WO2019132450A1 - Catalyseur métallocène supporté et procédé de préparation de polypropylène faisant appel à celui-ci - Google Patents

Catalyseur métallocène supporté et procédé de préparation de polypropylène faisant appel à celui-ci Download PDF

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WO2019132450A1
WO2019132450A1 PCT/KR2018/016504 KR2018016504W WO2019132450A1 WO 2019132450 A1 WO2019132450 A1 WO 2019132450A1 KR 2018016504 W KR2018016504 W KR 2018016504W WO 2019132450 A1 WO2019132450 A1 WO 2019132450A1
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Prior art keywords
carbon atoms
formula
metallocene
catalyst
halogen
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PCT/KR2018/016504
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English (en)
Korean (ko)
Inventor
정재엽
권헌용
홍대식
전상진
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주식회사 엘지화학
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Priority claimed from KR1020180166737A external-priority patent/KR102343937B1/ko
Application filed by 주식회사 엘지화학 filed Critical 주식회사 엘지화학
Priority to CN201880083882.9A priority Critical patent/CN111556878B/zh
Priority to US16/957,962 priority patent/US11358979B2/en
Priority to EP18895226.1A priority patent/EP3715382B1/fr
Publication of WO2019132450A1 publication Critical patent/WO2019132450A1/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
    • C08F4/52—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 selected from boron, aluminium, gallium, indium, thallium or rare earths
    • 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
    • C08F4/646—Catalysts comprising at least two different metals, in metallic form or as compounds thereof, in addition to the component covered by group C08F4/64
    • 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

Definitions

  • the present invention relates to a process for preparing a supported catalyst and the polypropylene using the same metallocene.
  • the present invention is by using a supported catalyst comprising a metallocene compound of a single metal, the polypropylene has a relatively narrow molecular weight distribution and the SPAN value Can be produced with high activity.
  • Olefin polymerization catalyst systems can be classified into Ziegler-Natta and metallocene catalyst systems, both of which have been developed for their respective characteristics.
  • the Ziegler-Natta catalyst has been widely applied to conventional commercial processes since the invention of the 50's.
  • the Ziegler-Natta catalyst is a multi-site catalyst containing a plurality of active sites, the molecular weight distribution of the polymer is broad, Is not uniform, so that it is difficult to secure desired properties.
  • the metallocene catalyst is composed of a combination of a main catalyst mainly composed of a transition metal compound and a cocatalyst, which is an organometallic compound mainly composed of aluminum.
  • Such a catalyst is a single site catalyst as a homogeneous complex catalyst, .
  • the polymer has a narrow molecular weight distribution according to the single active site property and a 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, the stereoregularity of the polymer, Crystallinity and so on.
  • U.S. Patent No. 5,032,562 discloses two transition metal catalysts, one And supported on a catalyst bed to produce a polymerization catalyst. This is a method of producing a bimodal distribution polymer by supporting a Ziegler-Natta catalyst of a titanium (Ti) series which generates a high molecular weight and a metallocene catalyst of a zirconium (Zr) , The supporting process is complicated and the morphology of the polymer is deteriorated due to the co-catalyst.
  • Ti titanium
  • Zr zirconium
  • U.S. Patent No. 5,552,678 discloses a method of using a catalyst system for olefin polymerization in which a metallocene compound and a non-metallocene compound are simultaneously supported on a carrier to polymerize a high molecular weight polymer and a low molecular weight polymer simultaneously .
  • This is a disadvantage in that the metallocene compound and the non-metallocene compound must be supported separately and the carrier must be pretreated with various compounds for the supporting reaction.
  • U.S. Patent No. 5,914,289 discloses a method of controlling the molecular weight and molecular weight distribution of a polymer by using a metallocene catalyst supported on each carrier.
  • the amount of the solvent used in the preparation of the supported catalyst and the production time And it is troublesome to carry 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 carrying a double-nucleated metallocene catalyst and a single nuclear metallocene catalyst together with an activating agent in a carrier to change and polymerize the combination of catalysts in the reactor have.
  • this method has a limitation in simultaneously realizing the characteristics of the respective catalysts, and also has a disadvantage in that the metallocene catalyst portion is liberated from the carrier component of the finished catalyst, thereby causing fouling to the reactor.
  • the present invention aims to provide a metallocene supported catalyst comprising a novel metallocene compound capable of producing polypropylene having a relatively narrow molecular weight distribution and SPAN value with high activity. 2019/132450 1 »(: 1 ⁇ 1 ⁇ 2018/016504
  • a metallocene supported catalyst comprising a metallocene compound represented by the following formula (1) and a carrier.
