WO2015190874A1 - Catalyseur de zinc organique, procédé de fabrication de ce dernier et procédé de préparation d'une résine de carbonate de polyalkylène à l'aide d'un catalyseur de zinc organique - Google Patents
Catalyseur de zinc organique, procédé de fabrication de ce dernier et procédé de préparation d'une résine de carbonate de polyalkylène à l'aide d'un catalyseur de zinc organique Download PDFInfo
- Publication number
- WO2015190874A1 WO2015190874A1 PCT/KR2015/005951 KR2015005951W WO2015190874A1 WO 2015190874 A1 WO2015190874 A1 WO 2015190874A1 KR 2015005951 W KR2015005951 W KR 2015005951W WO 2015190874 A1 WO2015190874 A1 WO 2015190874A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- zinc
- catalyst
- acid
- dispersant
- precursor
- Prior art date
Links
Classifications
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/06—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of zinc, cadmium or mercury
-
- 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
Definitions
- the present invention provides an organic zinc catalyst having a more uniform and fine particle diameter and exhibiting improved activity in a polymerization process for producing a polyalkylene carbonate resin, a method for preparing the same, and a polyalkylene carbonate resin using the organic zinc catalyst. It relates to a manufacturing method. .
- Such a zinc dicarboxylate-based catalyst typically a zinc glutarate catalyst, is formed by reacting a zinc precursor with dicarboxylic acids such as glutaric acid and has a form of fine crystalline particles.
- a zinc dicarboxylate catalyst in the form of crystalline particles was difficult to be controlled to have a uniform and fine particle diameter in the preparation process.
- Conventional zinc dicarboxylate-based catalysts have a nanometer-scale particle size, but as the aggregates of the catalyst particles in the medium form agglomerates having a larger particle size and a smaller surface area, the preparation of polyalkylene carbonate resins using the same There is a problem in that the catalytic activity is lowered.
- the smaller the size of the zinc precursor used in the preparation of the zinc dicarboxylate-based catalyst was found to have a significant effect on the activity increase of the resulting catalyst.
- zinc oxide powders used as zinc sources (zinc precursors) for the production of zinc dicarboxylate catalysts are ion-bonded particles having a particle size of tens to hundreds of nanometers and a specific surface area of about 10 m 2 / g. to be.
- the zinc oxide powder has a very high polarity and is well dispersed in a polar solvent, but in a nonpolar solvent, the particles aggregate together to form a very large aggregate.
- a nonuniform reaction occurs when the whole reaction system is examined.
- the heterogeneity of the resulting catalyst crystallinity is increased, thereby lowering the activity of the catalyst.
- WO 2011/107577 discloses a method of synthesizing a catalyst after surface treatment of a zinc source used for producing an organic zinc catalyst with an organic silane to increase the specific surface area of the zinc source.
- the method has several limitations (steps of reaction, screening, drying, etc.) prior to the surface modification of the zinc source using the organic silane, and thus there is a limitation that the manufacturing process is not efficient compared to the effect of improving the catalytic activity.
- an organic zinc catalyst having a more uniform and finer particle diameter and exhibiting improved activity in the process of polymerization for producing a polyalkylene carbonate resin is provided.
- the present invention provides a method for producing a polyalkylene carbonate resin using an organic zinc catalyst obtained through the above production method.
- the method comprises the steps of surface treatment of the zinc precursor with at least one dispersant selected from the group consisting of anionic surfactants, cationic surfactants, and amphiphiUc surfactants; And reacting the surface-treated zinc precursor with a dicarboxylic acid having 3 to 20 carbon atoms to form a zinc dicarboxylate-based catalyst.
- the surface treated with at least one dispersant selected from the group consisting of anionic surfactants, cationic surfactants, and amphoteric surfactants A zinc dicarboxylate catalyst obtained by reacting a zinc precursor with a dicarboxylic acid having 3 to 20 carbon atoms, wherein an organic zinc catalyst having 0.001 to 5% by weight of the dispersant is present on the catalyst based on the weight of the catalyst. .
- a method for producing a polyalkylene carbonate resin comprising the step of polymerizing a monomer comprising an epoxide and carbon dioxide in the presence of an organic zinc catalyst prepared by the above method.
