WO2018097472A1 - Catalyseur supporté de type métallocène et procédé de production de polypropylène l'utilisant - Google Patents

Catalyseur supporté de type métallocène et procédé de production de polypropylène l'utilisant Download PDF

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WO2018097472A1
WO2018097472A1 PCT/KR2017/011190 KR2017011190W WO2018097472A1 WO 2018097472 A1 WO2018097472 A1 WO 2018097472A1 KR 2017011190 W KR2017011190 W KR 2017011190W WO 2018097472 A1 WO2018097472 A1 WO 2018097472A1
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metallocene
formula
carbon atoms
group
supported catalyst
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PCT/KR2017/011190
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English (en)
Korean (ko)
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박종우
이혜경
김병석
전상진
정재엽
박희광
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주식회사 엘지화학
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Priority claimed from KR1020170007187A external-priority patent/KR102064411B1/ko
Application filed by 주식회사 엘지화학 filed Critical 주식회사 엘지화학
Priority to US16/088,610 priority Critical patent/US10815322B2/en
Priority to CN201780023096.5A priority patent/CN109071699B/zh
Priority to EP17872934.9A priority patent/EP3421506B1/fr
Publication of WO2018097472A1 publication Critical patent/WO2018097472A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F10/04—Monomers containing three or four carbon atoms
    • C08F10/06—Propene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/38—Polymerisation using regulators, e.g. chain terminating agents, e.g. telomerisation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/62—Refractory metals or compounds thereof
    • C08F4/622—Component covered by group C08F4/62 with an organo-aluminium compound
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/62—Refractory metals or compounds thereof
    • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
    • C08F4/642—Component covered by group C08F4/64 with an organo-aluminium compound
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/62—Refractory metals or compounds thereof
    • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
    • C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/62—Refractory metals or compounds thereof
    • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
    • C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
    • C08F4/6592—Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

Definitions

  • the present invention relates to a metallocene supported catalyst and a method for producing polypropylene using the same. More specifically, the present invention relates to a supported catalyst comprising a novel single metallocene compound and a method for producing a polypropylene having a broad molecular weight distribution using the same, and a polypropylene obtained therefrom.
  • Olefin polymerization catalyst systems can be classified into Ziegler-Natta and metallocene catalyst systems, and these two highly active catalyst systems have been developed for their respective characteristics.
  • the Ziegler-Natta catalyst has been widely applied to the existing commercial processes since the invention in the 50s.
  • the Ziegler-Natta catalyst has a broad molecular weight distribution because of its multiple active point multi-site catalyst. , There is a problem in that the composition distribution of the comonomer is not uniform and there is a limit in securing desired physical properties.
  • the metallocene catalyst is composed of a combination of a main catalyst composed mainly of transition metal compounds and a cocatalyst composed of an organometallic compound composed mainly of aluminum, and such a catalyst is a homogeneous complex catalyst.
  • catalyst the molecular weight distribution is narrow according to the characteristics of the single active site, the homogeneous composition distribution of the comonomer is obtained, the stereoregularity of the polymer according to the modification of the ligand structure and the polymerization conditions of the catalyst, copolymerization characteristics, It has the characteristic to change molecular weight, crystallinity, etc.
  • U. S. Patent No. 5, 032, 562 describes a process for preparing a polymerization catalyst by supporting two different transition metal catalysts on one supported catalyst. It is a bimodal di str ibut ion polymer supported by a titanium (Ti) -based Ziegler-Natta catalyst that generates high molecular weight and a zirconium (Zr) -based metallocene catalyst that produces low molecular weight on one support.
  • Ti titanium
  • Zr zirconium
  • U.S. Patent No. 5,525,678 discloses a method of using a catalyst system for olefin polymerization in which a metallocene compound and a nonmetallocene compound are simultaneously supported on a carrier to polymerize a high molecular weight polymer and a low molecular weight polymer simultaneously. It is described. This has the disadvantage that the metallocene compound and the non-metallocene compound must be separately supported, and the carrier must be pretreated with various compounds for supporting reaction.
  • U.S. Patent No. 5,914,289 describes a method for controlling the molecular weight and molecular weight distribution of a polymer using a metallocene catalyst supported on each carrier, but the amount and time of solvent used in preparing the supported catalyst This takes a lot, and the hassle of having to support the metallocene catalyst to be used on the carrier, respectively.
  • Korean Patent Application No. 2003-12308 discloses a method for controlling the molecular weight distribution by supporting a binuclear metallocene catalyst and a mononuclear metallocene catalyst on a carrier together with an activator to polymerize by changing a combination of catalysts in a reaction vessel. Doing.