  • each is independently an aryl having 6 to 20 carbon atoms or an aryl having 6 to 20 carbon atoms and substituted with alkyl having 1 to 20 carbon atoms;
  • 3 ⁇ 4 is an alkyl group having 1 to 20 carbon atoms
  • the show is carbon, silicon or germanium
  • the group of Formula 1 may be dimethylamine, dipropylamine, diisopropylamine, diphenylamine, methylpropylamine, methylphenylamine, or isopropylphenylamine.
  • the compound represented by the formula (1) may be one of the compounds represented by the following structural formulas. ⁇ ⁇ 0 2019/132450 1 »(: 1/10 ⁇ 018/016504
  • the carrier may further comprise one or more promoter compounds selected from the group consisting of compounds represented by the following general formulas (2), (3) and (4) (2)
  • the seedlings are neutral or cationic Lewis acids
  • the carrier may be at least one selected from the group consisting of silica, alumina, magnesia, and mixtures thereof.
  • the mass ratio of the transition metal to the carrier of the metallocene compound may be about 1:10 to about 1: 1,000.
  • Polymerization of such a profile X is from about 25 to about 5001: about 1 may be carried out by reaction for about 24 hours under a pressure of the temperature and from about 1 to ⁇ £ / 011 2 to about 10, at this time, the weight of the propylene In the presence of a hydrogen (3 ⁇ 4) gas of from about 30 to about 25 atm. 2019/132450 1 »(: 1 ⁇ 1 ⁇ 2018/016504
  • the metallocene supported catalyst of the present invention can produce polypropylene having a relatively narrow molecular weight distribution and SPAN value with high activity.
  • a metallocene supported catalyst comprising a metallocene 25 compound represented by the following formula (1) and a carrier.
  • 3 ⁇ 4 is an alkyl group having 1 to 20 carbon atoms
  • 3 ⁇ 4 is a tertiary amine having an alkyl group having 1 to 10 carbon atoms
  • the show is carbon, silicon or germanium
  • 0 X are the same or different and each independently represents a halogen or an alkyl group having 1 to 20 carbon atoms.
  • the group of Formula 1 may be dimethylamine, dipropylamine, diisopropylamine, diphenylamine, methylpropylamine, methylphenylamine, or isopropylphenylamine.
  • the compound represented by Formula 1 may be one of the compounds represented by the following formulas. 2019/132450 1 »(: 1/10 ⁇ 018/016504
  • the polypropylene polymerized metal for metallocene catalysts are the raw bulk (1 1 ⁇ go through a loading process to be applied to the polymerization, when the process of the supported non-well-demanding and supporting step on the problem ⁇ 0 13 ⁇ 4 etc.) wig
  • Conventional metallocene catalysts have a problem in that they undergo prepolymerization (1 3 ⁇ 4 - 1501 >, 11161 011 ) before the polymerization in order to avoid process problems.
  • the inventors of the present invention have found that by synthesizing a novel type catalyst in which a tethering catalyst having a specific structure capable of inducing a supported reaction is bonded, 2019/132450 1 »(: 1 ⁇ 1 ⁇ 2018/016504
  • the alkylene group of a certain length is introduced in the bridge group connecting the indenyl groups, and then the alkylene group having a relatively high electron density Group and an amine group including nitrogen may be connected, which may have very large nucleophilicity.
  • the carrier can be bonded more strongly to the carrier than the existing metallocene compound, and the single active species can be increased relative to the conventional one, so that the homogeneous activity can be exhibited in the propylene polymerization reaction.
  • the polypropylene weed in the presence of the supported catalyst according to an example of the present invention can have uniform physical properties such as a relatively narrow molecular weight distribution and a narrow SPAN value as compared with the prior art.
  • the metallocene supported catalyst according to one aspect of the present invention can exhibit high catalytic efficiency in the propylene polymerization reaction even when no extra promoter is added.
  • the metallocene compound of the formula (I) is indene to prepare a 25 derivative thereof connected to a bridge compound with a ligand compound, and then added to the metal precursor compound to the metal-ray line ⁇ 1 Seen 10! 1) it can be obtained by carrying out, but is not limited to this.
  • the compound or its lithium salt and a metal precursor compound are mixed and reacted for about 12 hours to about 24 hours until the reaction is completed, and then the reaction product is filtered and dried under reduced pressure to obtain the metallocene compound represented by the formula
  • the method for preparing the metallocene compound of Formula 1 will be described in the following Examples.