- a method for preparing an organic zinc catalyst according to embodiments of the present invention, an organic zinc catalyst obtained through the same, and a method for producing a polyalkylene carbonate resin using the same will be described in detail.
- an organic zinc catalyst comprising a.
- a method for producing an organic zinc catalyst comprising a.
- the effect can be better realized by applying a dispersant having a phosphate functional group (for example, a phosphoric acid group, a phosphonic acid group, etc.) to the surface treatment of the zinc precursor.
- a dispersant having a phosphate functional group for example, a phosphoric acid group, a phosphonic acid group, etc.
- the reason for this is that the strong adhesion (gravity) between the phosphate-based functional group and the zinc precursor of the dispersant acts, which induces a steric hindrance effect, so that the zinc precursors can remain dispersed without being coagulated with each other.
- an organic zinc catalyst showing better activity can be obtained as a particle form having finer and more uniform particle size.
- the fine and uniform particle size of such catalyst particles can be obtained. Due to this, dispersion and control of the catalyst particles in the reaction solution can be made easier. Therefore, such an organic zinc catalyst can be very preferably applied to the production of polyalkylene carbonate resins by reaction of carbon dioxide and epoxide.
- the zinc precursor is surface-treated with a dispersant, compared to the surface treatment with a dispersant, it is possible to minimize the formation of zinc precursors in the medium, and to exhibit improved dispersion stability Can be.
- the surface-treated zinc precursor is dicarboxylic acid It is possible to maintain a fine, uniform and stable dispersion state during the reaction.
- a surface treatment of the zinc precursor with a dispersant is performed.
- the step may be carried out by mixing the zinc precursor and the dispersant under a solvent. That is, the step is a wet process, wherein the solvent in the step may be any organic or aqueous solvent capable of smoothly surface treatment of the zinc precursor with the dispersant. Examples of such a solvent include at least one solvent selected from the group consisting of toluene, nucleic acid, dimethylformamide, ethane, and water.
- the liquid medium may preferably have the same properties as the solvent used in the surface treatment step.
- the zinc precursor any zinc precursor that has been used for the preparation of a zinc dicarboxylate catalyst can be used without any limitation.
- the zinc precursor is zinc oxide (ZnO), zinc sulfate (ZnS0 4 ), zinc chlorate (Zn (C10 3 ) 2 ), zinc nitrate (Zn (N0 3 ) 2 ), zinc acetate (Zn (OAc) 2 ), And zinc hydroxide (Zn (OH) 2 ).
- the dispersant is a component capable of dispersing the zinc precursor in a medium in a uniform and non-aggregated state, and includes anionic surfactants, cationic surfactants, and amphiphilic surfactants. It may be one or more compounds selected from the group consisting of. As the anionic, cationic, or amphoteric surfactant, compounds conventional in the art to which the present invention pertains may be applied without particular limitation. In addition, the dispersant may be appropriately selected in consideration of the type and nature of the medium used in the preparation of the zinc precursor and the zinc dicarboxylate catalyst.
- the dispersant may be a surfactant having a part having an ionic functional group capable of physically or chemically adsorbing on the surface of the zinc precursor and a hydrocarbon part having good compatibility with a solvent in the molecule.
- the dispersant may be a copolymer, preferably a surfactant having a structure of a block copolymer.
- a phosphate dispersant having a phosphate functional group may be preferably used. More preferably, the phosphoric acid-based dispersant may be used at least one compound selected from the group consisting of an anionic surfactant having a phosphoric acid group or a phosphorous acid group and an amphoteric surfactant.
- the phosphate-based functional group exhibits a strong adhesion (tension) to the zinc precursor, which leads to a stable steric hindrance effect around the zinc precursor, so that the zinc precursors may be dispersed without being coagulated with each other.
- the dispersing agent is 0.01 to 10 parts by weight with respect to zinc precursor 0/0, or 0.1 to 10 parts by weight 0/0, or 1 to 10 parts by weight 0/0, or 1 to Z5 weight 0/0, or used as a 1 to 5% by weight Can be. That is, in order to allow the surface treatment of the zinc precursor can be made sufficiently layer, the dispersing agent is preferably used in 0.01 0/0 or higher with respect to the zinc precursor. However, when the dispersant is mixed in an excessive amount, the dispersant may participate in reaction and cause side reactions, or may affect the composition of the medium, thereby lowering the crystallinity of the catalyst, which may cause the coarseness of the zinc precursor. May appear. Thus, the dispersing agent is preferably used at or below 10 increased 0/0 with respect to the zinc precursor.