  • this method has a limitation in realizing the characteristics of each catalyst at the same time, and also has the disadvantage that the metallocene catalyst portion is liberated in the carrier component of the finished catalyst to cause fouling during the reaction.
  • a metallocene catalyst for producing a polypropylene generally goes through a supporting process in order to be applied to a bulk polymerization. If the supporting process is difficult and poorly supported, a process problem (such as foul ing) occurs.
  • the metallocene supported catalyst is characterized by having a very narrow molecular weight distribution.
  • disadvantages in terms of processability, etc. there is a disadvantage in products requiring a wide molecular weight distribution.
  • a method of using a mixed metallocene catalyst capable of providing polypropylene having different molecular weight has been introduced.However, a method of improving the processability of polypropylene by using a metallocene catalyst can still be improved. This is not being developed. Therefore, a situation that requires research to improve the workability by adjusting the molecular weight distribution of the polypropylene polymerized with a single metallocene catalyst.
  • the present invention includes a novel metallocene compound that can be produced with high catalytic activity as a polymer in powder form without fouling polypropylene having excellent mechanical properties, processability, flowability, crystallinity, and the like. It is intended to provide a metallocene supported catalyst.
  • the present invention is to provide a method for producing a polypropylene having a wide molecular weight distribution using the metallocene supported catalyst.
  • a metallocene supported catalyst comprising a metallocene compound represented by the following formula (1), a cocatalyst compound, and a carrier.
  • R 1 and R 2 are the same as or different from each other, and each independently an alkyl group having 1 to 20 carbon atoms substituted with alkoxy having 1 to 20 carbon atoms;
  • R 3 and R 4 are the same as or different from each other, and each independently an alkyl group having 1 to 20 carbon atoms;
  • A is carbon, silicon or germanium
  • X is the same as or different from each other, and each independently represents a halogen or an alkyl group having 1 to 20 carbon atoms.
  • R 1 and R 2 in Chemical Formula 1 may be -butoxymethylene group, mesoxymethylene group, epoxymethylene group, / -propoxymethylene group, or phenoxymethylene group, respectively.
  • the metallocene compound may be one of the following structural formulas.
  • the carrier may be selected from the group consisting of silica, alumina, magnesia, and mixtures thereof.
  • the carrier may be further supported by at least one of the compounds represented by the following formula (2), (3) or (4) as a cocatalyst.
  • R 5 may be the same or different from each other, and each independently halogen; Hydrocarbons having 1 to 20 carbon atoms; Or a hydrocarbon having 1 to 20 carbon atoms substituted with halogen;
  • n is an integer of 2 or more
  • R 6 may be the same or different from each other, and each independently halogen; Hydrocarbons having 1 to 20 carbon atoms; Or a hydrocarbon having 1 to 20 carbon atoms substituted with halogen;
  • J is aluminum or boron
  • ⁇ is a neutral or cationic Lewis acid
  • ⁇ is a hydrogen atom
  • ⁇ is a Group 13 element
  • a ' may be the same as or different from each other, and each independently one or more hydrogen atoms are unsubstituted or substituted with halogen, a hydrocarbon having 1 to 20 carbon atoms, alkoxy or phenoxy, an aryl group having 6 to 20 carbon atoms or an alkyl group having 1 to 20 carbon atoms to be.
  • the mass ratio of the transition metal to the carrier of the metallocene compound may be 1:10 to 1: 1,000.
  • a method for producing polypropylene comprising the step of polymerizing propylene in the presence of the metallocene supported catalyst.
  • the polymerization of the propylene may be carried out by reacting for 1 to 24 hours at a temperature of 25 to 500 ° C and a pressure of 1 to 100 kgf / cm 2 , 30 to 2,000 ppm relative to the weight of the propylene Under hydrogen (3 ⁇ 4) gas.
  • a novel metallocene compound capable of producing polypropylene having excellent mechanical properties, processability, flowability, crystallinity, etc. as a polymer in powder form without fouling, with high catalytic activity of Provided are a metallocene supported catalyst.
  • first and second are used to describe various components, and the terms are used only for the purpose of distinguishing one component from other components.
  • a metallocene supported catalyst comprising a metallocene compound, a promoter compound, and a carrier represented by the following formula (1).
  • R 1 and R 2 are the same as or different from each other, and each independently an alkyl group having 1 to 20 carbon atoms substituted with alkoxy having 1 to 20 carbon atoms;
  • R 3 and R 4 are the same as or different from each other, and each independently an alkyl group having 1 to 20 carbon atoms;
  • A is carbon, silicon or germanium
  • X is the same as or different from each other, and each independently halogen or carbon number
  • R 1 and R 2 in Formula 1 may be each substituted with one or more hydrogen of the alkyl group having 1 to 20 carbon atoms to alkoxy having 1 to 20 carbon atoms, that is, an alkoxyalkylene group having 2 to 40 carbon atoms.