  • a carrier containing a hydroxyl group or siloxane group on its surface may be used.
  • a carrier containing a hydroxyl group or a siloxane group having high reactivity by removing moisture on the surface by drying at a high temperature may be used.
  • examples of the carrier include silica, alumina, magnesia, and mixtures thereof.
  • the carrier may be at least one selected from the group consisting of silica, silica-alumina, and silica-magnesia.
  • the support has a number of days will be dried at a high temperature, they typically can contain the Na 20, 3 ⁇ 400 3, 6 3 ⁇ 4804 and Mg (N0 3) 2 such as an oxide, carbonate, sulfate, nitrate component.
  • the amount of the hydroxy group is controlled by the preparation method of the carrier, the preparation conditions, the drying conditions (temperature, time, drying method, etc.), and the like. number, and 0.1 to 10_ 01 are preferred, more preferably from 0.1 to 1 11,111,101 / silver, and more preferably from 0.1 to 0.5 11,111,101 / it is. supported to reduce the side reaction by some of the hydroxy group remaining in the dry purpurea
  • a siloxane group having high reactivity may be used while a carrier in which the hydroxyl group is chemically removed may be used.
  • the carrier may further contain at least one compound represented by the following general formula (2), (3), or (4) as a promoter.
  • 01 is an integer of 2 or more
  • 1 is aluminum or boron
  • Non-limiting examples of the cocatalyst represented by the general formula (2) include methyl aluminoxane, ethyl aluminoxane, isobutyl aluminoxane and -butyl aluminoxane, and more preferred examples thereof include methyl aluminoxane.
  • Examples of the compound represented by the formula (3) include trimethyl aluminum, Tra-ethyl aluminum, triisobutyl aluminum, tripropyl aluminum, tributyl aluminum, dimethyl chloro-aluminum, tri-isopropyl aluminum, tri-butyl aluminum, tri-cyclopentyl-aluminum, tri Triphenyl aluminum, tri- 1> tolyl aluminum, dimethyl aluminum methoxide, dimethyl aluminum ethoxide, trimethyl boron, triphenyl aluminum, triisopentyl aluminum, triisopentyl aluminum, trioctyl aluminum, Triethylboron, triisobutylboron, tripropylboron, tributylboron and the like, and more preferred compounds are selected from trimethylaluminum, triethylaluminum and triisobutylaluminum. 2019/132450 1 »(: 1 ⁇ 1 ⁇ 2018/016504
  • Examples of the compound represented by Formula 4 include triethylammonium tetraphenylboron, tributylammonium tetraphenylboron, trimethylammonium tetraphenylboron, tripropylammonium tetraphenylboron, trimethylammonium tetra-tolyl) boron , Trimethylammoniumtetra ( 0, / 7- dimethylphenyl) boron, tributylammoniumtetra-trifluoromethylphenyl) boron, trimethylammoniumtetra-trifluoromethylphenyl) boron,
  • Triphenylcarbonium tetrakis pentafluorophenylboron and the like Triphenylcarbonium tetrakis pentafluorophenylboron and the like.
  • aluminoxane may preferably be used, and more preferably alkyl aluminoxane such as methyl aluminoxane
  • the cocatalyst can be used in an appropriate amount so that the activation of the metallocene compound, which is a catalyst precursor, can proceed sufficiently. 2019/132450 1 »(: 1 ⁇ 1 ⁇ 2018/016504
  • the metallocene catalyst of the present invention can be prepared by a method comprising: 1) contacting a metallocene compound represented by Formula 1 with a compound represented by Formula 2 or 3 to obtain a mixture; And 2) adding the compound represented by Formula 4 to the mixture.
  • the metallocene supported catalyst according to the present invention can be prepared by a method of contacting the metallocene compound represented by Formula 1 and the compound represented by Formula 2 as a second method.
  • the molar ratio of the metallocene compound represented by Formula 1 to the compound represented by Formula 2 or Formula 3 is preferably 1 / 5,000 to 1/2, More preferably from 1/1000 to 1/10, and most preferably from 1/500 to 1/20.
  • the amount of the alkylating agent is very small, If the molar ratio is less than 1/5000, the alkylation of the metal compound is performed, but the alkylated metal compound is not fully activated due to the side reaction between the excess alkylating agent and the activating agent.
