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WO2018034549A1 - Composition catalytique pour la préparation d'un composé de type polycétone, système catalytique mixte à base de palladium, procédé de préparation d'un composé de type polycétone l'utilisant et polymère de polycétone - Google Patents

Composition catalytique pour la préparation d'un composé de type polycétone, système catalytique mixte à base de palladium, procédé de préparation d'un composé de type polycétone l'utilisant et polymère de polycétone Download PDF

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WO2018034549A1
WO2018034549A1 PCT/KR2017/009060 KR2017009060W WO2018034549A1 WO 2018034549 A1 WO2018034549 A1 WO 2018034549A1 KR 2017009060 W KR2017009060 W KR 2017009060W WO 2018034549 A1 WO2018034549 A1 WO 2018034549A1
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Prior art keywords
polyketone
carrier
compound
formula
catalyst
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PCT/KR2017/009060
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English (en)
Korean (ko)
Inventor
장혜영
이분열
임유나
손성욱
박노진
강신영
노형완
정연주
Original Assignee
아주대학교산학협력단
성균관대학교산학협력단
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Priority claimed from KR1020160105779A external-priority patent/KR101881159B1/ko
Priority claimed from KR1020170061232A external-priority patent/KR101828292B1/ko
Application filed by 아주대학교산학협력단, 성균관대학교산학협력단 filed Critical 아주대학교산학협력단
Priority to CN201780035036.5A priority Critical patent/CN109312145B/zh
Publication of WO2018034549A1 publication Critical patent/WO2018034549A1/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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
    • B01J23/44—Palladium
    • 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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
    • 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
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0201—Impregnation
    • B01J37/0207—Pretreatment of the support
    • 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
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C309/00—Sulfonic acids; Halides, esters, or anhydrides thereof
    • C07C309/01—Sulfonic acids
    • C07C309/28—Sulfonic acids having sulfo groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton
    • C07C309/29—Sulfonic acids having sulfo groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton of non-condensed six-membered aromatic rings
    • C07C309/32—Sulfonic acids having sulfo groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton of non-condensed six-membered aromatic rings containing at least two non-condensed six-membered aromatic rings in the carbon skeleton
    • 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
    • C08G67/00—Macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing oxygen or oxygen and carbon, not provided for in groups C08G2/00 - C08G65/00
    • C08G67/02—Copolymers of carbon monoxide and aliphatic unsaturated compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • 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
    • B01J2235/30—Scanning electron microscopy; Transmission electron microscopy

Definitions

  • the present invention relates to a palladium mixed catalyst system capable of preventing fouling while showing high activity in polyketone production, a method for preparing a polyketone compound using the mixed catalyst system, and a polyketone polymer prepared therefrom.
  • Polyketones are polymers also known as carbon monoxide / olefin copolymers. Recently, polyketone is being actively used as a raw material such as high-strength fibers and engineering plastics, and demand is increasing. The synthesis of such polyketones has excellent industrial applicability in terms of converting carbon monoxide into useful materials and providing polymer compounds having excellent physical properties.
  • the catalyst is dissolved in methanol and then introduced into a reactor to polymerize carbon monoxide and ethylene to polyketone under pressure.
  • the polymerization reaction proceeds in a homogeneous state dissolved in methanol, and as a result, polyketone (copolymer of carbon monoxide and ethylene) in the form of an amorphous slurry having no solubility in the solvent is formed.
  • the polyketone prepared in the form of a conventional amorphous slurry has a low apparent density because the particle shape is not controlled, and there is a problem of low productivity per unit volume of the reactor.
  • Such polyketone particles in the form of amorphous slurry are attached to the reactor surface, the stirring device and the conveying piping, causing fouling problems in the mass production process.
  • the conventional polyketone manufacturing method is difficult to increase the activity to the level of industrial usefulness without using additives such as sulfonic acid (sulfonic acid) directly, but the problem that fouling occurs easily when using a strong acid additive There is a difficulty in applying to the mass production process.
  • One object of the present invention is to uniformly control the shape and size of the finally produced polyketone, thereby improving the apparent density, to prevent fouling during the process, and to improve the stability and activity of the polymerization reaction It is to provide a catalyst composition which can be improved.
  • Another object of the present invention is to provide a palladium mixed catalyst system capable of preventing fouling while showing high activity in polyketone production by using an onium salt compound substituted with carboxylic acid as an additive.
  • Still another object of the present invention is to prevent fouling by using the catalyst composition and the palladium mixed catalyst system described above, omission of seed can be omitted, and a method for producing a polyketone compound having excellent stability and activity during a polymerization reaction, and It is to provide a polyketone polymer of apparent high density prepared therefrom.
  • One embodiment of the present invention is an onium salt compound having 5 to 40 carbon atoms containing a carrier or a carboxylic acid surface-modified sulfonic acid group; And palladium-based catalysts; It relates to a catalyst composition for producing a polyketone compound comprising a.
  • Another embodiment of the present invention relates to a palladium mixed catalyst system for producing a polyketone compound including the above-described catalyst composition for producing a polyketone compound and using olefin and carbon monoxide as reactants.
  • Another embodiment of the present invention relates to a polyketone production method comprising the step of dispersing a catalyst composition for preparing a polyketone compound in a solvent and adding olefin and carbon monoxide to the dispersed catalyst composition.
  • Another embodiment of the present invention relates to a polyketone polymer formed by a polyketone production method and having an apparent density of 0.1 to 0.5 g / ml.
  • the present invention can provide a catalyst composition capable of preventing fouling while showing high activity in polyketone production, and a palladium mixed catalyst system including the same, and can prevent fouling using the mixed catalyst system, It is possible to control the shape and size of the polyketone, omission of seed input, it is possible to provide a method for producing a polyketone compound having excellent stability and activity during the polymerization reaction and the apparent high density polyketone polymer prepared therefrom.