  • R 1 and R 2 may be an alkyl group having 1 to 6 carbon atoms substituted with alkoxy having 1 to 6 carbon atoms.
  • the role of the alkoxy group is a functional group capable of chemical reaction with the silica carrier in preparing the supported catalyst, so that all of the substituents Ri,, and Zr in the metallocene compound have multiple active sites that can react with the carrier. A wide molecular weight distribution can be exhibited.
  • R ⁇ 1> and R ⁇ 2> may be a pentoxymethylene group, a methoxymethylene group, an epoxy methylene group, a /-propoxymethylene group, or a phenoxymethylene group, respectively.
  • R 3 and R 4 each represent a methyl group (Me), an ethyl group (Et), ⁇ propyl group O—Pr), 2 ”butyl group O—Bu), pentyl group O Pent), or nucleophilic group Hex).
  • X may be the same or different halogen from each other.
  • the compound represented may be one of the following structural formulas.
  • the metallocene compound of Formula 1 may polymerize polypropylene having excellent activity and a wide molecular weight distribution.
  • the present invention synthesized a novel catalyst in the form of a tether (Tether) that can induce effective supported reaction, and the co-catalyst such as MA0 on the silica (si li ca) carrier under the influence of tether (tether)
  • the metallocene compound can be effectively supported in 2 steps of 1 step each.
  • a polymer in powder form can be obtained without fouling during the polymerization process, and a polymer having a wide molecular weight distribution can be prepared using a single catalyst during polypropylene homopolymerization. That is, a wide molecular weight distribution can be realized even if only the metallocene compound represented by Chemical Formula 1 is supported, without hybridly supporting other metallocene compounds with the catalyst compound.
  • MWD molecular weight distribution
  • existing metallocene catalyst has a feature that can produce a polypropylene excellent in processability difficult to implement.
  • the metallocene compound of Chemical Formula 1 is prepared by connecting a indene derivative with a bridge compound to prepare a ligand compound, and then performing a metal lat ion by adding a metal precursor compound. It may be, but is not limited thereto.
  • a lithium salt is prepared by reacting an indene derivative with an organolithium compound such as yrBuLi, a halogenated compound of a bridge compound is mixed, and then the mixture is reacted to prepare a ligand compound.
  • the metallocene compound represented by Formula 1 above by mixing the ligand compound or a lithium precursor thereof with a metal precursor compound, reacting the reaction mixture about 12 hours to about 24 hours until the reaction is complete, and drying the reaction product under filtration and reduced pressure. Can be obtained. Method for producing a metallocene compound of Formula 1 will be described in detail in the Examples to be described later.
  • a carrier containing a hydroxyl group or a siloxane group may be used as a carrier.
  • the carrier may be a carrier containing a hydroxyl group or a siloxane group having high reaction properties by drying at a high temperature to remove moisture on the surface.
  • silica, alumina, magnesia or a mixture thereof may be used as the carrier.
  • the carrier may be at least one member selected from the group consisting of silica, silica-alumina, and silica-magnesia.
  • the carrier may be dried at a high temperature, and they may typically include oxides, carbonates, sulfates, nitrates, such as Na 2 O, K 2 CO 3) BaS0 4 and Mg (N0 3 ) 2 .
  • the amount of the hydroxy group can be controlled by the preparation method, preparation conditions and drying conditions (temperature, time, drying method, etc.) of the carrier, and preferably from 0.1 to 10 Pa ol / g, more preferably from 0.1 to 1 1 ⁇ ol / g, more preferably 0.1 to 0.5 ⁇ ol / g.
  • a carrier having a large amount of the semi-aromatic siloxane groups participating in the supported chemical group may be used while the hydroxy group is chemically removed.
  • the carrier may be additionally supported by at least one compound of formula (2), (3) or compound represented by the formula as a promoter.
  • R 5 may be the same or different from each other, and each independently halogen; Hydrocarbons having 1 to 20 carbon atoms; Or a hydrocarbon having 1 to 20 carbon atoms substituted with halogen;
  • n is an integer of 2 or more
  • R 6 may be the same or different from each other, and each independently halogen; Hydrocarbons having 1 to 20 carbon atoms; Or a hydrocarbon having 1 to 20 carbon atoms substituted with halogen;
  • J is aluminum or boron
  • E is a neutral or cationic Lewis acid
  • H is a hydrogen atom
  • Z is a Group 13 element
  • a 1 may be the same or different from each other, and each independently one or more hydrogen atoms are unsubstituted or substituted with a halogen, a hydrocarbon having 1 to 20 carbon atoms, alkoxy or phenoxy, an aryl group having 6 to 20 carbon atoms or an alkyl group having 1 to 20 carbon atoms. to be.
