WO2019045418A1 - Procédé de production d'un catalyseur de zinc organique et catalyseur de zinc organique produit par ce procédé, et procédé de préparation de résine de carbonate de polyalkylène utilisant ce catalyseur - Google Patents

Procédé de production d'un catalyseur de zinc organique et catalyseur de zinc organique produit par ce procédé, et procédé de préparation de résine de carbonate de polyalkylène utilisant ce catalyseur Download PDF

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WO2019045418A1
WO2019045418A1 PCT/KR2018/009925 KR2018009925W WO2019045418A1 WO 2019045418 A1 WO2019045418 A1 WO 2019045418A1 KR 2018009925 W KR2018009925 W KR 2018009925W WO 2019045418 A1 WO2019045418 A1 WO 2019045418A1
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zinc
zirconium
catalyst
acid
precursor
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PCT/KR2018/009925
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English (en)
Korean (ko)
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방정업
박교성
박승영
황교현
최병희
김성경
방용주
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주식회사 엘지화학
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Priority to JP2019526250A priority Critical patent/JP6783391B2/ja
Priority to EP18851658.7A priority patent/EP3527286A4/fr
Priority to US16/469,421 priority patent/US11219887B2/en
Priority to CN201880015411.4A priority patent/CN110382114A/zh
Priority claimed from KR1020180101027A external-priority patent/KR102176690B1/ko
Publication of WO2019045418A1 publication Critical patent/WO2019045418A1/fr

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    • 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
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/12—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides
    • 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
    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/04—Mixing
    • 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
    • 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
    • B01J2235/00—Indexing scheme associated with group B01J35/00, related to the analysis techniques used to determine the catalysts form or properties