  • FIG. 2 is a SEM photograph of a carrier surface-modified with the sulfonic acid group of Preparation Example 1, which was collected after the polymerization reaction of Example 1.
  • Example 5 is a photograph of the polyketone prepared in Example 1.
  • Example 6 is a photograph of the polyketone prepared in Example 3.
  • Example 7 is a photograph of the polyketone prepared in Example 4.
  • FIG. 10 shows a carrier 100 surface-modified with a sulfonic acid group of the first embodiment of the present invention.
  • FIG. 11 shows a carrier 200 surface-modified with a sulfonic acid group of the second embodiment of the present invention.
  • One embodiment of the present invention is an onium salt compound having 5 to 40 carbon atoms containing a carrier or a carboxylic acid surface-modified sulfonic acid group; And palladium-based catalysts; It relates to a catalyst composition for producing a polyketone compound comprising a.
  • the present invention can provide a catalyst composition and a palladium mixed catalyst system including the same, which exhibits high activity in polyketone production and can prevent fouling, and prevents fouling by using the mixed catalyst system. And it is possible to omit the seed input, it is possible to provide a method for producing a polyketone compound excellent in stability and activity during the polymerization reaction and the apparent high density polyketone polymer prepared therefrom.
  • the catalyst composition for producing a polyketone compound of the present invention and a palladium mixed catalyst system using the same can prevent fouling generated in the conventional catalyst system for producing polyketone and at the same time increase the reaction activity to an excellent level, and add a separate seed.
  • a polyketone polymer having excellent apparent density can be prepared.
  • the carrier surface-modified with the sulfonic acid group is included as a hetero material for a palladium-based catalyst.
  • hetero material refers to a material included as a component included in a catalyst composition as a mixture with a palladium-based catalyst.
  • the surface-modified carrier of the sulfonic acid group of the present invention and a palladium-based catalyst;
  • the catalyst composition in a mixed form has, for example, a state different from a catalyst in which a palladium-based catalyst is supported on a surface modified with a sulfonic acid group, and is applied to a polyketone polymerization process.
  • the shape and size of the final polyketone can be uniformly controlled, thereby improving the apparent density of the polyketone, preventing fouling during the process, and improving the stability and activity of the polymerization reaction. have.
  • the equivalent ratio of the surface-modified carrier and the palladium-based catalyst in the catalyst composition may be 1: 0.1 to 1:10, specifically 1: 0.1 to 1: 2. More specifically, the equivalent ratio may be 1: 0.1 to 1: 1.2. It is possible to obtain higher catalyst activity and apparent density of a high polyketone polymer without fouling during polyketone polymerization using the catalyst composition in the above range.
  • the carrier surface-modified with the sulfonic acid group in the catalyst composition and the palladium-based catalyst may be included in a dispersed form in a solvent.
  • the solvent may be an alcohol solvent, more specifically an alcohol compound having 1 to 20 carbon atoms, for example methanol.
  • the surface-modified carrier with the sulfonic acid group can uniformly control the shape and size of the polyketone to be polymerized, prevent fouling during the polymerization reaction, and serve to further improve the apparent density of the polyketone particles formed.
  • the sulfonic acid group of the carrier surface-modified with the sulfonic acid group interacts with the palladium-based catalyst during the polymerization reaction to more effectively prevent fouling, and to form a polyketone in powder form having a high apparent density, There is no adverse effect on the activity, and the effect of maintaining high catalytic activity is excellent.
  • the carrier surface-modified by the sulfonic acid group may include a structure in which a functional group represented by any one of the following Formulas 1-1 to 1-3 is bonded to the surface of the carrier.
  • R 21 to R 26 are each independently hydrogen or alkyl of C1 to C20; * Means the part bonded to the surface of the carrier.
  • R 31 to R 34 are each independently hydrogen or alkyl of C1 to C20; * Denotes the part that is bonded to the carrier surface. it means.
  • * in Chemical Formulas 1-1 to 1-3 may be a bonding site connected to the surface of the carrier to form a C-C bond or a Si-C bond.
  • the carrier and the functional group represented by any one of Formulas 1-1 to 1-3 may be linked to a C-C bond or Si-C bond having excellent binding strength, and thus may have high stability and improved fixing force to the carrier.
  • the carrier is a porous particle containing pores, it is possible to control the surface area, pore radius, pore, volume, etc. of the polyketone during the polymerization reaction.
  • the carrier may be silica, zeolite, graphite, carbon black, graphene, carbon nanotube, activated carbon, polystyrene, microporous organic network, metal organic structure (MOF), zeolite-like structure (ZIF), organic skeleton It may comprise one or more of a biopolymer including a structure (COF) and cellulose.
  • MOF metal organic structure
  • ZIF zeolite-like structure
  • organic skeleton It may comprise one or more of a biopolymer including a structure (COF) and cellulose.
  • COF structure
  • the effect of preventing fouling can be further improved while uniformly controlling the shape and size of the polyketone during the polymerization reaction, and excellent handling properties of the catalyst composition and the polyketone prepared therefrom, It may have more advantageous properties.
  • the carrier may include one or more of silica, zeolite-like structures, polystyrene, and microporous organic network polymers.
  • the effect of preventing fouling can be further improved while controlling the shape and size of the polyketone, and commercial usability can be further increased.
  • microporous organic network polymer microporous organic network
  • the kind thereof is not particularly limited.
  • the leaving group may be used in the Sonogashira coupling reaction, Suzuki coupling reaction or other known cross coupling reaction, but is not limited thereto.
  • the leaving group (X) is halogen, tosylate, triflate, mesylate, mesylate, boronic acid, boronic ester, -N 2 + X - may be a living group available for the coupling reaction, or the like.