  • Non-limiting examples of the cocatalyst represented by the formula (2) include methyl aluminoxane ethyl aluminoxane, isobutyl aluminoxane or tert- butyl aluminoxane, and the like, and more preferred compound may be methyl aluminoxane.
  • Examples of the compound represented by Formula 3 include trimethylaluminum triethylaluminum, triisobutylaluminum tripropylaluminum tributylaluminum, dimethylchloroaluminum, triisopropylaluminum, tri- butylaluminum, tricyclopentylaluminum and tripentylaluminum Triisopentyl aluminum, trinuclear silaluminum, trioctyl aluminum ethyl dimethyl aluminum, methyl diethyl aluminum, triphenyl aluminum, triryl aluminum, dimethyl aluminum hydroxide, dimethyl aluminum ethoxide trimethyl boron triethyl boron triisobutyl boron, tri Propylboron tributylboron and the like, and more preferred compounds are selected from trimethylaluminum triethylaluminum and triisobutylaluminum.
  • Examples of the compound represented by Formula 4 include triethylammonium tetraphenylboron, tributylammonium tetraphenylboron, trimethylammonium tetraphenylboron, tripropylammonium tetraphenylboron, and trimethylammoniumtetra boron , Trimethyl ammonium tetra (0 ,; dimethylphenyl) boron, tributyl ammonium tetra trifluoromethylphenyl) boron, trimethyl ammonium tetra trichloromethylphenyl) boron, tributyl ammonium tetrapentafluorophenyl boron Diethylanilinium tetraphenylboron, Sea diethylanilinium tetrapentafluorophenylboron, Diethylammonium 1 tetrapentafluorophenylboron, triphenylphosphon
  • aluminoxane may be preferably used, and more preferably methylaluminoxane (MA0), which is an alkylaluminoxane, may be used.
  • the cocatalyst may be used in an appropriate amount so that activation of the metallocene compound, which is a catalyst precursor, may proceed in detail.
  • the metallocene supported catalyst according to the present invention comprises the steps of 1) contacting the metallocene compound represented by Formula 1 with the compound represented by Formula 2 or Formula 3 to obtain a mixture; And 2) adding the compound represented by Chemical Formula 4 to the mixture.
  • the metallocene supported catalyst according to the present invention may be prepared by contacting the metallocene compound represented by Chemical Formula 1 with the compound represented by Chemical Formula 2 as a second method.
  • the molar ratio of the metallocene compound represented by Formula 1 / the compound represented by Formula 2 or Formula 3 is preferably 1/5, 000 to 1/2 More preferably 1/1, 000 to 1/10, and most preferably 1/500 to 1/20.
  • the amount of the alkylating agent is so small that the alkylation of the metal compound may not be fully performed.
  • the molar ratio of the metallocene compound represented by Chemical Formula 1 / the compound represented by Chemical Formula 4 is preferably 1/25 to 1, more preferably 1/10 to 1, and most preferably 1 /. 5 to 1.
  • the amount of the activator is relatively small, and thus, the supported catalyst is not formed completely. If the activity is inferior, and if the molar ratio is less than 1/25, the metal compound is fully activated, but there is a problem that the unit cost of the catalyst supported by the remaining excess activator is not economical or the purity of the produced polymer is inferior.
  • the molar ratio of the metallocene compound represented by the formula (1) / compound represented by the formula (2) is preferably 1/10, 000 to 1/10, more preferably Preferably 1/5, 000 to 1/100, most preferably 1/3, 000 to 1/500. If the molar ratio is greater than 1/10, the amount of the activator is relatively small, so that the activity of the supported catalyst generated due to the incomplete activation of the metal compound is inferior, and in the case of less than 1/10, 000, the metal Although the compound is completely activated, there is a problem that the cost of the supported catalyst is not economical or the purity of the resulting polymer is inferior with the remaining excess activator.
  • a hydrocarbon solvent such as pentane, nucleic acid, heptane, or the like, or an aromatic solvent such as benzene or toluene may be used.
  • the metallocene compound when the supported catalyst supports the metallocene compound and the cocatalyst compound on a carrier, the metallocene compound is about 0.5 to about 20 parts by weight, and the promoter is about 1 to about 1, based on 100 parts by weight of the support. It may be included in 000 parts by weight.
  • the metallocene compound may be included in an amount of about 1 to about 15 parts by weight, and the promoter may be included in an amount of about 10 to about 500 parts by weight, and most preferably, about 100 parts by weight of the carrier
  • the metallocene compound may be included in an amount of about 1 to about 100 parts by weight, and the promoter may be included in an amount of about 40 to about 150 parts by weight.