Definitions

  • the present invention relates to a process for producing an organic zinc catalyst, an organic zinc catalyst prepared by the process, and a process for producing a polyalkylene carbonate resin using the catalyst.
  • the present invention relates to a method for producing an organic zinc catalyst capable of exhibiting enhanced activity in a polymerization process for producing a polyalkylene carbonate resin, an organic zinc catalyst prepared by the method, and a method for producing a polyalkylene carbonate resin using the catalyst .
  • the polyalkylene carbonate is an amorphous transparent resin, unlike an aromatic carbonate which is a similar engineering plastic, has only an aliphatic structure, and is synthesized by a copolymerization reaction under a catalyst using carbon dioxide and epoxide as monomers.
  • These polyalkylene carbonates have excellent transparency, elongation and oxygen barrier properties, exhibit biodegradability, and are completely decomposed into carbon dioxide and water during combustion, leaving no carbon residue.
  • zinc dicarboxylate-based catalysts such as zinc glutarate catalysts having zinc and dicarboxylic acid bonded thereto are known as typical catalysts.
  • These zinc dicarboxylate catalyst typically a zinc glutarate catalyst is formed by reacting a dicarboxylic acid such as a zinc precursor and glutaric acid, and takes on a fine grain, crystalline particle form.
  • a dicarboxylic acid such as a zinc precursor and glutaric acid
  • the conventional zinc dicarboxylate catalyst causes depolymerization of the polyalkylene carbonate resin after backbiting, it is necessary to remove the resin from the resin after completion of the polymerization.
  • removal of the zinc dicarboxylate-based catalyst using these methods requires a lot of energy and further processing including a step of lowering the viscosity by further adding a solvent, removing the catalyst and then removing the solvent, There is a problem that the catalyst used in the polymerization is difficult to be reused.
  • zinc glutarate catalysts are greatly influenced by activity as well as acid-base characteristics and distance between Zn and Zn. Therefore, it is important to increase the activity by controlling the distance between Zn and Zn in the catalyst.
  • the present invention provides a process for preparing an organozinc catalyst which exhibits better catalytic activity than conventional catalysts for the production of polyalkylene carbonate resins. Also, the present invention provides an organic zinc catalyst prepared by the above method. In addition, the present invention provides a method for producing a polyalkylene carbonate resin using the organic zinc catalyst.
  • a process for producing a zirconium-containing catalyst comprising the steps of counteracting a zinc precursor with a dicarboxylic acid having a carbon number of 3 to 20 and a zirconium-
  • the zirconium-based co-catalyst is a zirconium-containing metal organic structure (Zr- metal organic framework, MOF) and a Zr precursor.
  • the present invention also provides a method for producing an organic zinc catalyst.
  • the zirconium element is comprised of a zirconium-based co-catalyst selected from the group consisting of a zirconium-containing metal organic framework (MOF) and a Zr precursor.
  • a zirconium-based co-catalyst selected from the group consisting of a zirconium-containing metal organic framework (MOF) and a Zr precursor.
  • a process for producing a polyalkylene carbonate resin which comprises polymerizing a monomer containing an epoxide and carbon dioxide in the presence of the organic zinc catalyst.
  • an organic zinc catalyst according to embodiments of the present invention, a method for producing the same, and a method for producing a polyalkylene carbonate resin using the catalyst will be described in detail.
  • organic zinc catalyst refers to an organic zinc catalyst, which is formed on the surface of a zinc dicarboxylate catalyst (hereinafter referred to as ZnGA) having activity in the production of a polyalkylene carbonate resin, May refer to the presence of a fixed Zr element component by chemical bonding, or by physical force such as adhesion, adhesion, adsorption, or at least partly embedded.
  • ZnGA zinc dicarboxylate catalyst
  • a method for producing a zirconium-containing cobalt-containing catalyst comprising the steps of: reacting a zinc precursor with a dicarboxylic acid and a zirconium-based cocatalyst having 3 to 20 carbon atoms, organofunctional organometallic framework, M0F), and Zr precursors can be provided.
  • Such a catalyst is used in the synthesis of a polyalkylene carbonate resin to exhibit high activity, thereby improving the synthesis yield of polyalkylene carbonate.
  • the present invention is characterized in that a zirconium-based material is used as a cocatalyst, and a small amount of a zirconium element is bonded on the surface of an organic zinc catalyst used for synthesis of a polyalkylene carbonate resin.
  • the method of the present invention can be expected to increase the catalytic activity as compared with a method using a transition metal such as general zinc or cobalt or a simple surface coating method.
  • the method of the present invention can exhibit the effect of enhancing the activity of the catalyst as compared with a catalyst made of zinc alone, a transition metal such as cobalt in addition to zirconium, or a method of simply coating a catalyst surface using a transition metal.
