyl group having 1 to 5 carbon atoms.
  • epoxides include ethylene oxide, propylene oxide, butene oxide, pentene oxide, nuxene oxide, octene oxide, decene oxide, dodecene oxad, tetradecene oxide, nuxadecene oxide, octadecene oxide, butadiene monooxide, 1 , 2-epoxy-7-octene, epifluorohydrin, epichlorohydrin, epibromohydrin, isopropyl glycidyl ether, butyl glycidyl ether, t-butyl glycidyl ether, 2-ethyl Nucleosil glycidyl ether, allyl glycidyl ether, cyclopentene oxide, cyclonuxene oxide, cyclooctene oxide, cyclododecene oxide, alpha-pinene oxide, 2,3-epoxynor
  • solution polymerization described above may be performed at about 50 to 100 ° C. and about 15 to 50 bar for about 1 to 60 hours. In addition, the solution polymerization is about
  • the polymerization process and conditions may be followed by conventional polymerization conditions for preparing the polyalkylene carbonate resin, and thus, further description thereof will be omitted.
  • Example 2 Preparation of Organic Zinc Catalyst
  • Example 2 An organic zinc catalyst of Example 2 was prepared in the same manner as in Example 1, except that lauric acid was used instead of valeric acid in Example 1, and the chemical structure thereof was confirmed. In addition, such an organic zinc catalyst was confirmed through SEM analysis, and as a result, the organic zinc catalyst of Example 2 was confirmed to have a standard deviation of an average particle diameter? Of about 0.48 and a particle diameter of about 0.28.
  • Example 3 Preparation of Organic Zinc Catalyst
  • Example 3 An organic zinc catalyst of Example 3 was prepared in the same manner as in Example 1, except that acetoacetic acid was used instead of valeric acid in Example 1, and the chemical structure thereof was confirmed. In addition, such an organic zinc catalyst was confirmed through SEM analysis, and as a result, the organic zinc catalyst of Example 3 was found to have a standard deviation of an average particle diameter of about 0.57 and a particle diameter of about 0.23.
  • Example 4 Preparation of Organic Zinc Catalyst
  • the organic zinc catalyst of Example 4 was prepared in the same manner as in Example 1, except that 5-hydroxy-4-oxo-4H-pyran-2-carboxylic acid was used instead of valeric acid in Example 1. The chemical structure was confirmed. In addition, such an organic zinc catalyst was confirmed through SEM analysis, and as a result, the organic zinc catalyst of Example 4 was confirmed to have a standard deviation of an average particle diameter of about 0.51 mm 3 and a particle diameter of about 0.28 mm. Comparative Example 1: Preparation of Organic Zinc Catalyst
  • An organic zinc catalyst of Comparative Example 2 was prepared in the same manner as in Example 1, except that propionic acid was used instead of valeric acid in Example 1, and the chemical structure thereof was confirmed. In addition, such an organic zinc catalyst was confirmed through SEM analysis, and as a result, the organic zinc catalyst of 2 was found to have a standard deviation of an average particle diameter of about 0.73 mm 3 and a particle diameter of about 0.34 1. 1 and 2, and the respective examples and comparative examples described above, Examples 1 to 2
  • An organic zinc catalyst prepared using a monocarboxylic acid having an aliphatic hydrocarbon group having 3 to 15 carbon atoms at 4 does not use such a monocarboxylic acid (Comparative Example 1), or a monocarboxylic acid having a hydrocarbon group having less than 3 carbon atoms bonded thereto. It was confirmed to have a more uniform and finer particle diameter compared to the organic zinc catalyst prepared using (propionic acid) (Comparative Example 2). Polymerization Example:
  • Polyethylene carbonate was polymerized and prepared in the following manner using the catalysts of Examples 1 to 4 and Comparative Examples 1 and 2.