  • the mass ratio of the total transition metal to the carrier included in the metallocene compound may be 1:10 to 1: 1,000.
  • the mass ratio of the promoter compound to the carrier may be from 1: 1 to 1: 100.
  • the metallocene supported catalyst may further include additives and auxiliaries which are commonly employed in the art to which the present invention pertains, in addition to the above components.
  • a method for producing polypropylene comprising the step of polymerizing propylene in the presence of the metallocene supported catalyst.
  • the metallocene-supported catalyst is a polypropylene having a high catalytic activity and a broad molecular weight distribution with high catalytic activity by using a catalyst including a metallocene compound of Formula 1 containing an indene ligand having a specific substituent.
  • a catalyst including a metallocene compound of Formula 1 containing an indene ligand having a specific substituent can be provided.
  • the supported catalyst including the metallocene compound of Formula 1 has improved catalytic activity than the existing Ziegler-Natta catalyst or the metallocene catalyst, even if the supported conditions of the metallocene compound change, that is, reaction temperature, reaction time It is possible to produce polypropylene with improved activity even if the supported amount of the silica type or metallocene compound is changed.
  • the polymerization of propylene may be carried out by reacting for about 1 to about 24 hours at a temperature of about 25 to about 500 ° C and a pressure of about 1 to about 100 kgf / cm 2 .
  • the polymerization reaction temperature is preferably about 25 to about 200 ° C, more preferably about 50 to about 100 ° C.
  • the polymerization reaction pressure is preferably about 1 to about 70 kgf / cm 2 , more preferably about 5 to about 50 kgf / cm 2 .
  • the polymerization reaction time is preferably about 1 to about 5 hours.
  • the method for preparing polypropylene of the present invention may be performed by contacting propylene with a catalyst containing a metallocene compound represented by Formula 1 above.
  • the polymerization of propylene may be carried out under hydrogen gas.
  • the hydrogen gas serves to activate the inert site of the metallocene catalyst and to control the molecular weight by generating a chain transfer react ion.
  • the metallocene compound of the present invention is excellent in hydrogen reaction properties, and thus, by controlling the amount of hydrogen gas used in the polymerization process, a polypropylene having a desired molecular weight and a melt index can be effectively obtained.
  • the hydrogen gas may be introduced to about 30 to about 2,000 ppm, or about 50 to about 1, 500 ppm, or about 50 to about 500 ppm, relative to the weight of propylene.
  • the molecular weight distribution and melt index (MI) of the polypropylene produced while exhibiting sufficient catalytic activity can be adjusted within a desired range, and accordingly the poly Propylene can be prepared.
  • the metallocene catalyst of the present invention has a very good hydrogen reactivity so that the chain transfer reaction is activated as the amount of hydrogen gas is increased, thereby obtaining a polypropylene having a reduced molecular weight and a high melt index. Can be.
  • the polypropylene manufacturing method may be performed by a solution polymerization process, a slurry process, or a gas phase process using one continuous slurry polymerization reactor, a loop slurry reactor, a gas phase reactor, or a solution reactor.
  • the catalyst is an aliphatic hydrocarbon solvent having 5 to 12 carbon atoms, such as pentane, nucleic acid, heptane, nonane, decane, and isomers thereof suitable for the polymerization process of olefinic monomers. It can be injected by dissolving or diluting aromatic hydrocarbon solvents such as toluene and benzene, hydrocarbon solvents substituted with chlorine atoms such as dichloromethane and chlorobenzene.
  • the solvent used here is a small amount of alkylaluminum It is preferable to remove and use a small amount of water or air which acts as a catalyst poison by treating.
  • the polypropylene manufacturing method may further include a step generally employed in the art.
  • a polypropylene obtained by the above-described manufacturing method is provided.
  • the present invention by using a catalyst containing the novel metallocene compound, a poly-based polymer having high polymerization activity with excellent processability and wide molecular weight distribution as compared with the case of using a conventional metallocene compound Propylene can be obtained.
  • the present invention introduces an aryl substituent at a specific position of a ligand in an indene-based ansa-metallocene catalyst, and has a functional group having Lewis base properties such as alkoxy having 1 to 20 carbon atoms in the aryl substituent.
  • the polypropylene may be used as a packaging container, a film, a sheet, an injection molded product, a textile product, etc., in which processing characteristics are low, and transparency and fluidity are required.
  • the weight average molecular weight (Mw) of the produced polypropylene is based on the amount of hydrogen used during the polymerization process. According to the weight average molecular weight (Mw) of about 30, 000 to about 9,000,000 g / mol or about 80, 000 to about 1,000,000 g / mol, or about 10, 000 to about 1,000, 000 g / mol.