- the zinc precursor surface-treated with the dispersant may have a D 90 particle size distribution of 10 or less, or 1 to 10, or 1.5 to 8 ⁇ , or 3 to 7.5 pi, as measured under ethanol solvent.
- the above D 90 means the particle diameter at which the cumulative frequency of the volume distribution reaches 90% by accumulating from the particle having the smaller particle size.
- the particle diameter of the surface-treated zinc precursor is a hole between the zinc precursor in the state where the zinc precursor is added to the medium for reaction with the dicarboxylic acid. It means the diameter of the aggregated particles formed by.
- the particle size distribution can be stably maintained during reaction with the dicarboxylic acid.
- a zinc precursor having a D 90 particle size distribution of more than 10 is used in reaction with the dicarboxylic acid, not only uniform reaction with the dicarboxylic acid is difficult, but also the zinc precursor precipitates before the reaction is completed. Stable dispersion cannot be maintained.
- the step of reacting the surface-treated zinc precursor with dicarboxylic acid to form a zinc dicarboxylate catalyst is performed.
- the dicarboxylic acid may be aliphatic dicarboxylic acid such as malonic acid, glutaric acid, succinic acid, and adipic acid; Aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, homophthalic acid, and phenylglutaric acid.
- various aliphatic or aromatic dicarboxylic acids having 3 to 20 carbon atoms may be used.
- the dicarboxylic acid is glutaric acid in view of the activity of the catalyst.
- the organic zinc catalyst is a zinc glutarate-based catalyst.
- the dicarboxylic acid may be used in an equivalent or excess mole of the zinc precursor, and specifically, about 1 to 1.5 moles, or about 11 to 1.3 moles per mole of the zinc precursor.
- the dicarboxylic acid may proceed slowly in the form of dicarboxylic acid molecules or silver surrounded by a uniformly dispersed zinc precursor. Accordingly, an organic zinc catalyst can be obtained in which the zinc precursors can react with dicarboxylic acids without hardly agglomeration with each other, and have a more uniform and fine particle diameter and exhibit improved activity.
- the reaction step may be performed under a liquid medium in which a reaction product containing a surface-treated zinc precursor and dicarboxylic acid is present (for example, in a solution or dispersion in which the reaction product is dissolved or dispersed). have.
- the The solution or dispersion containing dicarboxylic acid may be added while dividing the solution or dispersion containing the surface-treated zinc precursor into two or more times. That is, a part of the solution or dispersion containing the surface-treated zinc precursor is first added to the solution or dispersion containing the dicarboxylic acid, followed by reaction, and then the remainder of the solution or dispersion containing the surface-treated zinc precursor is divided. You can proceed with the rest of the reaction.
- the whole reaction step can be carried out while maintaining the molar ratio of the zinc precursor and the dicarboxylic acid in the reaction system, from which an organic zinc catalyst having a more uniform and fine particle diameter and exhibiting improved activity can be obtained.
- the entire reaction step may be performed while uniformly dropping the solution or dispersion containing the surface-treated zinc precursor in the form of droplets to the solution or dispersion containing the dicarboxylic acid.
- the reaction of the surface-treated zinc precursor and dicarboxylic acid may proceed under a liquid medium.
- a liquid medium any organic or aqueous solvent known to be capable of uniformly dissolving or dispersing the surface-treated zinc precursor and / or dicarboxylic acid may be used.
- the liquid medium may be at least one solvent selected from the group consisting of toluene, nucleic acid, dimethylformamide, ethanol, and water.
- the reaction of the surface-treated zinc precursor and the dicarboxylic acid may be performed for about 1 to 10 hours at a temperature of about 50 to 130 ° C.
- zinc precursors surface-treated at equal intervals may be dividedly added to the total reaction time increase, and the reaction rate of the reaction product in the reaction system may be maintained throughout the reaction process.
- Zinc dicarboxylate obtained by reacting a zinc precursor surface-treated with at least one dispersant selected from the group consisting of anionic surfactants, cationic surfactants, and amphoteric surfactants with dicarboxylic acids having 3 to 20 carbon atoms.
