WO2015072814A1 - Procédé de préparation de résine de polycarbonate d'alkylène - Google Patents

Procédé de préparation de résine de polycarbonate d'alkylène Download PDF

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Publication number
WO2015072814A1
WO2015072814A1 PCT/KR2014/011080 KR2014011080W WO2015072814A1 WO 2015072814 A1 WO2015072814 A1 WO 2015072814A1 KR 2014011080 W KR2014011080 W KR 2014011080W WO 2015072814 A1 WO2015072814 A1 WO 2015072814A1
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WO
WIPO (PCT)
Prior art keywords
acid
zinc
carbonate resin
catalyst
polyalkylene carbonate
Prior art date
Application number
PCT/KR2014/011080
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English (en)
Korean (ko)
Inventor
김성경
조현주
강성균
박승영
최현
Original Assignee
주식회사 엘지화학
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 주식회사 엘지화학 filed Critical 주식회사 엘지화학
Priority to EP14862413.3A priority Critical patent/EP3048128B1/fr
Priority to US15/035,458 priority patent/US9732187B2/en
Priority to CN201480062879.0A priority patent/CN105722888B/zh
Priority to JP2016526103A priority patent/JP6272473B2/ja
Priority claimed from KR1020140160730A external-priority patent/KR101703275B1/ko
Publication of WO2015072814A1 publication Critical patent/WO2015072814A1/fr