  • an organic zinc catalyst exhibiting high activity can be simply produced through a simple process in which a specific zirconium-based co-catalyst containing a small amount of Zr component is mixed with a zinc precursor and a dicarboxylic acid. Accordingly, in the present invention, the productivity of the polyalkylene carbonate can be improved by improving the anti-maleic properties by using the catalyst in the production of the polyalkylene carbonate resin which is a heterogeneous catalyst surface.
  • the zirconium-based co-catalyst is used as a van-gun precursor, and the zirconium-based co-catalyst is not included in the final organic zinc catalyst structure.
  • the final organozinc catalyst only a small amount of the zirconium element component contained in the added zirconium co-catalyst is bound to the surface of the zinc dicarboxylate catalyst in a predetermined amount.
  • Zr partially contained in the ZnGA surface in a specific amount acts as a cocatalyst to increase the activity in the polyalkylene carbonate resin synthesis reaction have.
  • a substance containing zirconium as a source may be used as the zirconium-based co-catalyst.
  • the zirconium-based co-catalyst may be any one selected from the group consisting of Zr-metal organic framework (Zr-MOF) containing zirconium and Zr precursor.
  • Zr-MOF Zr-metal organic framework
  • the promoter may be any Zr-metal-containing organic structure containing zirconium or a Zr precursor.
  • the zirconium metal is an organic structure containing the UiO-66 (Zi rconium 1, 4-dicarboxybenzene MOF), UiO-66-NH 2, Ui0-66-NH 3+, UiO-67, Ui0-68 and Nu-1000 and so on.
  • the zirconium-based co-catalyst may be used in an amount of 0.1 to 100 parts by weight or 0.2 to 60 parts by weight based on 100 parts by weight of the zinc precursor.
  • the content of the zirconium co-catalyst is calculated in terms of the molar ratio, 0.1 mol to 0.5 mol of the zirconium co-catalyst may be used per mol of the zinc precursor.
  • the content of the zirconium co-catalyst is 0.1 part by weight (0.1 m mole ratio) or less, there is a problem that Zr is not added to the surface of ZnGA.
  • the amount is more than 100 parts by weight (0.5 mole ratio) Which can reduce efficiency.
  • the method of the present invention can be carried out by preparing a mixture of a dicarboxylic acid and a zirconium-based co-catalyst, and adding a zinc precursor thereto.
  • the dicarboxylic acid and zirconium-based impurities may be provided by a dispersing method. According to a preferred embodiment, by dispersing the dicarboxylic acid and the zirconium-base promoter in a solvent under reflux and then heating, the mixture is provided .
  • the heating may be carried out at a temperature of 25 [ deg.] C to 100 [ deg.] C for 1 h to 24 h.
  • an organic zinc catalyst can be prepared through the reaction of a zinc precursor with a dicarboxylic acid by adding a zinc precursor material to the mixture.
  • the zinc dicarboxylate compound is formed by the reaction between the zinc precursor and the dicarboxylic acid, and at the same time, the above-described specific zirconium-based co-catalyst is added, The Zr component is fixed on the surface, and the zirconium element can be supported or substituted on the surface.
  • the reaction between the zinc precursor and the dicarboxylic acid may be carried out in the presence of a solvent capable of uniformly dispersing or dissolving the dicarboxylic acid.
  • the reaction can be carried out by adding a solvent, a dicarboxylic acid and the zirconium-based co-catalyst into a reactor capable of stirring, adding a zinc precursor thereto and stirring the mixture.
  • the bed may proceed type half the zirconium in the bath unggi catalyst with zinc and then added to the precursor solvent and a dicarboxylic acid by a "reaction cycle.
  • the zinc precursor may be zinc oxide (ZnO), zinc sulfate (ZnSO 4 ), zinc chlorate (Zn (C10 3 ) 2 ), zinc nitrate (Zn (NO 3 ) 2 ) 0Ac) 2 ), and zinc hydroxide (Zn (OH) 2 ) can be used.
  • the dicarboxylic acid having 3 to 20 carbon atoms may be at least one compound selected from the group consisting of malonic acid, glutaric acid, succinic acid, adipic acid, terephthalic acid, isophthalic acid, homophthalic acid, and phenylglutaric acid. Can be used.
  • the dicarboxylic acid may be obtained by using glutaric acid, which is excellent in catalytic performance.
  • the dicarboxylic acid may be used in the same or an excessive molar amount as the zinc precursor.
  • the reaction step may be carried out at a molar ratio of 1 mole of the zinc precursor to 1 to 1.5 moles of the dicarboxylic acid, or about 1.1 to 1.3 moles of the zinc precursor.
  • the uniformly dispersed zinc precursor The dicarboxylic acid molecule and the ions can be slowly surrounded by the surroundings.
  • the solvent any organic or aqueous solvent known to be capable of uniformly dispersing or dissolving the dicarboxylic acid may be used. Specific examples of such solvents include at least one solvent selected from the group consisting of uranols, nucleic acids, dimethylformamide, acetone, methane, ethanol, and water.
  • the solvent may be added in an appropriate amount to subdivide the raw material components, preferably 2 to 1000 mol based on 1 mol of the dicarboxylic acid. More preferably, the solvent is a dicarboxylic acid 5 to 100 moles, or 10 to 50 moles, based on 1 mole. In the above range, the dicarboxylic acid is appropriately dispersed in the solvent so that the progress of the catalyst synthesis reaction can be effectively performed.