- a system catalyst An organic zinc catalyst is provided in which the dispersant is present in the catalyst at a weight of ⁇ to 5% by weight relative to the weight of the catalyst.
- the organic zinc catalyst is obtained by reacting a zinc precursor and a dicarboxylic acid surface-treated with a dispersant, and can be preferably obtained by the above-described manufacturing method. That is, the organic zinc catalyst is prepared through reaction with dicarboxylic acid in a state where the dispersion of the surface-treated zinc precursor is optimized as described above.
- the organic zinc catalyst according to the present invention may have a uniform particle shape having an average particle diameter of about 0.5 urn or less, or about 0.1 to 0.4 / m, or about 0.2 / ⁇ .
- the mean particle size of the catalyst means the size of the catalyst particles themselves in a state incompatible with the medium. Such primary particle size can be measured through an electron microscope or the like.
- the "secondary particle size" of the catalyst refers to the size of the aggregate formed by the intervesage between the catalyst particles in a state in which it is mixed with the medium.
- the organic zinc catalyst since the organic zinc catalyst has a fine and uniform particle diameter, the organic zinc catalyst may have a surface area that is about 1.5 to 6 times increased compared to the surface area of the general organic zinc catalyst (for example, about 1.1 to 1.3 ltf / g). have.
- the dispersant used in the surface treatment of the zinc precursor not only improves the dispersibility of the zinc precursor, but also contributes to the dispersibility of the finally produced organic zinc catalyst. That is, the organic zinc catalyst is formed by reaction of the zinc precursor and the dicarboxylic acid surface-treated with the dispersant, and some of the dispersants separated in the process may stabilize the finally produced organic zinc catalyst.
- the particle size (the secondary particle size) of the organic zinc catalyst is measured in an ethanol solvent
- the organic zinc catalyst is less than 5 urn, or 1 to 5 kPa, or 1 to 3, or 1 to 5.5 D 50 particle size distribution.
- the D 50 means a particle diameter at which the cumulative frequency of the volume distribution reaches 50% by accumulating from the particle having the smaller particle size.
- the amount of dispersing agent present on the catalyst is preferably 5 parts by weight 0/0 or less, based on the weight of the catalyst.
- a dispersant having a degree of forming a dispersant layer having a thickness of 10 nm or more on the surface of the catalyst should be used.
- a 10 nm thick dispersant layer (assuming a density of about 1 g / ciii) covering the surface of a typical zinc glutarate catalyst (density about 2.1 g / cirf) having a surface area of 10 to 20 rif / g theoretically
- the organic zinc catalyst according to embodiments of the invention are prepared by the method described above, while having an enhanced surface area than the prior catalyst, weight ratio of the zinc precursor used in the synthesis of the catalyst 5 weight 0/0 or less Stable dispersibility of the catalyst can be ensured only by the dispersant content of. This would not only that amount less than the amount (10 to 25 parts by weight 0/0, based on the weight of the catalyst) of the theoretically required dispersant, given the increased surface area available for the remarkably small amount.
- the organic zinc catalyst when used to prepare a polyalkylene carbonate resin by copolymerization of carbon dioxide and epoxide, an increased contact area between the catalyst particles and the semiungmul can be secured and improved activity can be expected.
- a method for producing a polyalkylene carbonate resin comprising the step of polymerizing a monomer comprising an epoxide and carbon dioxide in the presence of an organic zinc catalyst prepared by the above-described method .
- 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 semi-heat 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, N-methyl-2-pyrididone, dimethyl sulfoxide , Nitromethane, 1,4-dioxane, nucleic acid, toluene, tetrahydrofuran, methyl ethyl ketone, methyl amine ketone, methyl isobutyl ketone, acetone, cyclonuxanone, trichloro ethylene, methyl acetate, vinyl acetate, ethyl acetate At least one selected from the group consisting of propyl acetate, butyrolactone, caprolactone, nitropropane, benzene, styrene, xylene and methyl propasol can be used.
- methylene chloride ethylene dichloride
- the solvent may be used in a weight ratio of about 1: 0.5 to 1: 100 relative to the epoxide, and suitably 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 low, resulting in lower productivity, lower molecular weight, or increased side reaction of the finally formed resin.