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Classifications

    • 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 relates to a method for producing a polyalkylene carbonate resin in which aggregation between catalyst particles is suppressed during polymerization and excellent catalyst activity can be maintained during the polymerization process.
  • such zinc dicarboxylate-based catalysts typically zinc glutarate catalysts, are formed by reacting dicarboxylic acids such as zinc precursors and glutaric acid, and have a form of fine crystalline particles.
  • the zinc dicarboxylate-based catalyst in the form of crystalline particles has often caused a void between the catalyst particles during the polymerization process. If a cross between these catalyst particles occurs, When proceeding the polymerization process for the production of polyalkylene carbonate resin, there is a disadvantage that the sufficient contact area between the reactant and the catalyst is not secured, the polymerization activity by the catalyst is not sufficiently expressed.
  • the present invention provides a method for producing a polyalkylene carbonate resin in which aggregation between catalyst particles is suppressed in polymerization, so that excellent catalytic activity can be maintained during the polymerization process.
  • the present invention includes a step of polymerizing a zinc dicarboxylate-based organic zinc catalyst and a monomer including an epoxide and carbon dioxide in the presence of a dispersant, wherein the dispersant is an alkyl acrylate having 1 to 10 carbon atoms and 1 to 1 carbon atoms.
  • At least one selected from the group consisting of 10 alkylmethacrylates, monocarboxylic acids having 1 to 20 carbon atoms having oxo (0X0) groups in the molecular structure and polyether polymers having alkylene oxide repeat units having 2 to 6 carbon atoms It provides a method for producing a polyalkylene carbonate resin comprising a.
  • a method for preparing a polyalkylene carbonate resin according to an embodiment of the present invention will be described in detail.
  • an epoxide in the presence of a zinc dicarboxylate organic zinc catalyst and a dispersant. And polymerizing a monomer comprising carbon dioxide,
  • the dispersant is an alkyl acrylate having 1 to 10 carbon atoms, an alkyl methacrylate having 1 to 10 carbon atoms, a monocarboxylic acid having 1 to 20 carbon atoms having an oxo (0X0) group in the molecular structure, and an alkylene oxide having 2 to 6 carbon atoms.
  • a method for producing a polyalkylene carbonate resin comprising at least one member selected from the group consisting of polyether polymers having units.
  • a predetermined dispersant more specifically alkyl acrylates of 1 to 10 carbon atoms, alkyl methacrylate of 1 to 10 carbon atoms
  • Particular dispersants of polyether based polymers having monocarboxylic acids having 1 to 20 carbon atoms or alkylene oxide repeating units having 2 to 6 carbon atoms having an oxo (0X0) group in the molecular structure are used.
  • the organozinc catalyst can maintain a more uniform and fine particle state during the polymerization, and thus the contact area with the monomers is in contact with the monomer throughout the polymerization. It can exhibit excellent activity.
  • alkyl acrylate or alkyl having 1 to 10, or 3 to 8 carbon atoms alkyl acrylate or alkyl having 1 to 10, or 3 to 8 carbon atoms.
  • a specific dispersant in the copolymer increases, more specific, examples of such dispersants, haeksil methacrylic jjeyi agent, 3,5-dioxo-nuclear Sano acid, 3,5,7- tree-oxo-dodecanoyl acid, or propylene An oxide (P0) -ethylene oxide (EO) block copolymer etc. are mentioned, Of course, 2 or more types selected from these can also be used together.
  • a zinc dicarboxylate type organic zinc catalyst is used,
  • This organic zinc catalyst is a zinc precursor, C3-C20 aliphatic dicarboxylic acid, or C8-C40. It can be used as a catalyst obtained by reacting an aromatic dicarboxylic acid.
  • the zinc precursor may be zinc oxide, zinc hydroxide, zinc acetate (Zn (0 2 CCH 3 ) 2 ), zinc nitrate (Zn (NO 3 ) 2 ) or zinc sulfate
  • zinc precursor that has previously been used for the preparation of zinc dicarboxylate catalysts such as (ZnSO 4 ) and the like can be used without any particular limitation.
  • any aliphatic dicarboxylic acid having 3 to 20 carbon atoms or aromatic dicarboxylic acid having 8 to 40 carbon atoms can be used.
  • aliphatic dicarboxylic acid selected from the group consisting of malonic acid, glutaric acid, succinic acid and adipic acid, or aromatic dicarboxylic acid selected from the group consisting of terephthalic acid, isophthalic acid, homophthalic acid and phenylglutaric acid Acids and the like can be used.
  • the aliphatic dicarboxylic acid for example, glutaric acid
  • glutaric acid may be used to convert the zinc dicarboxylate-based organic zinc catalyst into a zinc glutarate-based catalyst. proper.
  • the dicarboxylic acid is from about 1.0 to 1 mole of the zinc precursor. 1.5 mol, or about 1.1 to 1.4 mol.
  • the production of the organic zinc catalyst by the reaction of the zinc precursor and dicarboxylic acid may proceed in a liquid medium, the liquid medium can uniformly dissolve or disperse the zinc precursor and / or dicarboxylic acid.
  • Any organic solvent known to be used can be used. Specific examples of such organic solvents include one or more organic solvents selected from the group consisting of toluene, DMF (dimethylformamide), ethane and methane.
  • reaction step between the zinc precursor and the dicarboxylic acid may proceed for about 5 to 24 hours at a temperature of about 30 to "0 ° C.
  • the organic zinc catalyst prepared under such conditions has a more uniform and finer particle diameter. Together can exhibit excellent catalytic activity.
  • the aforementioned organic zinc catalyst has a finer average particle diameter of about 0.3 to 1.0, black about 0.3 to 0.8 ⁇ , black about 0.5 to 0.7, and about 0.3 or less, black about 0.05 to 0.3 / m, or about 0.05 to 0.2 / zm, or in the form of uniform particles having a standard deviation of a particle diameter of about 0.05 to 0.1.