  • the polypropylene thus prepared has a molecular weight distribution (Mw / Mn) of about
  • the catalyst compound does not commonly carry other metallocene compounds, Since only a metallocene compound represented by 1 can be supported to realize a wide molecular weight distribution, it is possible to prevent a problem in which other physical properties such as XS, fine powder content, and thermal properties change in addition to the molecular weight distribution when using a common supported catalyst. .
  • the xylene soluble fraction (Xs) of the polypropylene exhibits high tacticity of about 2.0% by weight or less, preferably about 1.5% by weight, more preferably about 1.0% by weight or less.
  • Xylene solubles are the content (% by weight) of polymer soluble in cold xylene determined by dissolving the polypropylene in xylene and crystallizing the insoluble portion from the cooling solution.
  • Xylene solubles contain polymer chains of low stereoregularity, and the lower the content of xylene solubles, the higher the stereoregularity.
  • the fine powder having a particle diameter of 75 fm or less has a fine powder content of about 5.0 weight 3 ⁇ 4 "or less, preferably about 3.0 weight% or less, and more preferably about 2.0 weight% or less.
  • the occurrence of fouling and the resulting process instability can be prevented, and the problem of scattering particles during product processing can be reduced.
  • the polypropylenes produced according to the invention exhibit high flowability.
  • the polypropylene prepared according to the present invention when measured at 230 V, 2.16 kg, is about 1 g / 10 min or more, for example, about 1 to about 2,500 g / lOmin, preferably about 5 to Polypropylene having a broad melt index (MI) of about 1,500 g / 10min and a melt index can be adjusted according to the amount of hydrogen used during the polymerization process, thereby producing a polypropylene having an appropriate melt index according to the application.
  • MI melt index
  • preferred embodiments are presented. However, the following examples are merely provided to more easily understand the present invention, and the contents of the present invention are not limited thereto.
  • Step 2 Synthesis of 7- (4-erH3utoxymethyl) phenyl) -2-methyl-l / Hndene l-bromo-4- (ie i-butoxymethyl) benzene (4.52 g, 18.6 ⁇ ol) was dissolved in anhydrous THF (20 mL) under argon (Ar). The silver was lowered to -78 ° C and n-butyllithium solution ( ⁇ BuLi, 2.5 M in hexane, 8.2 mL) was added, followed by stirring at room temperature for 30 minutes. The temperature was lowered back to -78 ° C and trimethyl borate (6.2 mL, 55.6 ⁇ ol) was added, followed by stirring at room temperature overnight. Sat. NH 4 C1 was added and extracted with MTBE. Anhydrous MgSO 4 was added and filtered to remove water. The solution was concentrated under reduced pressure and the next reaction was carried out without further purification.
  • Step 1-3 Synthesis of bis (4- (4-ferf-butoxymethyl) phenyl) -2-methyl-L ⁇ — inden l-yl) dimethylsi lane
  • Step 1-4 Synthesis of dimetylsi lanyl-bis (4- (4- ⁇ er -butoxymethyl) phenyl) to 2-methyl-l Mnden-l-yl) Zirconium dichloride
  • the solvent was distilled off under reduced pressure in vacuo and ZrCl 4 (THF) 2 (1.18 g, 3.12 ⁇ ol) was placed in a glove box and the temperature was lowered to -78 ° C. Diethyl ether (20 mL) was added to the mixture, and the temperature was raised to room temperature and stirred overnight. The solvent was distilled off under reduced pressure and dissolved in CH 2 C1 2 to remove the solid.
  • ZrCl 4 (THF) 2 (1.18 g, 3.12 ⁇ ol) was placed in a glove box and the temperature was lowered to -78 ° C. Diethyl ether (20 mL) was added to the mixture, and the temperature was raised to room temperature and stirred overnight.
  • the solvent was distilled off under reduced pressure and dissolved in CH 2 C1 2 to remove the solid.
  • the supported catalyst was prepared by supporting the metallocene compound obtained in step 1-4 after supporting methylaluminoxane on silica in the following manner.
  • silica (3 g) was placed in a 250 mL Schlenk flask under argon, and methylaluminoxane (MA0, 23 mL, 30 ⁇ l) was slowly injected at room temperature and stirred at 95 ° C for 18 hours. . After the reaction, at room temperature After cooling and standing for 15 minutes, the upper layer of the solvent was removed. Toluene (25 mL) was added thereto, stirred for 1 minute, left for 20 minutes, and the solvent was removed from the upper layer. After dissolving the metallocene compound (180 ⁇ ) obtained in steps 1-4 in toluene (20 mL), the flask was added with a cannula and washed with toluene (5 mL).