- 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 sufficient catalytic activity during solution polymerization. On the contrary, if the ratio is excessively large, an excessive amount of catalyst is used to produce inefficient 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 is halogen or carbon number
- An alkylene oxide of 2 to 20 carbon atoms unsubstituted or substituted with an alkyl group of 1 to 5 may be used.
- epoxides include ethylene oxide, propylene oxide, butene oxide, pentene oxide, nucene oxide, octene oxide, decene oxide, dodecene oxide, tetradecene oxide, nucledecene oxide, octadecene oxide, butadiene monooxide, 1, 2-epoxy-7-octene, epifluorohydrin, epichlorohydrin, epibromohydrin, isopropyl glycidyl ether, butyl glycidyl ether, t-butyl glycidyl ether, 2-ethylnuclear Glycidyl ether, allyl glycidyl ether, cyclopentene oxide, cyclonuxene oxide, cyclooctene oxide, cyclododecene oxide, alpha-pinene oxide, 2,3-epoxynorbornene, limonene
- 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 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.
- the catalyst preparation process is optimized, so that an organic zinc catalyst for producing a polyalkylene carbonate resin having finer and uniform particle size and exhibiting excellent activity can be prepared and provided.
- [Brief Description of Drawings] 1 is a graph showing the results of particle size analysis of zinc precursors used in the catalyst preparation of Examples and Comparative Examples.
- the reaction vessel was then cooled to room temperature, the precipitate was separated by filtration, and the separated precipitate was washed three times or more with acetone.
- the washed precipitate was dried in a vacuum oven at 85 ° C. for 12 hours, finally giving 9.3 g of zinc glutarate (ZnGA) catalyst (about 95% yield).
- Example 3 Phosphoric acid amphoteric surfactant (DISPERBYK-180, manufactured by BYK; 94 mg KOH / g of amine value, 94 mg KOH / g of acid value, 1.08 g / ml of) instead of the phosphate anionic surfactant in preparation of ZnO dispersion 8.8 g of ZnGA catalyst was obtained in the same manner as in Example 1, except that density at 20 ° C.) was used (about 90% yield).
- DISPERBYK-180 manufactured by BYK; 94 mg KOH / g of amine value, 94 mg KOH / g of acid value, 1.08 g / ml of
- Phosphoric anionic surfactant (DISPERBYK-102, manufactured by BYK; poly (oxy-l / 2-ethanediyl), alpha-isotridecyl-omega-hydroxy-, phosphate, etc.) in preparation of ZnO dispersion, the same as in Example 1
- the method gave 9.2 g of ZnGA catalyst (about 94% yield).
- ZnGA catalyst 9.3 g of ZnGA catalyst was obtained in the same manner as in Example 1, except that a phosphoric anionic surfactant (D1544, manufactured by TCI; di (polyethylene glycol 4-nonylphenyl) phosphate)!-Was used in preparing the ZnO dispersion (about 95% yield).
- a phosphoric anionic surfactant D1544, manufactured by TCI; di (polyethylene glycol 4-nonylphenyl) phosphate)!-Was used in preparing the ZnO dispersion (about 95% yield).
- ZnGA catalyst 9.1 g of ZnGA catalyst was prepared in the same manner as in Example 1, except that a nonionic surfactant (Pluronic P-123, manufactured by BASF) represented by the following formula was used instead of the phosphate anionic surfactant in preparing the ZnO dispersion. Obtained (yield about 93%).
- a nonionic surfactant Pluronic P-123, manufactured by BASF
- ZnGA catalyst 9.4 g was obtained in the same manner as in Comparative Example 1, except that a phosphoric anionic surfactant (Crodafos CS2A, manufactured by CRODA) was added at the time when reaction of ZnO and glutaric acid was completed (about 96% of Yield)
- a phosphoric anionic surfactant (Crodafos CS2A, manufactured by CRODA) was added at the time when reaction of ZnO and glutaric acid was completed (about 96% of Yield)
- the particle size distribution of ZnO in ethanol solvent was analyzed using a particle size analyzer (MASTERSIZER 3000), and the results are shown in Table 1 below. 1 is shown.