  • the compound including the leaving group may be a dinitrogen compound (RN 2+ ), a dialkyl ether compound (R-OR 2 + ), a triflate compound (R-OSO 2 R F ), a tosylate compound (R -OTf), halides (R-Cl, R-Br, RI, RF), mesylate compounds (R-OMs), nitrate compounds (R-ONO 2 ), phosphate compounds (R-OPO (OH) 2 ) , A thioether compound (R-SR 2 + ), a carboxylate compound (R-OCOR), and also a compound containing two or more leaving groups, RN 2 X, R-OSO 2 R, R-OSO 2 F, SO 2 -R, SOR, R-SR , IPhX, IROTf, I (OH) OTs, RCOCl, R-SO 2 -Cl, RN 2+ X -, R-OSO 2 CF 3, R-OSOSO
  • Rf is perfluoroalkyl
  • Tf is triflate
  • Ms is mesylate
  • X is halogen
  • R is substituted or unsubstituted hydrocarbon having 1 to 20 carbon atoms
  • Ar is aromatic hydrocarbon having 6 to 20 carbon atoms.
  • the compound including a leaving group may be a compound represented by the following formula (A).
  • R 10 is an alkylene group having 1 to 20 carbon atoms or an arylene group having 1 to 20 carbon atoms, and each X is independently an ethyne group, a halogen group, a boronic acid group, a boronic acid ester group, and a triflate group.
  • Z is a carbon atom, a nitrogen atom or a hydrocarbon having 3 to 10 carbon atoms, and p is 2 to 6 carbon atoms.
  • the compounds may be in the form of a skeleton structure of each of the formulas A1 to A4.
  • each X is independently an ethyne group, a halogen group, a boronic acid group, a boronic acid ester group, a triflate group
  • Z is a carbon atom, a nitrogen atom, or a hydrocarbon having 3 to 10 carbon atoms.
  • the hydrocarbon having 3 to 10 carbon atoms may be a cyclic hydrocarbon or a hydrocarbon having a three-dimensional structure.
  • Z may be an adamantane structure to which 4 is linked.
  • the carrier may have an average particle diameter of 0.01 ⁇ m to 5 ⁇ m. More specifically, it may be 0.05 ⁇ m to 2 ⁇ m, 0.45 ⁇ m to 1.8 ⁇ m. Within this range, the shape and size of the polyketone can be more uniformly controlled and the apparent density can be improved.
  • the average particle diameter of the carrier can be adjusted according to, for example, the shape and size of the desired polyketone particles.
  • the carrier may be a surface area of 5 m 2 / g to 2000m 2 / g. More specifically, it may be 20 m 2 / g to 1800m 2 / g, 30 m 2 / g to 1700m 2 / g or 30 m 2 / g to 900m 2 / g. Within this range, the shape and size of the polyketone can be more uniformly controlled and the apparent density can be improved.
  • the surface area of the carrier can be adjusted according to, for example, the shape and size of the desired polyketone particles.
  • the carrier may have an average pore radius of 0.1 nm to 25 nm. More specifically, it may be 0.5 nm to 10 nm, or 1 nm to 6 nm. Within this range, the shape and size of the polyketone can be more uniformly controlled and the apparent density can be improved.
  • the average pore radius of the carrier can be adjusted, for example, according to the shape and size of the desired polyketone particles.
  • the carrier may have a pore volume of 0.01 mL / g to 1.0 mL / g. More specifically, it may be 0.02 mL / g to 0.7 mL / g, or 0.04 mL / g to 0.5 mL / g. Within this range, the shape and size of the polyketone can be more uniformly controlled and the apparent density can be improved.
  • the average pore volume of the carrier can be adjusted, for example, according to the shape and size of the desired polyketone particles.
  • the carrier may comprise an aromatic ring in the structure.
  • the stability of the carrier is excellent, and when the surface is modified with sulfonic acid, it is possible to realize excellent surface modification efficiency.
  • the carrier surface-modified with a sulfonic acid group may be a hollow structure including a microporous organic network polymer having a repeating unit represented by the following Chemical Formula 1-4.
  • A is a linking portion of an atom.
  • the carrier 100 surface-modified with the sulfonic acid group of the first embodiment is exemplarily illustrated in FIG. 10.
  • the carrier 100 surface-modified with the sulfonic acid group of the first embodiment is a hollow structure 101 formed of a hollow structure in which the interior 102 is empty, and the hollow structure 101 is represented by the above formula. It may be formed of a microporous organic network polymer having a repeating unit represented by 1-4.
  • the hollow structure 101 is connected to A of one repeating unit represented by Formula 1-4 with A of another repeating unit represented by Formula 1-4 in a single bond to form an organic network. It contains microporous inside.
  • the hollow structure 101 of FIG. 10 may use a zeolite-like structure as a template for allowing the microporous organic network polymer having a repeating unit represented by Chemical Formula 1-4 to have a hollow structure.
  • the carrier 100 surface-modified with sulfonic acid group may include a microporous organic network polymer and a zeolite-like structure as a carrier.
  • the zeolite-like structure used as the template may be used in a state of being removed through an etching process.
  • the structure of the hollow structure 101 is represented by a spherical shape for convenience of expression, but the shape thereof is not limited as long as it includes the hollow structure.
  • the hollow structure 101 may have an internal structure. It may include the shape of an empty polyhedron.
  • the carrier surface-modified by the sulfonic acid group includes a microporous organic network polymer layer having a silica carrier and a repeating unit represented by the following Chemical Formula 1-5 formed on the surface of the silica carrier.
  • each A ′ independently represents a linking site or a linking site between repeating units of an atom to be bonded to a carrier, and at least one of A ′ is a linking site of atoms to be bonded to a carrier, and at least At least one is the link between repeat units.
  • the carrier 200 surface-modified with the sulfonic acid group of the second embodiment includes a silica carrier 202 and a microporous organic network polymer layer 201 formed on the surface of the silica carrier.