  • a dispersant during the polymerization process, it is possible to maintain such a uniform and fine particle diameter even in the polymerization process for the production of polyalkylene carbonate resin, so that a sufficient contact area with the reactants such as the monomer is maintained throughout the polymerization and excellent Catalytic activity can be shown during polymerization.
  • the organic zinc catalyst may be used as a heterogeneous catalyst
  • the polymerization step may be carried out by solution polymerization in an organic solvent.
  • solvents include methylene chloride, ethylene dichloride, trichloroethane, tetrachloroethane, chloroform, Acetonitrile, propionitrile, dimethylformamide, ⁇ -methyl-2-pyridone, dimethyl sulfoxide, nitromethane, 1,4-dioxane, nucleic acid, toluene, tetrahydrofuran, methylethylketone, methylamine Ketones, methyl isobutyl ketone, acetone, cyclonuxanonone, trichloroethylene, methyl acetate, vinyl acetate, ethyl acetate, propyl acetate, butyrolactone, caprolactone, nitropropane, benzene, styrene, xylene and methylpropazole ( Methyl propas) may be used one or more selected from the group consisting of. Also in the
  • the solvent is about 1: 0.5 to 1: 1 relative to the epoxide . It can be used in the weight ratio of 100, Preferably it can be used in the weight ratio of about 1: 1-1: 10. At this time, if the ratio is too small, less than about 1: 0.5, the solvent may not function properly as the 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 at 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 exhibit sufficient catalytic activity during solution polymerization. On the contrary, if the ratio is excessively large, an excessive amount of catalyst may be used, resulting in inefficient by-products, or back-biting of the resin due to heating in the presence of a catalyst. This can happen.
  • 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 a C 2 to C 20 unsubstituted or substituted with a halogen or an alkyl group having 1 to 5 carbon atoms.
  • Alkylene oxides can be used. Specific examples of such epoxides include ethylene oxide, propylene oxide, butene oxide, pentene oxide, nuxene oxide, octene oxide, decene oxide, dodecene oxide, 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 Hexyl glycidyl ether, allyl glycidyl ether, cyclopentene oxide, cyclonuxene oxide, cyclooctene oxide, cyclododecene oxide, alpha-pinene oxide, 2,3-
  • 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.
  • solution polymerization is more suitably carried out at about 70 to 90 ° C and about 20 to 40 bar, for about 3 to 40 hours.
  • the puncturing between the catalyst particles can be effectively suppressed. Therefore, during the polymerization process, the organic zinc catalyst can maintain a more uniform and finer particle state during the polymerization, and thus can exhibit excellent activity throughout the polymerization while contacting the monomer with a sufficient contact area. Thus, according to one embodiment, excellent catalytic activity is maintained continuously during the polymerization, so that the polyalkylene carbonate resin can be produced more effectively with excellent yield.
  • the organic zinc catalyst of Preparation Example 1 was prepared, and its chemical structure was confirmed. In addition, such an organic zinc catalyst was confirmed through SEM analysis, and as a result, it was confirmed that the organic zinc catalyst of Preparation Example 1 had a standard deviation of an average particle diameter of about 0.6 / im and a particle diameter of about 0.18 /.
  • Example 1
  • Example 1 polyethylene carbonate was prepared in the same manner as in Example 1, except that 10 mg of 3,5,7-trioxo-dodecanoic acid was used instead of nucleus methacrylate as the dispersant. The remaining solids were quantified after complete drying to determine the amount of polyethylene carbonate produced. The activity and yield of the catalyst according to the polymerization results are summarized in Table 1 below.
  • Example 3
  • Example 1 polyethylene carbonate was prepared in the same manner as in Example 1, except that 10 mg of 3,5-dioxonuxanoic acid was used instead of nucleus methacrylate as the dispersant. The remaining solids were quantified after complete drying to determine the amount of polyethylene carbonate produced. The activity and yield of the catalyst according to the polymerization results are summarized in Table 1 below.
  • Example 4 The activity and yield of the catalyst according to the polymerization results are summarized in Table 1 below.
  • Example 1 In Example 1, except that 10 mg of propylene oxide (PO) -ethylene oxide (EO) block copolymer (Mw: 8000; Sigma Aldrich Co. I) was used as dispersant instead of nucleus methacrylate. In the same manner, polyethylene carbonate was prepared. The remaining solids were quantified after complete drying to determine the amount of polyethylene carbonate produced. The activity and yield of the catalyst according to the polymerization results are summarized in Table 1 below. Comparative Example 1:
  • Example 1 polyethylene carbonate was prepared in the same manner as in Example 1, except that no dispersant was used. The remaining solids were quantified after complete drying to determine the ' amount of polyethylene carbonate prepared. The activity and yield of the catalyst according to the polymerization results are summarized in Table 1 below. Comparative Example 2:
  • Example 1 instead of nucleus methacrylate as the dispersant, 10 mg of Polyethylene carbonate was prepared in the same manner as in Example 1 except for using propionic acid. The remaining solids were quantified after complete drying to determine the amount of polyethylene carbonate produced. According to the polymerization results, the activity and yield of the catalyst are summarized in Table 1 below.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Inorganic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Polyesters Or Polycarbonates (AREA)