- the residual amount of the dispersant present on the surface of the organic zinc catalyst was calculated by subtracting the mass of the dispersant detected from the filtrate from the mass of the dispersant added to the catalyst synthesis reaction.
- the residual amount of the dispersant is shown in Table 1 in terms of percent by weight of the catalyst.
- ZnO contained in the ZnO dispersion or reaction solution was prepared using a dispersion stability meter (LumiSizer). The sedimentation rate of the particles was measured. The sedimentation rate was measured at the rate at which particles moved to the bottom of the vessel in solution under a centrifugal force of 5 G, and the results are shown in Table 1 below.
- the average value was calculated by measuring the amount of phosphorus (P) in the sample twice using an ICP-OES (Optima 7300DV) instrument.
- the catalyst of Example 1 was found to contain about 510 mg-P / kg-catalyst, and the catalyst of Comparative Example 1 contained less than 0.5 ( ⁇ 0.5) mg-P / kg-catalyst of phosphorus. That is, the catalyst of Example 1 prepared by using a dispersing agent having a phosphoric acid-based functional group has, and the phosphorus (P) of about 0.05 0/0 residual, translates them as a dispersant by weight approximately coming from 7 to 1.2 parts by weight 0/0 It appeared as a level, it was confirmed that similar to the results of Test Example 2.
- Polyethylene carbonate (PEC) was prepared by the following method using the ZnGA catalysts of Examples and Comparative Examples.
- the pores of the zinc precursor were significantly reduced, and the catalyst prepared using it was found to have a much finer and more uniform size and exhibit high activity.
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Catalysts (AREA)
- Polyesters Or Polycarbonates (AREA)
Abstract
La présente invention concerne : un catalyseur de zinc organique et un procédé de fabrication de ce dernier. Le catalyseur de zinc organique possède une granulométrie plus uniforme et plus fine et présente une activité améliorée dans une procédure de polymérisation de la préparation d'une résine de carbonate de polyalkylène ; et un procédé de préparation d'une résine de carbonate de polyalkylène à l'aide du catalyseur organique de zinc. Le procédé de fabrication d'un catalyseur de zinc organique comprend les étapes consistant : à traiter la surface d'un précurseur de zinc à l'aide d'un dispersant ; et à faire réagir le précurseur de zinc traité en surface avec un acide dicarboxylique pour former un catalyseur à base de zinc dicarboxylate.
Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US15/303,349 US10100147B2 (en) | 2014-06-13 | 2015-06-12 | Organic zinc catalyst, preparation method thereof, and method of preparing poly(alkylene carbonate) resin using the same |
EP15807026.8A EP3127607B1 (fr) | 2014-06-13 | 2015-06-12 | Catalyseur de zinc organique, procédé de fabrication de ce dernier et procédé de préparation d'une résine de carbonate de polyalkylène à l'aide d'un catalyseur de zinc organique |
CN201580027965.2A CN106457212B (zh) | 2014-06-13 | 2015-06-12 | 有机锌催化剂及其制备方法,以及使用该有机锌催化剂制备聚(碳酸亚烃酯)的方法 |
Applications Claiming Priority (6)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