  • the microporous organic network polymer layer 201 is formed of a microporous organic network polymer having a repeating unit represented by Chemical Formula 1-5, and a carrier 200 surface-modified with the sulfonic acid group of the second embodiment. ) May be a form in which the inside of the microporous organic network polymer layer 201 is filled with the silica carrier 202.
  • the microporous organic network polymer layer 201 includes a polymer having a repeating unit represented by Formula 1-5, wherein at least one A 'of one repeating unit is single with A' of an adjacent repeating unit. Are bonded to form an organic network, and at least one A ′ forms an Si—C bond with the silica carrier 202.
  • the microporous organic network polymer layer 201 of FIG. 11 uses silica as a template, and the microporous organic network polymer layer 201 having a repeating unit represented by Chemical Formula 1-5 is a silica carrier. It may be formed on the surface of the (202).
  • the carrier 200 surface-modified with sulfonic acid groups may include a microporous organic network polymer and silica as a carrier.
  • the structure of the silica carrier 202 is expressed as a spherical structure for convenience of expression, but the shape thereof is not limited thereto and may include, for example, a polyhedron shape.
  • the carrier surface-modified by the sulfonic acid group may include a polystyrene compound having a repeating unit represented by the following Chemical Formula 1-6.
  • R 6 is a sulfonic acid group, a para-toluenesulfonic acid group, or a benzene sulfonic acid group, and n is 10 to 20,000.
  • the catalyst composition can further improve the apparent density and uniformity while further miniaturizing the particles of the finally produced polyketone.
  • polystyrene compound may be a copolymer including the repeating unit represented by Chemical Formula 1-6.
  • the polystyrene compound may be a copolymer of the repeating unit of Formula 1-6 and divinylbenzene.
  • the carrier surface-modified by the sulfonic acid group may have a structure in which a functional group represented by any one of the above-described formulas 1-2 and 1-3 is Si-C bonded.
  • the stability of the catalyst composition may be further improved and the effect of preventing fouling may be better.
  • the carrier surface-modified by the sulfonic acid group may be prepared by adding sulfuric acid or chlorosulfuric acid to the carrier, for example, the surface-modified carrier.
  • Producing a carrier surface-modified with a sulfonic acid group may include preparing a carrier and sulfonating the surface of the carrier to surface-modify the sulfonic acid group.
  • the carrier may be silica, zeolite, graphite, carbon black, graphene, carbon nanotube, activated carbon, polystyrene, microporous organic network, metal organic structure (MOF), zeolite-like structure (ZIF) as described above. ), Organic framework (COF) and may include one or more of the biopolymer (biopolymer) including cellulose.
  • the carrier may be used or manufactured by using a commercially available product. In this case, the effect of preventing fouling can be further improved while uniformly controlling the shape and size of the polyketone during the polymerization reaction, and the handleability of the catalyst composition and the polyketone prepared therefrom can be further improved.
  • the carrier may include one or more of silica, zeolite-like structures, polystyrene, and microporous organic network polymers.
  • the carrier may include one or more of silica, zeolite-like structures, polystyrene, and microporous organic network polymers.
  • preparing the carrier may include reacting the prepared carrier with a compound represented by the following Formula 5 or 6 after preparing the carrier.
  • Ar is benzyl or phenyl
  • Mg is magnesium
  • X is halogen
  • the halogen in Formula 5 to Formula 6 may be, for example, Cl, Br, F or I, more specifically I, Cl or Br.
  • the reaction rate can be further improved.
  • the step of preparing a carrier is reacting a zeolite-like structure with tetra- (4-ethynylphenyl) -methane as a template and the compound of Formula 1-6 under Pd (PPh 3 ) 2 Cl 2 and CuI catalyst
  • the carrier can be prepared by the method.
  • the prepared carrier is subjected to sulfonation of a surface to provide a carrier modified with sulfonic acid, which is a hollow structure including a microporous organic network polymer having a repeating unit represented by Chemical Formula 1-4. can do.
  • the preparing of the carrier may be performed by reacting silica with tetra- (4-ethynylphenyl) -methane as a template and the compound of Chemical Formula 1-6 under Pd (PPh 3 ) 2 Cl 2 and CuI catalyst.
  • Carriers can be prepared.
  • the carrier prepared is a sulfonic acid including a microporous organic network polymer layer having a silica carrier and a repeating unit represented by Formula 1-5 described above formed on the surface of the silica carrier through sulfonation of the surface.
  • a surface modified carrier can be provided.
  • the preparing of the carrier may include dispersing the dehydrated carrier in a solvent and then adding the compound represented by Chemical Formula 5 and reacting the same to bind an aromatic functional group to the surface of the carrier.
  • the surface modification efficiency and carrier stability in the sulfonation step can be further improved.
  • the dehydration treatment of the carrier may be performed by supplying nitrogen gas or argon gas at 600 ° C. to 900 ° C. using a heating furnace.
  • the solvent in which the dehydrated carrier is dispersed may be an ether solvent, more specifically an alkyl ether solvent, and may be, for example, a diethyl ether solvent.
  • the dispersibility can be further improved.
  • the carrier is silica and Ar is benzyl in Chemical Formula 5
  • the carrier prepared is sulfonated on a surface thereof to which the silica carrier and the functional group represented by Chemical Formula 1-2 are bonded to Si-C.
  • a carrier modified with a sulfonic acid group having a structure can be provided.
  • the carrier is silica and Ar is phenyl in Formula 5
  • the prepared carrier is sulfonated on the surface to which the silica carrier and the functional group represented by Formula 1-3 are bonded to Si-C.
  • a carrier modified with a sulfonic acid group having a structure can be provided.
  • Sulfonation of the surface of the carrier to surface-modify the sulfonic acid group may include sulfonation (sulfonation) by adding sulfuric acid or chlorosulfuric acid to the prepared carrier.