  • MA0, 23 mL, 30 ⁇ l methylaluminoxane
  • Step 2-2 7- (4-metoxymethyl) phenyl) -2-inethyl-: Ltf— indene synthesis
  • l-bromo-4- (methoxymethyl) benzene (9.3 g, 46.3 mmol) was dissolved in anhydrous THF (40 mL) under argon (Ar). The temperature was lowered to -78 ° C and n_butyllithium solution (n-BuLi, 2.5 M in hexane, 20.4 mL) was added, followed by stirring at room temperature for 30 minutes. The temperature was lowered to -78 ° C and trimethyl borate (15.5 mL, 139 ⁇ ol) was added, followed by stirring at room temperature overnight. Sat. NH 4 C1 was added and extracted with MTBE. Anhydrous MgSO 4 was added and filtered to remove water. The solution was concentrated under reduced pressure and the next reaction was carried out without further purification.
  • n_butyllithium solution n-BuLi, 2.5 M in hexane, 20.4 mL
  • trimethyl borate (15.5 mL, 139 ⁇ ol
  • Step 2-3 Synthesis of bis (4- (4-metoxymethyl) phenyl) -2-methy 1-l ⁇ i nden-yDdimethylsi lane
  • Step 2-4 Synthesis of dimetylsi 1 any 1 -bis (4- (4-met oxymet hy 1) phenyl) -2-methyl- nden- 1-y 1) Zirconium dichloride
  • the solvent was distilled off under reduced pressure in vacuo and ZrCl 4 (THF) 2 (2.04 g, 5.39 Pa ol) was placed in a glove box and the temperature was lowered to -78 ° C. Diethyl ether (30 mL) was added to the mixture, and the mixture was stirred with iced and stirred overnight. The solvent was distilled off under reduced pressure and dissolved in C3 ⁇ 4C1 2 to remove the solid.
  • ZrCl 4 (THF) 2 (2.04 g, 5.39 Pa ol) was placed in a glove box and the temperature was lowered to -78 ° C.
  • Diethyl ether (30 mL) was added to the mixture, and the mixture was stirred with iced and stirred overnight.
  • the solvent was distilled off under reduced pressure and dissolved in C3 ⁇ 4C1 2 to remove the solid.
  • the supported catalyst was prepared by supporting the metallocene compound obtained in the step 2-4 after supporting the methylaluminoxane on silica in the following manner. First, add silica (3 g) to a 250 mL Schlenk f lask under argon and slowly inject methylaluminoxane (MA0, 23 mL, 30 ⁇ l) at room temperature and stir at 95 ° C for 18 hours. It was. After the reaction was completed, the mixture was cooled to room temperature and left for 15 minutes, and then the upper portion of the solvent was removed. Toluene (25 mL) was added thereto, stirred for 1 minute, left for 20 minutes, and the solvent was removed from the upper layer.
  • silica 3 g
  • methylaluminoxane MA0, 23 mL, 30 ⁇ l
  • Step 3-1 Preparation of (6-butoxynucleosil) dichloromethylsilane
  • Step 3-2 Preparation of butoxynucleosil) (methyl) -bis (2-methyl-4- (4-f-butyl) phenylindenyl) silane
  • Step 3-3 Preparation of [(6-f-butoxynucleosilmethylsilane-diyl) -bis (2-methyl-4- (4-f-butyl) phenylindenyl)] zirconium dichloride
  • Step 3-4 Preparation of the supported catalyst
  • the supported catalyst was prepared by supporting the metallocene compound obtained in step 3-3 after supporting methylaluminoxane on silica in the following manner.
  • silica (3 g) was added to a 250 mL Schlenk flask under argon, and methylaluminoxane (MA0, 23 mL, 30 ⁇ l) was slowly injected at room temperature and stirred at 95 ° C for 18 hours. . After the reaction was completed, the mixture was cooled to room temperature and left for 15 minutes, and then the upper portion of the solvent was removed. Toluene (25 mL) was added thereto, stirred for 1 minute, left for 20 minutes, and the solvent was removed from the upper layer.
  • MA0, 23 mL, 30 ⁇ l methylaluminoxane
  • Step 4-1 Preparation of Dimethylbis (2-Methyl-4phenylindenyl) silane
  • Step 4-2 Preparation of [dimethylsilanediylbis (2-methyl-4—phenylindenyl)] zirconium dichloride
  • the supported catalyst was prepared by supporting the metallocene compound obtained in step 4-2 after supporting methylaluminoxane on silica in the following manner.
  • silica (3 g) was placed in a 250 mL Schlenk flask under argon, and methylaluminoxane (MA0, 23 mL, 30 ⁇ l) was slowly injected at room temperature and stirred at 95 ° C for 18 hours. . After the reaction was completed, the mixture was cooled to room temperature and left for 15 minutes, and then the upper portion of the solvent was removed. Toluene (25 mL) was added thereto, stirred for 1 minute, left for 20 minutes, and the solvent was removed from the upper layer.