KR10-2014-0072347 | 2014-06-13 | ||
KR20140072346 | 2014-06-13 | ||
KR10-2014-0072346 | 2014-06-13 | ||
KR20140072347 | 2014-06-13 | ||
KR10-2015-0082527 | 2015-06-11 | ||
KR1020150082527A KR101729300B1 (ko) | 2014-06-13 | 2015-06-11 | 유기 아연 촉매, 이의 제조 방법 및 상기 촉매를 이용한 폴리알킬렌 카보네이트 수지의 제조 방법 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2015190874A1 true WO2015190874A1 (fr) | 2015-12-17 |
Family
ID=54833875
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/KR2015/005951 WO2015190874A1 (fr) | 2014-06-13 | 2015-06-12 | Catalyseur de zinc organique, procédé de fabrication de ce dernier et procédé de préparation d'une résine de carbonate de polyalkylène à l'aide d'un catalyseur de zinc organique |
Country Status (1)
Country | Link |
---|---|
WO (1) | WO2015190874A1 (fr) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
KR20170048222A (ko) * | 2015-10-26 | 2017-05-08 | 주식회사 엘지화학 | 유기 아연 촉매, 이의 제조 방법 및 상기 촉매를 이용한 폴리알킬렌 카보네이트 수지의 제조 방법 |
KR20170105435A (ko) * | 2016-03-09 | 2017-09-19 | 주식회사 엘지화학 | 유기 아연 촉매, 이의 제조 방법 및 상기 촉매를 이용한 폴리알킬렌 카보네이트 수지의 제조 방법 |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
KR20030097236A (ko) * | 2002-06-20 | 2003-12-31 | 주식회사 포스코 | 지방족 폴리카보네이트 중합용 촉매의 제조 방법 및 이를사용한 지방족 폴리카보네이트의 중합 방법 |
KR20030097237A (ko) * | 2002-06-20 | 2003-12-31 | 주식회사 포스코 | 지방족 폴리카보네이트 중합용 촉매의 제조 방법 및 이를사용한 지방족 폴리카보네이트의 중합 방법 |
EP1508599A1 (fr) * | 2003-08-22 | 2005-02-23 | Degussa AG | Oxyde de zinc traitée en surface |
US20120123066A1 (en) * | 2009-05-22 | 2012-05-17 | Sumitomo Seika Chemicals Co., Ltd. | Method for producing aliphatic polycarbonate |
KR20140062130A (ko) * | 2011-09-09 | 2014-05-22 | 바스프 에스이 | 아연 디카르복실레이트의 제조 방법 |
-
2015
- 2015-06-12 WO PCT/KR2015/005951 patent/WO2015190874A1/fr active Application Filing
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
KR20030097236A (ko) * | 2002-06-20 | 2003-12-31 | 주식회사 포스코 | 지방족 폴리카보네이트 중합용 촉매의 제조 방법 및 이를사용한 지방족 폴리카보네이트의 중합 방법 |
KR20030097237A (ko) * | 2002-06-20 | 2003-12-31 | 주식회사 포스코 | 지방족 폴리카보네이트 중합용 촉매의 제조 방법 및 이를사용한 지방족 폴리카보네이트의 중합 방법 |
EP1508599A1 (fr) * | 2003-08-22 | 2005-02-23 | Degussa AG | Oxyde de zinc traitée en surface |
US20120123066A1 (en) * | 2009-05-22 | 2012-05-17 | Sumitomo Seika Chemicals Co., Ltd. | Method for producing aliphatic polycarbonate |
KR20140062130A (ko) * | 2011-09-09 | 2014-05-22 | 바스프 에스이 | 아연 디카르복실레이트의 제조 방법 |
Cited By (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
KR20170048222A (ko) * | 2015-10-26 | 2017-05-08 | 주식회사 엘지화학 | 유기 아연 촉매, 이의 제조 방법 및 상기 촉매를 이용한 폴리알킬렌 카보네이트 수지의 제조 방법 |
KR102233983B1 (ko) | 2015-10-26 | 2021-03-30 | 주식회사 엘지화학 | 유기 아연 촉매, 이의 제조 방법 및 상기 촉매를 이용한 폴리알킬렌 카보네이트 수지의 제조 방법 |
KR20170105435A (ko) * | 2016-03-09 | 2017-09-19 | 주식회사 엘지화학 | 유기 아연 촉매, 이의 제조 방법 및 상기 촉매를 이용한 폴리알킬렌 카보네이트 수지의 제조 방법 |
JP2018530651A (ja) * | 2016-03-09 | 2018-10-18 | エルジー・ケム・リミテッド | 有機亜鉛触媒、その製造方法および前記触媒を利用したポリアルキレンカーボネート樹脂の製造方法 |
US10633488B2 (en) | 2016-03-09 | 2020-04-28 | Lg Chem Ltd. | Organic zinc catalyst, preparation method thereof, and method for preparing polyalkylene carbonate resin using the catalyst |
KR102109788B1 (ko) | 2016-03-09 | 2020-05-12 | 주식회사 엘지화학 | 유기 아연 촉매, 이의 제조 방법 및 상기 촉매를 이용한 폴리알킬렌 카보네이트 수지의 제조 방법 |