Abstract

La présente invention concerne un procédé de préparation d'une résine de polycarbonate d'alkylène, dans lequel des activités catalytiques remarquables peuvent être maintenues pendant une étape de polymérisation par inhibition de l'agrégation entre les particules de catalyseur pendant la polymérisation. Le procédé de préparation d'une résine de polycarbonate d'alkylène peut comprendre une étape de polymérisation de monomères comprenant un époxyde et du dioxyde de carbone en présence d'un catalyseur au zinc organique à base de dicarboxylate de zinc et d'un dispersant, et le dispersant peut comprendre au moins l'un choisi dans le groupe constitué d'un acrylate d'alkyle en C1-10, un méthacrylate d'alkyle en C1-10, un acide monocarboxylique en C1-20 ayant un groupe oxo dans une structure moléclaire, et un polymère à base de polyéther ayant un motif de répétition d'oxyde d'alkylène en C2-6.
PCT/KR2014/011080 2013-11-18 2014-11-18 Procédé de préparation de résine de polycarbonate d'alkylène WO2015072814A1 (fr)

Priority Applications (4)

Application Number Priority Date Filing Date Title
EP14862413.3A EP3048128B1 (fr) 2013-11-18 2014-11-18 Procédé de préparation de résine de polycarbonate d'alkylène
US15/035,458 US9732187B2 (en) 2013-11-18 2014-11-18 Manufacturing method of polyalkylene carbonate resin
CN201480062879.0A CN105722888B (zh) 2013-11-18 2014-11-18 聚亚烷基碳酸酯树脂的制备方法
JP2016526103A JP6272473B2 (ja) 2013-11-18 2014-11-18 ポリアルキレンカーボネート樹脂の製造方法

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
KR10-2013-0140000 2013-11-18
KR20130140000 2013-11-18
KR1020140160730A KR101703275B1 (ko) 2013-11-18 2014-11-18 폴리알킬렌 카보네이트 수지의 제조 방법
KR10-2014-0160730 2014-11-18

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2021038264A (ja) * 2016-09-30 2021-03-11 ダイキン工業株式会社 カルボン酸塩又はスルホン酸塩、及び、界面活性剤

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4943677A (en) * 1989-06-08 1990-07-24 Air Products And Chemicals, Inc. Making poly(alkylene carbonates) of controlled molecular weight
US4981948A (en) * 1988-08-09 1991-01-01 Mitsui Petrochemical Industries, Ltd. Zinc-containing solid catalyst, process of preparing same and process for preparing polyalkylene carbonate
KR20030097237A (ko) * 2002-06-20 2003-12-31 주식회사 포스코 지방족 폴리카보네이트 중합용 촉매의 제조 방법 및 이를사용한 지방족 폴리카보네이트의 중합 방법
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
US4981948A (en) * 1988-08-09 1991-01-01 Mitsui Petrochemical Industries, Ltd. Zinc-containing solid catalyst, process of preparing same and process for preparing polyalkylene carbonate
KR930003163B1 (ko) * 1988-08-09 1993-04-23 미쓰이 세끼유 가가꾸 고오교오 가부시끼가이샤 폴리알킬렌 카보네이트 제조용 아연함유 고체촉매와 그의 제조방법
US4943677A (en) * 1989-06-08 1990-07-24 Air Products And Chemicals, Inc. Making poly(alkylene carbonates) of controlled molecular weight
KR20030097237A (ko) * 2002-06-20 2003-12-31 주식회사 포스코 지방족 폴리카보네이트 중합용 촉매의 제조 방법 및 이를사용한 지방족 폴리카보네이트의 중합 방법
KR20120023820A (ko) * 2009-05-22 2012-03-13 스미또모 세이까 가부시키가이샤 지방족 폴리카보네이트의 제조 방법

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2021038264A (ja) * 2016-09-30 2021-03-11 ダイキン工業株式会社 カルボン酸塩又はスルホン酸塩、及び、界面活性剤

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