  • MA0, 23 mL, 30 ⁇ l methylaluminoxane
  • the vacuum was dried at 65 ° C. for 2 L stainless steel, and the mixture was chopped, triethylaluminum 3.0 ⁇ ol was added at room temperature, hydrogen was added 2 bar, and 770 g of propylene was sequentially added.
  • Catalyst activity calculated as the ratio of the weight of the resulting polymer (kg PP) per catalyst content (mmol and g of catalyst) used based on unit time (h).
  • polypropylene having a wide molecular weight distribution can be produced even when a single metallocene catalyst is used during polypropylene homopolymerization.
  • polypropylene having such a wide molecular weight distribution is expected to have an excellent effect on workability.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)

Abstract

La présente invention concerne un catalyseur supporté comprenant un nouveau composé métallocène ayant une excellente activité de polymérisation, et un procédé de production de polypropylène ayant une excellente aptitude au traitement et une large distribution de poids moléculaire, par utilisation du catalyseur supporté.
PCT/KR2017/011190 2016-11-22 2017-10-11 Catalyseur supporté de type métallocène et procédé de production de polypropylène l'utilisant WO2018097472A1 (fr)

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US16/088,610 US10815322B2 (en) 2016-11-22 2017-10-11 Metallocene supported catalyst and method for preparing polypropylene using the same
CN201780023096.5A CN109071699B (zh) 2016-11-22 2017-10-11 茂金属负载型催化剂和使用其制备聚丙烯的方法
EP17872934.9A EP3421506B1 (fr) 2016-11-22 2017-10-11 Catalyseur supporté de type métallocène et procédé de production de polypropylène l'utilisant

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Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5032562A (en) 1989-12-27 1991-07-16 Mobil Oil Corporation Catalyst composition and process for polymerizing polymers having multimodal molecular weight distribution
US5525678A (en) 1994-09-22 1996-06-11 Mobil Oil Corporation Process for controlling the MWD of a broad/bimodal resin produced in a single reactor
KR19990039714A (ko) * 1997-11-14 1999-06-05 전원중 폴리프로필렌의 제조방법
US5914289A (en) 1996-02-19 1999-06-22 Fina Research, S.A. Supported metallocene-alumoxane catalysts for the preparation of polyethylene having a broad monomodal molecular weight distribution
KR20030012308A (ko) 2001-07-31 2003-02-12 주식회사 예스아이비 배팅형 복권 시스템 및 배팅 방법
US20050054520A1 (en) * 2000-06-30 2005-03-10 Hart James R. Metallocenes and catalyst compositions derived therefrom
KR20120076160A (ko) * 2010-12-29 2012-07-09 호남석유화학 주식회사 폴리올레핀 제조용 메탈로센 촉매 및 이를 이용한 폴리올레핀의 제조방법
KR20150037652A (ko) * 2013-09-30 2015-04-08 주식회사 엘지화학 폴리프로필렌의 제조방법 및 이로부터 수득되는 폴리프로필렌
KR20150091308A (ko) * 2012-10-18 2015-08-10 보레알리스 아게 중합 방법 및 촉매

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5032562A (en) 1989-12-27 1991-07-16 Mobil Oil Corporation Catalyst composition and process for polymerizing polymers having multimodal molecular weight distribution
US5525678A (en) 1994-09-22 1996-06-11 Mobil Oil Corporation Process for controlling the MWD of a broad/bimodal resin produced in a single reactor
US5914289A (en) 1996-02-19 1999-06-22 Fina Research, S.A. Supported metallocene-alumoxane catalysts for the preparation of polyethylene having a broad monomodal molecular weight distribution
KR19990039714A (ko) * 1997-11-14 1999-06-05 전원중 폴리프로필렌의 제조방법
US20050054520A1 (en) * 2000-06-30 2005-03-10 Hart James R. Metallocenes and catalyst compositions derived therefrom
KR20030012308A (ko) 2001-07-31 2003-02-12 주식회사 예스아이비 배팅형 복권 시스템 및 배팅 방법
KR20120076160A (ko) * 2010-12-29 2012-07-09 호남석유화학 주식회사 폴리올레핀 제조용 메탈로센 촉매 및 이를 이용한 폴리올레핀의 제조방법
KR20150091308A (ko) * 2012-10-18 2015-08-10 보레알리스 아게 중합 방법 및 촉매
KR20150037652A (ko) * 2013-09-30 2015-04-08 주식회사 엘지화학 폴리프로필렌의 제조방법 및 이로부터 수득되는 폴리프로필렌

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