  • the surface modification may be performed by treating sulfuric acid (95%) or chlorosulfuric acid on the prepared carrier to induce a sulfonation reaction on the benzene ring in the structure of the carrier.
  • sulfuric acid 95%) or chlorosulfuric acid
  • each carrier described above is modified with a functional group having a structure including a sulfonic acid group in the terminal benzene ring.
  • the conversion rate (surface modification rate) of the carrier by sulfonation is very excellent.
  • the formed C-C bonds or Si-C bonds are not broken, so that most of the functional groups are immobilized on the surface of the carrier.
  • sulfonation of the carrier may be carried out by the reaction of Scheme 1 below.
  • aromatic sulfonation of the carrier can be carried out by the reaction of Scheme 2 or Scheme 3 below.
  • the carrier surface-modified with a sulfonic acid group may include a sulfonic acid group as 0.1 mmol-H + / g to 3 mmol-H + / g.
  • the efficiency of the polyketone synthesis process by the sulfonic acid group can be further improved.
  • the onium salt compound including the carboxylic acid group serves to allow the palladium mixed catalyst system for producing polyketone of the present invention to implement a reaction mode different from the rapid increase in the initial reaction rate of polymerization occurring in the conventional catalyst system for producing polyketone. do.
  • the polyketone production method of the present invention using the catalyst composition for producing polyketone and the palladium mixed catalyst system omits the process of controlling the pressure, temperature, solvent, reaction time, reaction rate, and the like in the middle of the polymerization reaction. At the same time it can prevent fouling and achieve good activity. This property offers advantageous advantages for applications in mass production processes.
  • the salt of the onium salt compound containing the carboxylic acid group may interact with the palladium catalyst used for the polyketone polymerization to form a heterogeneous seed which is very small in size, and may be formed around the catalyst.
  • the shape of the polyketone polymer being synthesized can be controlled.
  • the onium salt compound including the carboxylic acid group is a carboxylic acid group substituted with the onium salt compound
  • the onium salt compound is at least one of a pnictogen element, a chalcogen element, and a halogen element It may include, for example, may be ammonium, oxonium, phosphonium, sulfonium compound and the like.
  • the onium salt compound including the carboxylic acid group may be represented by the following Formula 2-1.
  • Z is a hydrocarbon group having 1 to 20 carbon atoms containing nitrogen, phosphorus or sulfur;
  • [X] - is an anion (anion) containing a halogen, oxygen, boron, phosphorous, sulfur, or a combination thereof.
  • the compound of Formula 2 When the compound of Formula 2 is used as an onium salt compound containing a carboxylic acid group, the effect of preventing fouling while enhancing the reaction activity and increasing the apparent density of the polyketone compound prepared without adding a separate seed is further increased. Can be improved.
  • the hydrocarbon group of 1 to 20 carbon atoms is not particularly limited, but for example, an alkyl group of 1 to 20 carbon atoms, a cycloalkyl group of 1 to 20 carbon atoms, a heteroalkyl group of 1 to 20 carbon atoms, an aryl group of 6 to 20 carbon atoms, and 3 carbon atoms.
  • an alkyl group of 1 to 20 carbon atoms a cycloalkyl group of 1 to 20 carbon atoms
  • a heteroalkyl group of 1 to 20 carbon atoms an aryl group of 6 to 20 carbon atoms
  • 3 carbon atoms 3 carbon atoms.
  • Z may be an aromatic hetero ring group containing nitrogen, phosphorus, or sulfur, or a branched hetero alkyl group containing nitrogen, phosphorus, or sulfur.
  • hydrocarbon group having 1 to 20 carbon atoms may be independently substituted or unsubstituted, wherein the substituent may be, for example, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 20 carbon atoms, or a halogen group. have.
  • [X] - it is an anion (anion) containing bonded to the onium ion substituted with a carboxylic acid available halogen, oxygen, boron, phosphorous, sulfur, or a combination thereof.
  • the anion including the halogen, oxygen, boron, phosphorus, sulfur or a combination thereof may be independently substituted or unsubstituted, wherein the substituent is, for example, an alkyl group having 1 to 10 carbon atoms , An aryl group having 6 to 20 carbon atoms, a halogen group, or the like.
  • the compound of Formula 2 is, for example, glycine betaine hydrochloride (glycine betaine hydrochloride), trigonelline hydrochloride (trigonelline hydrochloride), 3- (carboxymethyl) -1-methyl-1H-imidazol-3-ium Bromide (3- (carboxymethyl) -1-mesityl-1H-imidazol-3-ium bromide), 3- (carboxymethyl) -1- (2,6-diisopropylphenyl) -1H-imidazol-3-ium Bromide (3- (carboxymethyl) -1- (2,6-diisopropylphenyl) -1H-imidazol-3-ium bromide), 3- (carboxymethyl) -1-methyl-1H-imidazol-3-ium bromide (3 -(carboxymethyl) -1-methyl-1H-imidazol-3-ium bromide), 3- (carboxymethyl) -1-methyl-1H-benzo [d] imida
  • the onium salt compound including the carboxylic acid group may be included in a molar concentration of 0.1 ⁇ 10 -3 M to 1.0 ⁇ 10 -3 M. In this case, the polymerization stability and the activation degree in the polyketone production method is further improved, it is possible to produce a polyketone compound with excellent yield.
  • the palladium-based catalyst used in the present invention is not particularly limited as long as it is a general palladium-based catalyst that can be used for polyketone polymerization.
  • the palladium-based catalyst is used that is not in a form supported on a carrier or the like.
  • the above-mentioned sulfonic acid group is not used in the form of being previously supported on the surface-modified carrier, and is added during polymerization in separate states. In this case, fouling can be more effectively reduced while reducing the loss of activity of the palladium-based catalyst.
  • a Pd catalyst used for polyketone polymerization may be used.
  • the palladium-based catalyst may be represented by any one of the following Chemical Formulas 3 to 5.