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  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Inorganic Chemistry (AREA)
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Abstract

La présente invention concerne : un catalyseur organozincique ayant une taille de particules plus uniforme et plus fine à cause de l'inhibition de l'agrégation parmi les particules de catalyseur pendant une étape de préparation, présentant ainsi des activités plus améliorées dans une étape de polymérisation permettant de préparer une résine polyalkylène carbonate ; son procédé de préparation ; et un procédé de préparation d'une résine polyalkylène carbonate en faisant appel à celui-ci. Le catalyseur organozincique est un catalyseur organozincique à base de dicarboxylate de zinc utilisé dans une réaction permettant de préparer une résine polyalkylène carbonate à partir de dioxyde de carbone et d'un époxyde, un résidu dérivé d'acide monocarboxylique comprenant un groupe hydrocarbure aliphatique en C3-15 (au moins un oxygène ou un groupe carboxyle pouvant ou non être inclus dans le groupe hydrocarbure aliphatique) étant couplé à au moins une extrémité du catalyseur organozincique à base de dicarboxylate de zinc.
PCT/KR2014/011081 2013-11-18 2014-11-18 Catalyseur organozincique, son procédé de préparation, et procédé pour la préparation d'une résine polyalkylène carbonate en faisant appel à celui-ci WO2015072815A1 (fr)

Priority Applications (4)

Application Number Priority Date Filing Date Title
EP14862667.4A EP3048129B1 (fr) 2013-11-18 2014-11-18 Catalyseur organozincique, son procédé de préparation, et procédé pour la préparation d'une résine polyalkylène carbonate en faisant appel à celui-ci
CN201480063125.7A CN105764954B (zh) 2013-11-18 2014-11-18 有机锌催化剂及其制备方法以及使用该催化剂制备聚碳酸亚烷基酯树脂的方法
US15/034,696 US10047196B2 (en) 2013-11-18 2014-11-18 Organic zinc catalyst, and manufacturing method thereof and manufacturing method of polyalkylene carbonate resin using the same (as amended)
JP2016526195A JP6364076B2 (ja) 2013-11-18 2014-11-18 有機亜鉛触媒、その製造方法およびこれを用いたポリアルキレンカーボネート樹脂の製造方法

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KR20130139987 2013-11-18
KR10-2013-0139987 2013-11-18
KR1020140160747A KR101650510B1 (ko) 2013-11-18 2014-11-18 유기 아연 촉매, 이의 제조 방법 및 이를 사용한 폴리알킬렌 카보네이트 수지의 제조 방법
KR10-2014-0160747 2014-11-18

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2732475B2 (ja) * 1988-08-09 1998-03-30 三井化学株式会社 亜鉛含有固体触媒およびこの触媒を用いたポリアルキレンカーボネートの製法
KR20030097237A (ko) * 2002-06-20 2003-12-31 주식회사 포스코 지방족 폴리카보네이트 중합용 촉매의 제조 방법 및 이를사용한 지방족 폴리카보네이트의 중합 방법
KR20090025219A (ko) * 2006-05-09 2009-03-10 스미또모 세이까 가부시키가이샤 유기 아연 촉매 및 그것을 사용한 폴리알킬렌카보네이트의 제조 방법
WO2011004730A1 (fr) * 2009-07-07 2011-01-13 住友精化株式会社 Procédé de production de particules de polycarbonate aliphatique
KR20120023820A (ko) * 2009-05-22 2012-03-13 스미또모 세이까 가부시키가이샤 지방족 폴리카보네이트의 제조 방법

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2732475B2 (ja) * 1988-08-09 1998-03-30 三井化学株式会社 亜鉛含有固体触媒およびこの触媒を用いたポリアルキレンカーボネートの製法
KR20030097237A (ko) * 2002-06-20 2003-12-31 주식회사 포스코 지방족 폴리카보네이트 중합용 촉매의 제조 방법 및 이를사용한 지방족 폴리카보네이트의 중합 방법
KR20090025219A (ko) * 2006-05-09 2009-03-10 스미또모 세이까 가부시키가이샤 유기 아연 촉매 및 그것을 사용한 폴리알킬렌카보네이트의 제조 방법
KR20120023820A (ko) * 2009-05-22 2012-03-13 스미또모 세이까 가부시키가이샤 지방족 폴리카보네이트의 제조 방법
WO2011004730A1 (fr) * 2009-07-07 2011-01-13 住友精化株式会社 Procédé de production de particules de polycarbonate aliphatique

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