  • the molar ratio of the metallocene compound represented by Formula 1 to the compound represented by Formula 4 is preferably 1/25 to 1, more preferably 1/10 to 1, and most preferably 1 / 5 to 1.
  • the molar ratio of the metallocene compound represented by Formula 1 to the compound represented by Formula 4 is more than 1, the amount of the activator is relatively small, There is a problem that the activity is inferior.
  • the molar ratio is less than 1/25, the activation of the metal compound is completely performed, but the unit price of the supported catalyst is insufficient due to the excess activating agent remaining or the purity of the produced polymer is low .
  • the ratio is preferably 1 / 10,000 to 1/10, more preferably 1 / 5,000 to 1/100, and most preferably 1/3 to 1/500.
  • the molar ratio exceeds 1/10
  • the activation of the metal compound is not achieved completely due to the relatively small amount of the activator, and the activity of the supported catalyst is low.
  • the metal catalyst is less than 1 / 10,000, There is a problem that the unit price of the zero-supported catalyst is not economical or the purity of the resulting polymer is low.
  • hydrocarbon solvents such as pentane, nucleic acid, heptane and the like or aromatic solvents such as benzene, toluene and the like may be used as a reaction solvent.
  • the amount of the metallocene compound is about 0.5 to about 20 parts by weight based on 100 parts by weight of the support
  • the cocatalyst is about 1 to about 1,000 parts by weight ≪ / RTI >
  • from about 1 to about 15 parts by weight of the metallocene compound and from about 10 to about 500 parts by weight of the cocatalyst may be included per 100 parts by weight of the support, and most preferably about 100 parts by weight of the support About 1 to about 100 parts by weight of the metallocene compound and about 40 to about 150 parts by weight of the cocatalyst.
  • the mass ratio of the total transition metal to the carrier contained in the metallocene compound may be 1:10 to 1: 1,000.
  • the weight ratio of the cocatalyst compound to the support may be in the range of 1: 1 to 1: 100.
  • the metallocene supported catalyst may further include additives and adjuvants commonly employed in the art to which the present invention belongs, in addition to the above-mentioned components.
  • a process for producing polypropylene comprising polymerizing propylenes in the presence of the metallocene supported catalyst. 2019/132450 1 »(: 1 ⁇ 1 ⁇ 2018/016504
  • the metallocene supported catalyst can provide a polypropylene having a narrow molecular weight distribution with high catalytic activity using a catalyst comprising a metallocene compound of the formula (1) containing an indene ligand having a specific substituent have.
  • the supported catalyst comprising the metallocene compound of Formula 1 has improved catalytic activity over conventional Ziegler-Natta catalysts or metallocene catalysts, and is capable of supporting the metallocene compound, that is, the reaction temperature, the reaction time, the type of silica ,
  • the polypropylene can be produced with improved activity even when the amount of the supported metallocene compound is changed.
  • the polymerization of propylenes can be carried out by reacting at a temperature of from about 25 to about 500 < 1 > and a pressure of from about 1 to about 1001 to about 111 2 for about 1 to about 24 hours.
  • the polymerization temperature is from about 25 to about 200 ⁇ 7 ⁇ is preferable, (about 50 to about 100 °:.
  • the polymerization pressure is from about 1 to about 701 3 ⁇ 4 £ 1 ⁇ 211 2 are preferred, about 5 to about 501 3 ⁇ 4 «! 1 2 is more preferable.
  • the polymerization reaction time is preferably about 1 to about 5 hours.
  • the process for producing the polypropylene of the present invention can be carried out by contacting propylenes with a catalyst containing a metallocene compound represented by the formula (1).
  • the polymerization of propylenes can be carried out under hydrogen gas.
  • the metallocene compound of the present invention is excellent in hydrogen reactivity, and therefore, polypropylene having a desired molecular weight and melt index can be effectively obtained by adjusting the amount of hydrogen gas used in the polymerization process.
  • the hydrogen gas may be introduced at a rate of from about 30 to about 2,000 psi, or from about 50 to about 1,5001 psi, or from about 50 to about 500 psi, based on the weight of propylene.
  • MI can be adjusted within a desired range, and accordingly, 2019/132450 1 »(: 1 ⁇ 1 ⁇ 2018/016504
  • Polypropylene having physical properties can be produced. More specifically, the metallocene catalyst of the present invention has very good hydrogen reactivity, thereby increasing the amount of hydrogen gas used, thereby activating the chain transfer reaction. As a result, a polypropylene having a reduced molecular weight and a high melt index can be obtained have.