  • R 1 to R 4 are each independently hydrogen, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, or an aromatic hydrocarbon group having 6 to 20 carbon atoms
  • Y 1 and Y 2 are Each independently is a halogen anion or an oxyacetate anion
  • Y 3 to Y 5 are each independently hydrogen, an alkyl group having 1 to 10 carbon atoms, an organosilicon group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, or 6 to 6 carbon atoms; It is a 20 aromatic hydrocarbon group
  • Y ⁇ 6> is a C1-C10 alkylene group, a C3-C10 cycloalkylene group, or a C6-C20 divalent aromatic hydrocarbon group.
  • each Y 6 may be substituted or unsubstituted, may or may not include one or more heteroatoms, and may be a monocyclic or polycyclic structure in the case of a ring structure.
  • the palladium-based catalyst may be used dispersed in a polymerization solvent (for example, an alcohol solvent).
  • a polymerization solvent for example, an alcohol solvent
  • the olefin gas and carbon monoxide gas are added to the mixture while stirring at room temperature and saturated, and the reactor is heated to copolymerize olefin and carbon monoxide.
  • the palladium-based catalyst represented by any one of Formulas 3 to 5 may improve the copolymerization activity of the olefin and carbon monoxide, it is possible to prepare a polyketone compound.
  • the palladium-based catalyst is not particularly limited, but for example, 1,3-Bis (di-o-methoxyphenylphosphino) propane] Pd (OAc) 2 catalyst, Pd (di-o-methoxyphenylphosphino) (diphenylphosphino) propane) (OAc) It may be at least one selected from the group consisting of 2 catalyst and Pd (1,3-bis (diphenylphosphino) propane) (OAc) 2 catalyst.
  • the copolymerization reactivity and activity of the olefin and carbon monoxide are more excellent, but also the effect of further preventing fouling phenomenon by interacting with the onium salt compound including the carboxylic acid group described above.
  • the activity is excellent, but also the fouling phenomenon can be further prevented and a uniformly polymerized polyketone can be formed.
  • the effect of controlling the morphology of the polyketone polymer synthesized around the catalyst by self aggregation of salt and palladium catalyst can be further improved.
  • the solvent of the catalyst system is an alcohol solvent, more specifically an alcohol compound having 1 to 20 carbon atoms, for example, methanol may be used.
  • the polyketone production method may have higher reactivity and activation, and a lower boiling point, which may be advantageous in the aftertreatment process.
  • Another embodiment of the present invention relates to a palladium mixed catalyst system for producing a polyketone compound including the above-described catalyst composition for producing a polyketone compound and using olefin and carbon monoxide as reactants.
  • specific contents of the catalyst composition are as described above.
  • Another embodiment of the present invention relates to a polyketone production method comprising the step of dispersing a catalyst composition for preparing a polyketone compound in a solvent and adding olefin and carbon monoxide to the dispersed catalyst composition.
  • a polyketone production method includes a catalyst in which a surface-modified carrier is mixed with a palladium-based catalyst as a hetiro material, for example, a catalyst in which a palladium-based catalyst is supported on a carrier surface-modified with a sulfonic acid group.
  • a catalyst in which a palladium-based catalyst is supported on a carrier surface-modified with a sulfonic acid group Has a distinct state, through which the shape and size of the final polyketone is uniformly adjusted when applied to the polyketone polymerization process, thereby improving the apparent density of the polyketone and preventing fouling during the process. The effect of improving the stability and activity of the polymerization reaction can be realized.
  • a polyketone production method includes a salt of an onium salt compound containing a carboxylic acid group and a palladium catalyst in interaction to generate a heterogeneous seed having a fine size in a reaction solution, wherein the aggregate formed has a size of about 100 It is possible to control the particle size and shape of polyketone polymers formed very small in and around nm and to increase the apparent density very much.
  • the polyketone production method of the present invention implements a high apparent density that is difficult to obtain by the conventional method of injecting a heterogeneous seed, and improves activity and prevents fouling by using only an additive while omitting seed addition. Can be.
  • Specific poly ketone is an onium salt compound having 5 to 40 carbon atoms containing a carrier or a carboxylic acid surface-modified sulfonic acid group used in the production method; And palladium-based catalyst; the details are as described above.
  • the solvent may be an alcohol compound having 1 to 20 carbon atoms.
  • the palladium-based catalyst may be included at a molar concentration of 0.1 ⁇ 10 ⁇ 3 M to 1.0 ⁇ 10 ⁇ 3 M. In this case, the polymerization stability and the activation degree in the polyketone production method is further improved, it is possible to produce a polyketone compound with excellent yield.
  • the onium salt compound including a carrier or a carboxylic acid group surface-modified by the sulfonic acid group in the polymerization reaction may be included in a molar concentration of 0.1 ⁇ 10 -3 M to 1.0 ⁇ 10 -3 M. In this case, the polymerization stability and the activation degree in the polyketone production method is further improved, it is possible to produce a polyketone compound with excellent yield.
  • the method for producing a polyketone compound may further include preparing a carrier modified with a sulfonic acid group by adding sulfuric acid or chlorosulfuric acid to the carrier. It may include. At this time, specific details of the method for producing a surface-modified carrier with the sulfonic acid group are as described above.
  • olefin for example, ethylene, propylene, 1-butene, 2-butene, 1-pentene, 1-hexene, 1-octene, 1-decene, 1-dodecene, cyclopentene, norbornene, dicyclopenta Dienes, cyclooctene, cyclododecene, styrene, alphaketylstyrene, alkyl esters of (meth) acrylic acid and (meth) acrylic acid, and the like can be used.
  • the said olefin can be used individually or in combination of 2 or more types.
  • ethylene, propylene, hexene and decene may be used alone, or a mixture thereof may be used.
  • the interaction with the catalyst is excellent, and the activity and yield of the polyketone polymer can be further increased.