US10836860B2 (en) | 2016-03-09 | 2020-11-17 | Lg Chem, Ltd. | Organic zinc catalyst, preparation method thereof, and method for preparing polyalkylene carbonate resin using the catalyst |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
KR101729300B1 (ko) | 유기 아연 촉매, 이의 제조 방법 및 상기 촉매를 이용한 폴리알킬렌 카보네이트 수지의 제조 방법 | |
WO2015065066A1 (fr) | Procédé de préparation d'un catalyseur d'organozinc et procédé de préparation de poly(alkylène carbonate) | |
Leng et al. | Amphiphilic porous polyhedral oligomeric silsesquioxanes (POSS) incorporated polyoxometalate-paired polymeric hybrids: Interfacial catalysts for epoxidation reactions | |
WO2015065067A1 (fr) | Catalyseur organozincique et son procédé de préparation | |
WO2015190874A1 (fr) | Catalyseur de zinc organique, procédé de fabrication de ce dernier et procédé de préparation d'une résine de carbonate de polyalkylène à l'aide d'un catalyseur de zinc organique | |
WO2017155307A2 (fr) | Catalyseur organozincique, son procédé de préparation et procédé de préparation d'une résine de carbonate de polyalkylène au moyen de ce catalyseur | |
JP5927184B2 (ja) | ポリアルキレンオキシド粒子及びその製造方法 | |
Moreno et al. | Synthesis and characterisation of (hydroxypropyl)-2-aminomethyl pyridine containing hybrid polymer–silica SBA-15 materials supporting Mo (VI) centres and their use as heterogeneous catalysts for oct-1-ene epoxidation | |
KR102084769B1 (ko) | 유기 아연 촉매의 제조 방법 | |
JP2018536737A (ja) | 有機亜鉛担持触媒およびその製造方法、並びに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 | |
Zhang et al. | POSS-based meso-/macroporous covalent networks: supporting and stabilizing Pd for Suzuki–Miyaura reaction at room temperature | |
US10047032B2 (en) | Preparation method of organic zinc catalyst and poly(alkylene carbonate) resin | |
KR20140038431A (ko) | 폴리알킬렌옥시드 입자 및 그의 제조방법 | |
Yang et al. | Surface activated zinc-glutarate for the copolymerization of CO 2 and epoxides | |
KR102082274B1 (ko) | 유기 아연 담지 촉매, 이의 제조 방법, 및 상기 촉매를 이용한 폴리알킬렌 카보네이트 수지의 제조 방법 | |
KR102323811B1 (ko) | 유기아연 촉매의 제조방법 및 이로부터 제조된 유기아연 촉매를 이용한 폴리알킬렌 카보네이트 수지의 제조방법 | |
KR20180060646A (ko) | 유기 아연 촉매, 이의 제조 방법 및 상기 촉매를 이용한 폴리알킬렌 카보네이트 수지의 제조 방법 | |
KR20170048222A (ko) | 유기 아연 촉매, 이의 제조 방법 및 상기 촉매를 이용한 폴리알킬렌 카보네이트 수지의 제조 방법 | |
KR102084770B1 (ko) | 유기 아연 촉매의 제조 방법 | |
EP3222626B1 (fr) | Composé complexe métallique, nanostructure métallique et composition de catalyseur comprenant celui-ci | |
KR102094449B1 (ko) | 유기 아연 담지 촉매, 이의 제조 방법, 및 상기 촉매를 이용한 폴리알킬렌 카보네이트 수지의 제조 방법 | |
KR101747399B1 (ko) | 유기 아연 촉매의 제조 방법 및 폴리알킬렌 카보네이트 수지의 제조 방법 | |
KR102042803B1 (ko) | 유기아연-카본블랙 복합체 촉매의 제조방법 | |
WO2015072815A1 (fr) | Catalyseur organozincique, son procédé de préparation, et procédé pour la préparation d'une résine polyalkylène carbonate en faisant appel à celui-ci |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 15807026 Country of ref document: EP Kind code of ref document: A1 |
|
REEP | Request for entry into the european phase |
Ref document number: 2015807026 Country of ref document: EP |
|
WWE | Wipo information: entry into national phase |
Ref document number: 2015807026 Country of ref document: EP |
|
WWE | Wipo information: entry into national phase |
Ref document number: 15303349 Country of ref document: US |
|
NENP | Non-entry into the national phase |
Ref country code: DE |