  • the process for producing the polypropylene can be carried out 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 and the like.
  • the catalyst may be an aliphatic hydrocarbon solvent having 5 to 12 carbon atoms suitable for the polymerization process of the olefin monomer, such as pentane, nucleic acid, heptane, nonane, decane, An aromatic hydrocarbon solvent such as toluene or benzene, a hydrocarbon solvent substituted with a chlorine atom such as dichloromethane or chlorobenzene, or the like. It is preferable to use a small amount of water or air, which acts as a catalyst poison, by using a small amount of alkylaluminum.
  • the method for producing the polypropylene may further include a step that is commonly employed in the technical field to which the present invention belongs, in addition to the above-described steps. According to another embodiment of the present invention, there is provided a polypropylene obtained by the above-mentioned production method.
  • the catalyst containing the novel metallocene compound by using the catalyst containing the novel metallocene compound, it is possible to obtain polypropylene having a high polymerization activity without excellent processability and fouling, compared with the case of using a conventional metallocene compound Can be obtained.
  • the polypropylene can be used as a packaging container, a film, a sheet, a neck-piece, a fiber product and the like which have low processing temperature and excellent transparency and fluidity and thus require such characteristics.
  • the weight average molecular weight when a polymerization process of propylene is carried out using a catalyst containing the metallocene compound, it may vary from about 50,000 to about 1,000,000 / 1110 , or about 80,000, About 500,000 g / mol, preferably about 100,000 to about 300,000 g / mol. Further, the polypropylene produced according to the present invention can have a relatively narrow molecular weight distribution and a SPAN value.
  • the polypropylene prepared according to an embodiment of the present invention may have a molecular weight distribution value measured by GPC of about 3 or less, preferably about 2.6 or less, and a SPAN value measured by an optical diffraction particle size analyzer About 1 or less, preferably about 0.9 or less, more preferably about Q.1 to about 0.8.
  • the SPAN value means the width of the particle size distribution diagram.
  • the polypropylene has a small SPAN value and a uniform particle size. Accordingly, it is possible to manufacture a product having a high transparency and less problematic taste or smell problem have.
  • the polypropylene produced according to an embodiment of the present invention has a weight-average molecular weight of about 1 to about 10 g / 10 min, preferably about 1 to about 7 g, as measured at 230 ° C and 2.16 kg, And a melt index (MI) of 10 min / 10 min.
  • MI melt index
  • such properties can be easily controlled according to the amount of hydrogen used in the polymerization process, , A molecular weight distribution, and a melt property.
  • Step 1 4- (6- (dichloro (methyl) silyl) hexyl) -N, N- synthesis
  • Step 1 Step 1: 4- (6- (bis (4- (4- (tert-butyl) phenyl) -2-methyl-1H- inden- -dimethylaniline synthesis
  • Step 1-3 Preparation of [4- (6- (bis (4- (4- (tert-butyl) phenyl) -2- yl) (methyl) silyl) hexyl) -N, N-dimethylaniline] Zirconium dichloride Synthesis
  • Phenyl) -2-methyl-1H-inden-1-yl) (methyl) silyl) hexyl) -N, N-dimethylaniline (6.74 g, , 9.83 mmol) was dissolved in argon (Ar) in a 50 mL Schlenk flask and diethyl ether (8.2 mL) was poured in. The temperature was lowered to -78 ° C and n-BuLi (2.5 M in hexane, 8.1 mL) was added thereto, followed by stirring at room temperature for 2 hours.
  • the metallocene compound (70 or 1 part 1) obtained in the above step 1-3 was dissolved in toluene (2011 part), and then the upper flask was equipped with a cannula rack 1111111 , And washed with toluene (511). After stirring at 501: for 5 hours, the mixture was cooled to room temperature, left for 15 minutes, and then the solvent in the upper layer was removed. Toluene (2511) was added, stirred for 3 minutes, left for 10 minutes, and the solvent in the upper layer was removed once.
  • dimethylaminoniumtetrakispentafluorophenylboron (13511/4) was dissolved in toluene (200 ° C) and then added to the flask using a cannula ( 11 ) and washed with toluene Respectively. After stirring for 5 hours at 5 ° C, the reaction mixture was cooled to room temperature, left for 10 minutes, and then the solvent was removed from the upper layer. The reaction mixture was stirred for 3 minutes and then left for 10 minutes, followed by removing the solvent in the upper layer. The same procedure was followed by the addition of nucleic acid (2511), stirring for 1 minute,
  • the supported metallocene compound obtained in the above step 1-3 was supported on methyl aluminoxane supported on silica by the following method to prepare a supported catalyst.