  • the mole ratio of the olefin and the carbon monoxide may be 95: 5 to 5:95, more specifically 5: 1 to 1: 5 may be used in a molar ratio.
  • the polyketone production method can further improve the reaction activity.
  • the olefin and the carbon monoxide may be included in a ratio of 10 to 20 bar: 30 to 40 bar.
  • the polyketone production method can further improve the reaction activity.
  • the equivalent ratio of the onium salt compound including the carrier or the carboxylic acid group, the surface-modified sulfonic acid group; and the palladium-based catalyst may be 1: 0.1 to 1:10.
  • the polyketone production method can further improve reaction activity and yield.
  • the equivalent ratio of the carrier and the palladium-based catalyst surface-modified with the palladium-based catalyst and sulfonic acid group may be 1: 0.1 to 1: 2. More specifically, the equivalent ratio may be 1: 0.1 to 1: 1.2. It is possible to obtain higher catalyst activity and apparent density of a high polyketone polymer without fouling during polyketone polymerization using the catalyst composition in the above range.
  • the equivalent ratio of the onium salt compound including the palladium-based catalyst and the carboxylic acid group may be 1: 0.1 to 1:10.
  • the polyketone production method can further improve reaction activity and yield.
  • the reaction temperature may be maintained in the range of 50 ° C to 150 ° C, more specifically 70 ° C to 130 ° C.
  • the polyketone production method can further improve the reaction activity.
  • the carbon monoxide and some olefins are gases at this temperature so that the polymerization reaction can be carried out in a pressure reactor.
  • the polyketone manufacturing method can further improve reactivity and activation.
  • the internal pressure of the reactor may be 200 atm or less, and more specifically 100 atm or less.
  • the polyketone manufacturing method can further improve reactivity and activation.
  • the palladium mixed catalyst system for producing polyketone described above may exist in a dispersed state in a solvent to catalyze a polymerization reaction.
  • the solvent is an alcohol solvent, more specifically an alcohol compound having 1 to 20 carbon atoms, for example, methanol can be used.
  • the polyketone production method may have higher reactivity and activation, and a lower boiling point, which may be advantageous in the aftertreatment process.
  • the carrier whose surface has been modified with the sulfonic acid group described above may be present in the form of a slurry without being dissolved in an organic solvent.
  • the polyketone production method using the onium salt compound containing the carboxylic acid group described above may be a seed non-injection method.
  • Yet another embodiment of the present invention relates to a polyketone polymer formed by the aforementioned polyketone production method.
  • the polyketone polymer formed by the above-described polyketone manufacturing method is that the carrier surface-modified by the sulfonic acid group is prepared by working with a palladium-based catalyst as a hetero material, the apparent density may be improved.
  • the polyketone polymer formed by the aforementioned polyketone production method is shaped by a fine size heterogeneous seed formed by agglomeration of a salt of an onium salt compound containing the carboxylic acid group and a palladium catalyst together in an interaction. Can be controlled.
  • the polyketone polymer formed with a very small aggregate size of about 100 nm may have a very high apparent density of 0.1 g / ml to 0.5 g / ml, for example, 0.27 g / ml to 0.47 g / ml. have.
  • Benzyl magnesium chloride (benzyl magnesium chloride) was added to the silica carrier prepared above, and reacted with stirring at room temperature in a nitrogen atmosphere.
  • Zinc nitrate hexahydrate (1 eq, 0.1 mol, 297.49 g / mol, 29.75 g) was dissolved in 500 mL methanol to prepare a zinc nitrate solution
  • CTAB Hexadecyltrimethyl ammonium bromide 99 +%, 0.25 eq, 0.025 mol, 364.45 g / mol, 9.1 g
  • 2-methyl imidazole (4 eq, 0.4 mol, 82.10 g / mol, 32.84 g) was dissolved in 500 mL methanol to prepare a solution (2-methylimidazole Solution).
  • Tetra- (4-ethynylphenyl) -methane (1 eq, 0.24 mmol, 416.51 g / mol, 0.1 g) and 1,4-Diiodobenzene (2 eq, 0.48 mmol, 329.90 g / mol, 0.1584 g) were added to the dispersion. And dispersed again in the Sonicator for 5 minutes. Thereafter, the reaction was performed at 100 ° C. for 24 h, cooled to room temperature, and a carrier (ZIF-8 @ MON) in the form of a hollow structure including the previously prepared carrier ZIF-8 synthesized as a centrifuge as a template was separated. The synthesized carrier was washed twice in the order of acetone, dichloromethane, methanol, acetone, and dried with a vacuum pump.
  • the carrier (ZIF-8 @ MON, 0.16 g) prepared above and 15 mL of methanol were dispersed in a Falcon tube, 20 mL of acetic acid was added thereto, followed by etching for 1 h. Etching further promoted the formation of a microporous organic network in the carrier. Then, the carrier (HMON) etched with Centrifuge was separated, washed 10 times with methanol (MeOH), twice with acetone (Acetone), dried with a vacuum pump and used for sulfonation.
  • the surface-modified carriers prepared with sulfonic acid groups were identified by SEM (a, b) and TEM (c) of FIG. 3, and the results are shown in FIG. 3.
  • silica carrier was prepared as a template by heating to dryness.
  • Tetra- (4-ethynylphenyl) -methane (1 eq, 0.24 mmol, 416.51 g / mol, 0.1 g) and 1,4-Diiodobenzene (2 eq, 0.48 mmol, 329.90 g / mol, 0.1584 g) were added to the dispersion. And dispersed again in the Sonicator for 5 minutes. Thereafter, after reacting at 100 ° C. for 24 h, the mixture was cooled to room temperature, and the carrier (SiO 2 @MON) containing the previously prepared silica carrier synthesized with Centrifuge as a template and containing a microporous organic network layer was separated. It was. The synthesized carrier was washed twice in the order of acetone, dichloromethane, methanol, acetone, and dried with a vacuum pump.