  • the reaction between the zinc precursor and the dicarboxylic acid can be carried out at a temperature of about 40 to 130 ° C for about 1 to 48 hours. According to one embodiment of the present invention, in the presence of the solvent, the reaction is carried out at a temperature of about 40 ° C for about 1 hour to 24 hours at a temperature of about 80 to 130 ° C for about 1 to 24 hours The reaction can proceed. By adjusting the reaction temperature or time, a catalyst in which the Zr component is uniformly fixed on the surface of the zinc dicarboxylate compound having a uniform shape can be produced.
  • washing and drying the prepared organic zinc catalyst may be further performed.
  • the washing step may be repeated several times using a solvent that can be used in the above-described reaction until the unreacted reaction product remains.
  • the drying step may be performed by vacuum drying at a temperature of 40 to 200 ° C.
  • a zinc dicarboxylate compound A zirconium element supported or substituted on the surface of the zinc dicarboxylate compound,
  • the zirconium element may be provided from an zirconium-based co-catalyst selected from the group consisting of a Zr-metal organic framework (MOF) containing zirconium and a Zr precursor.
  • MOF Zr-metal organic framework
  • the Zr catalyst according to the present invention may be substituted for Zr in the form of ZrO 2 or Zr 2 , and the specific content of zirconium may be bonded to the surface of the zinc dicarboxylate compound to exist in a supported or substituted form .
  • the content of the zirconium element on the surface of the zinc dicarboxylate compound may be 0.01 to 5% by weight based on the total weight of the total elements constituting the organic zinc catalyst. More preferably, the content of the zirconium element on the surface of the zinc dicarboxylate compound may be 0.01 to 1% by weight based on the total weight of the total elements constituting the organic zinc catalyst. At this time, if the content of the zirconium element is less than 0.01% by weight, there is a problem in that it is not effective in increasing the activity, and when it is more than 5% by weight, the activity is lowered.
  • the zirconium metal is an organic structure containing the UiO- 66 (Zi rconium 1, 4 -di carboxybenzene MOF), UiO-66-NH 2, UiO-66-NH 3+, UiO-67, Ui0-68 and Nu - 1000. ≪ / RTI >
  • the Zr precursor may be at least one selected from the group consisting of ZrSO 4 , zirconium acetate, zirconium iodide, zirconium fluoride, zirconium chloride, zirconium acetylacetonate, zirconium annexoxide, zirconium propoxide and Zr 4.
  • the organic zinc catalyst prepared in the present invention can exhibit high activity in the production of polyalkylene carbonate with a small amount of Zr contained in the surface of the ZnGA catalyst.
  • the zinc dicarboxylate compound for supporting the zirconium element on the surface by adding the zirconium-based co-catalyst is a bioproduct of the zinc precursor and the dicarboxylic acid having 3 to 20 carbon atoms as described above.
  • the zinc dicarboxylate compound may be at least one selected from zinc malonate, zinc glutarate, zinc succinate, zinc adipate, zinc terephthalate, At least one compound selected from the group consisting of zinc isophthalate, zinc homophthalate, and zinc phenyl glutarate.
  • zinc glutarate is advantageous as the zinc dicarboxylate compound in view of the activity of the organic zinc catalyst and the like.
  • a process for producing a polyalkylene carbonate resin which comprises polymerizing a monomer containing an epoxide and carbon dioxide in the presence of the above-mentioned organic zinc catalyst.
  • the organic zinc catalyst may be used as a heterogeneous catalyst, and the polymerization step may be carried out by solution polymerization in an organic solvent. That is, the polymerization step can proceed with solution polymerization capable of continuous contact of the organic zinc catalyst with the antimony compound, including epoxide, carbon dioxide and a 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.
  • the solvent includes, for example, dichloromethane, ethylene dichloride, trichloroethane, tetrachloroethane, chloroform, acetonitrile, propionitrile, dimethylformamide, N- , Nitromethane, 1, 4-dioxane, nucleic acid, dichloromethane, tetrahydrofuran, methyl ethyl ketone, methylamine ketone, methyl isobutyl ketone, acetone, cyclohexanone, trichlorethylene, methyl acetate, vinyl acetate, ethyl acetate , Propyl acetate, butylolactone, caprolactone, nitropropane, benzene, styrene, xylene, and methyl propasol may be used.
  • a chlorinated solvent such as dichloromethane, ethylene dichloride, trichloroethane, tetrach
  • the solvent may be used at a weight of 0.1 to 100 times the weight of the epoxide, and may be suitably used at a weight of 0.5 to 50 times. In this case, when the solvent is used at a weight of less than 0.1 times, It may be difficult to take advantage of the above-mentioned solution polymerization. In addition, when the solvent is used in a weight of more than 100 times, the concentration of epoxide or the like may be relatively low, resulting in a decrease in productivity and a decrease in the molecular weight of the finally formed resin or an increase in side reaction.
  • the carbon dioxide may be present in the reaction mixture in an amount of from about 1 to about 1 mole per mole of epoxide,
  • the carbon dioxide may be introduced at about 2 to 5 moles per mole of epoxide.
  • the amount of carbon dioxide is less than 1 mole, the content of the polyalkylene glycol in the byproduct tends to increase, and when it is used in excess of 10 moles, it is not effective due to the introduction of excess monomer.
  • organozinc catalyst may be used in a ratio of from about 1:50 to 1:
  • the organic zinc catalyst may be added in a molar ratio of about 1:70 to 1: 600, and black to about 1:80 to 1: 300, relative to the epoxide. If the proportion is too small, it is difficult to exhibit the catalytic activity of the solution during polymerization. On the contrary, if the amount is excessively large, it becomes inefficient due to the use of an excessive amount of the catalyst, or a by- t ing can occur.
  • an alkylene oxide having 2 to 20 carbon atoms which is substituted or unsubstituted with halogen or an alkyl group having 1 to 5 carbon atoms A cycloalkylene oxide having 4 to 20 carbon atoms substituted or unsubstituted with halogen or an alkyl group having 1 to 5 carbon atoms; And styrene oxide having 8 to 20 carbon atoms substituted or unsubstituted with halogen or an alkyl group having 1 to 5 carbon atoms.
  • an alkylene oxide having 2 to 20 carbon atoms, which is substituted or unsubstituted with a halogen or an alkyl group having 1 to 5 carbon atoms may be used.
  • epoxides include ethylene oxide, propylene oxide, butene oxide, pentene oxide, heptane oxide, octene oxide, decene oxide, dodecene oxide, tetradecene oxide, hexadecene oxide, octadecene oxide, butadiene monoxide, 2-epoxy-7-octene, epifluorohydrin, epichlorohydrin, epibromohydrin, isopropyl glycidyl ether, butyl glycidyl ether, t-butylglycidyl Ether, 2-ethylhexyl glycidyl ether, allyl glycidyl ether, cyclopentene oxide, cyclohexene oxide, cyclooctene oxide, cyclododecene oxide, alpha-pinene oxide, 2,3-epoxy norbornene, limon
  • the above-mentioned solution polymerization can be carried out at a temperature of 50 to 90 ° C and a pressure of 15 to 50 bar for 1 to 60 hours. It is more preferable that the solution polymerization is carried out at a temperature of 70 to 90 ° C and a pressure of 20 to 40 bar for 3 to 40 hours. Under these conditions, the polymerization reaction promoted by the organozinc catalyst according to one embodiment can proceed effectively.
  • the organic zinc catalyst may further include a step of thoroughly washing the catalyst or a vanishing unit containing the catalyst after polymerization and storing the catalyst in a solvent such that the catalyst is not dried. Accordingly, the stored organosilane catalyst can be reused in the next polymerization. Specifically, the stored organozinc catalyst can be used three or more times. Except for the above-mentioned matters, the other polymerization processes and conditions may depend on conventional polymerization conditions for the production of the polyalkylene carbonate resin, so that further explanation thereof will be omitted.
  • the organic zinc catalyst according to the present invention can be easily prepared through a simple process of adding a catalyst synthesizer Zr co-catalyst, and the organic zinc catalyst thus prepared can increase the catalytic activity in the synthesis of polyalkylene carbonate resin have. Particularly, in the present invention, it was confirmed that the catalytic activity was greatly improved even when a small amount of Zr component was contained on the surface of the ZnGA catalyst.
  • FIG. 1 shows the results of Zr3d narrow scan spectrum (XPS) according to the content of zirconium co-catalyst added to ZnGA.
  • Example 2 The formed solid was separated using a centrifuge. The separated solid was washed three times with acetone / ethanol and dried in a vacuum oven at 130 ° C to obtain 3.2 g of zinc glutarate supported catalyst.
  • Example 2 The formed solid was separated using a centrifuge. The separated solid was washed three times with acetone / ethanol and dried in a vacuum oven at 130 ° C to obtain 3.2 g of zinc glutarate supported catalyst.
  • Example 3 The formed solid was separated using a centrifuge. The separated solid was washed three times with acetone / ethanol and dried in a vacuum oven at 130 ° C to obtain 3.2 g of zinc glutarate supported catalyst.
  • Example 3 The formed solid was separated using a centrifuge. The separated solid was washed three times with acetone / ethanol and dried in a vacuum oven at 130 ° C to obtain 3.2 g of zinc glutarate supported catalyst.
  • Example 4 The formed solid was separated using a centrifuge. The separated solid was washed three times with acetone / ethanol and dried in a vacuum oven at 130 ° C to obtain 3.2 g of zinc glutarate supported catalyst.
  • Example 4
  • Example 5 The solid formed was separated using a centrifuge. The separated solid was washed three times with acetone / ethane and then dried in a vacuum oven at 130 ° C to obtain 3.2 g of zinc glutarate supported catalyst.
  • Example 5 The solid formed was separated using a centrifuge. The separated solid was washed three times with acetone / ethane and then dried in a vacuum oven at 130 ° C to obtain 3.2 g of zinc glutarate supported catalyst.
  • Example 6 The formed solid was separated using a centrifuge. The separated solid was washed three times with acetone / ethanol and dried in a vacuum oven at 130 ° C to obtain 3.2 g of zinc glutarate supported catalyst.
  • Example 6 The formed solid was separated using a centrifuge. The separated solid was washed three times with acetone / ethanol and dried in a vacuum oven at 130 ° C to obtain 3.2 g of zinc glutarate supported catalyst.
  • a zinc glutarate supported catalyst was prepared in the same manner as in Example 1, except that cobalt oxide was used instead of UiO-66. Test Example 1
  • the catalysts of Examples 1 to 6 exhibited very excellent catalytic activity as compared with the catalysts of Comparative Examples 1 to 3, and the difference is remarkable.
  • the Zr component is not contained on the surface of the organic zinc catalyst.