  • Styrene Purification Styrene stabilizer (4-tert-butylcatechol) removal
  • dichloromethane Add 30 mL of dichloromethane to 200 mL styrene. 50mL of 1M Sodium hydroxide solution is added to the mixed solution and extracted three times. After dehydration with magnesium sulfate, dichloromethane is removed using a vacuum pump. Refrigerated under argon after blocking light.
  • a carrier was prepared in the same manner as in Preparation Example 2, except that the sulfonation step was omitted.
  • Table 1 shows the physical properties of the carriers prepared in Preparation Examples 1 to 5.
  • FIG. 5 A photograph of the prepared polyketone is shown in FIG. 5, and it was visually confirmed that fouling did not occur.
  • the carrier surface-modified with the sulfonic acid group of Preparation Example 2 before the reaction had a diameter of 521 nm and a thickness of 20 nm, and changed to 625 nm in diameter and 120 nm in thickness after the reaction.
  • FIG. 7 A photograph of the prepared polyketone is shown in FIG. 7, and it was visually confirmed that fouling did not occur.
  • the palladium catalyst was used as above except that 0.8 mg of Pd (1,3-bis (diphenylphosphino) propane) (OAc) 2 was used instead of Pd (1,3-bis (di (2-methoxyphenyl) phosphinopropane) (OAc) 2 .
  • OAc Pd (1,3-bis (diphenylphosphino) propane
  • OAc Pd (1,3-bis (di (2-methoxyphenyl) phosphinopropane)
  • the preparation of the catalyst composition was carried out in the same manner as in Example 2, except that the carrier whose surface was modified was not added. (Catalytic activity 0.478 kg / g-Pd)
  • the preparation of the catalyst composition was carried out in the same manner as in Comparative Example 2, except that Amberlyst 15 was added as a carrier modified with a sulfonic acid group. 0.64 g of polyketone powder was obtained after the reaction. (Activity 3.01 kg / g-Pd; 0.388 kg / g-catalyst)
  • FIG. 9 A photograph of the prepared polyketone is shown in FIG. 9, and it was visually confirmed that fouling occurred.
  • Catalytic Activity 1 (kg / g-Pd)
  • Catalytic activity 2 (kg / g-catalyst)
  • Apparent density (g / mL) Fouling occurrence drawing
  • Example 1 33.84 1.29 0.297 radish 5
  • Example 2 23.26 0.9 0.309 radish -
  • Example 3 61.23 4.08 0.374 radish 6
  • Example 4 26.5 1.86 0.310 radish 7
  • Example 5 11.94 1.02 0.318 radish -
  • Comparative Example 3 0.771 Not measurable U - Comparative Example 4 3.00 0.388 Not measurable U 9
  • the polymerization reaction was carried out in the same manner as in Example 7, except that the composition of the component added to the reaction was changed as shown in Table 3 below.
  • Example 7 Catalyst A 2.0 / 1.5mg Additive 1A 1 / 0.3 mg
  • Example 8 Catalyst A 2.0 / 1.5mg Additive 1A 0.75 / 0.26 mg
  • Example 9 Catalyst A 2.0 / 1.5mg Additive 1A 0.5 / 0.15 mg
  • Example 10 Catalyst A 2.0 / 1.5mg Additive 1B 0.75 / 0.5 mg
  • Example 11 Catalyst A 2.0 / 1.5mg Additive 1C 0.75 / 0.3 mg
  • Example 12 Catalyst A 2.0 / 1.5mg Additive 1D 0.75 / 0.6 mg
  • Example 13 Catalyst A 2.0 / 1.5mg Additive 1E 0.75 / 0.3 mg
  • Example 14 Catalyst A 2.0 / 1.5mg Additive 1F 0.75 / 0.4 mg
  • the kinds of palladium catalysts used in Examples 7 to 22 and Comparative Examples 5 to 12 are as follows.
  • Examples 7 to 22 according to the polyketone production method of the present invention described above can prevent fouling by using an onium salt compound containing a carboxylic acid group as an additive , It was confirmed that the stability and activity in the polymerization reaction is excellent.
  • Comparative Example 5 which does not contain any additives, showed very low activity, and Comparative Examples 6 and 7 using strong acid para-toluenes (p-toluenesulfonic acid, TsOH) as additives confirmed that fouling occurred.
  • Comparative Examples 8 to 12 using No. 3 to No. 7 having a structure completely different from the present invention by not containing any carboxylic acid group or containing no onium salt compound had very low activity and sufficiently formed polyketone polymers. It was confirmed that fouling was not only difficult but also occurred.

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Abstract

La présente invention concerne une composition catalytique pour la préparation d'un composé de type polycétone, la composition catalytique comprenant : un composé à base d'un sel d'onium présentant 5 à 40 atomes de carbone et comprenant un groupe acide carboxylique ou un support modifié en surface par un groupe acide sulfonique ; et un catalyseur à base de palladium. Grâce à la composition catalytique, la présente invention permet d'obtenir : un système catalytique mixte à base de palladium, pouvant présenter une activité élevée et empêcher l'encrassement dans la préparation d'une polycétone ; un procédé de préparation d'un composé de type polycétone, le procédé permettant d'empêcher l'encrassement, de sauter l'étape d'alimentation de semences et d'atteindre une excellente stabilité et une excellente activité dans une réaction de polymérisation, à l'aide du système catalytique mixte à base de palladium ; et un polymère de polycétone présentant une densité apparente élevée préparé à partir du procédé.
PCT/KR2017/009060 2016-08-19 2017-08-18 Composition catalytique pour la préparation d'un composé de type polycétone, système catalytique mixte à base de palladium, procédé de préparation d'un composé de type polycétone l'utilisant et polymère de polycétone WO2018034549A1 (fr)

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