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Abstract

La présente invention concerne un procédé de production d'un catalyseur de zinc organique utilisé dans la synthèse d'une résine de carbonate de polyalkylène et un catalyseur de zinc organique ainsi obtenu. L'invention concerne en outre un procédé de préparation d'une résine de carbonate de polyalkylène à l'aide du catalyseur. Le catalyseur de zinc organique selon la présente invention comprend une quantité prédéterminée de Zr sur une surface par un procédé simple, et peut ainsi présenter une activité catalytique améliorée par comparaison avec un état de la technique classique dans une procédure de polymérisation pour préparer une résine de carbonate de polyalkylène.
PCT/KR2018/009925 2017-08-28 2018-08-28 Procédé de production d'un catalyseur de zinc organique et catalyseur de zinc organique produit par ce procédé, et procédé de préparation de résine de carbonate de polyalkylène utilisant ce catalyseur WO2019045418A1 (fr)

Priority Applications (4)

Application Number Priority Date Filing Date Title
JP2019526250A JP6783391B2 (ja) 2017-08-28 2018-08-28 有機亜鉛触媒の製造方法と前記方法で製造された有機亜鉛触媒、および前記触媒を用いたポリアルキレンカーボネート樹脂の製造方法
EP18851658.7A EP3527286A4 (fr) 2017-08-28 2018-08-28 Procédé de production d'un catalyseur de zinc organique et catalyseur de zinc organique produit par ce procédé, et procédé de préparation de résine de carbonate de polyalkylène utilisant ce catalyseur
US16/469,421 US11219887B2 (en) 2017-08-28 2018-08-28 Method for preparing organic zinc catalyst, organic zinc catalyst prepared by the method and method for preparing polyalkylene carbonate resin using the catalyst
CN201880015411.4A CN110382114A (zh) 2017-08-28 2018-08-28 制备有机锌催化剂的方法，通过该方法制备的有机锌催化剂以及采用该催化剂制备聚碳酸亚烷基酯树脂的方法

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KR20170108897 2017-08-28
KR10-2017-0108897 2017-08-28
KR1020180101027A KR102176690B1 (ko) 2017-08-28 2018-08-28 유기 아연 촉매의 제조 방법과 상기 방법으로 제조된 유기 아연 촉매, 및 상기 촉매를 이용한 폴리알킬렌 카보네이트 수지의 제조 방법
KR10-2018-0101027 2018-08-28

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115028845A (zh) * 2022-05-11 2022-09-09 烟台大学 一种锌配位聚合物催化剂及其制备方法和应用

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Publication number Priority date Publication date Assignee Title
US6617467B1 (en) * 2002-10-25 2003-09-09 Basf Aktiengesellschaft Process for producing polyalkylene carbonates
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