  • silica 3 was placed in a flask of 250 shore flasks in argon) was slowly injected at room temperature into methylaluminoxane show 0, 1911, 811111101)
  • Step 2-1 Preparation of (6- (tert-butoxy) hexyl) bis (4- (4- (tert- butyl) phenyl) -2-methyl-
  • the supported metallocene compound obtained in the step 2-2 was supported on silica supported on silica by the following method to prepare a supported catalyst.
  • silica (3 g) was placed in a 250 mL Schlenk flask under argon, and methylaluminoxane (MAO, 19 mL, 8 mmol) was slowly added at room temperature and stirred at 90 ° C for 18 hours. After completion of the reaction, the reaction mixture was cooled to room temperature and allowed to stand for 15 minutes. Then, the solvent in the upper layer was removed.
  • the metallocene compound (70 or 11101) obtained in the above step 2-2 was dissolved in toluene (20 mL), and the solution was stirred at room temperature for 3 minutes. After the solution was stirred for 3 minutes, the solvent in the upper layer was removed.
  • the can was added to the flask using a cannula and washed with toluene (5 mL). At 50 ° C
  • the supported metallocene compound obtained in the step 2-2 was supported on silica supported on silica by the following method to prepare a supported catalyst.
  • the metallocene compound (70 ⁇ 11101) on the metal obtained in the above 2-2 was dissolved in toluene (2011 ⁇ ) Then, a cannula 3 on the flask above! In using the 11111) and washed with toluene (5 11 ⁇ ). After stirring at 501: for 5 hours, it was cooled to room temperature and left for 15 minutes, and the solvent in the upper layer was removed. Put the toluene (25 11 ⁇ ) was stirred for 3 min and was carried out once the removal of the solvent in the upper layer was allowed to stand for 10 minutes. Into the nucleic acid (25 11 ⁇ ) in the same manner stirred for 1 minute and remove the solvent in the upper layer was allowed to stand for 20 minutes, and dried overnight then vacuum dried for 4 hours in an additional 45 ° 0.
  • each of the supported metallocene catalyst of 0.03 (the TMA prescribed nucleic acid 20 11 ⁇ as manufactured by Nitrogen pressure was applied to the reactor. After the reactor temperature was gradually increased to 70 ° C, the reactor was polymerized for 1 hour under a hydrogen input of 337 ppm and a pressure of 35 kg / cm 2 .
  • Catalytic activity Calculated as the ratio of the weight of the polymer produced per unit time (the catalyst content (mmol and g) of the catalyst used as the ratio (kg).
  • the metallocene compound according to the present invention as a supported catalyst exhibited a high activity in the production of polypropylene.
  • the aluminum borate-based co-catalyst was not used separately, Indicating that the activity was not significantly different.
  • Example 1 shows a relatively narrow molecular weight distribution even when compared with Comparative Example 1 in which other tether groups are introduced . It was confirmed that a homogeneous polypropylene having a low value of VII and a high value of a value and a show value can be produced.

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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 porte sur un nouveau catalyseur supporté contenant un composé métallocène, le catalyseur présentant une excellente activité de polymérisation, et sur un procédé de préparation de polypropylène par polymérisation de propylène en présence du catalyseur. Le catalyseur métallocène supporté selon la présente invention peut produire du polypropylène ayant une répartition de masse moléculaire relativement étroite et une valeur SPAN.
PCT/KR2018/016504 2017-12-26 2018-12-21 Catalyseur métallocène supporté et procédé de préparation de polypropylène faisant appel à celui-ci WO2019132450A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
CN201880083882.9A CN111556878B (zh) 2017-12-26 2018-12-21 负载型茂金属催化剂和使用该催化剂制备聚丙烯的方法
US16/957,962 US11358979B2 (en) 2017-12-26 2018-12-21 Metallocene-supported catalyst and method for preparing polypropylene using the same
EP18895226.1A EP3715382B1 (fr) 2017-12-26 2018-12-21 Catalyseur métallocène supporté et procédé de préparation de polypropylène faisant appel à celui-ci

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KR20170180268 2017-12-26
KR10-2017-0180268 2017-12-26
KR10-2018-0166737 2018-12-20
KR1020180166737A KR102343937B1 (ko) 2017-12-26 2018-12-20 메탈로센 담지 촉매 및 이를 이용한 폴리프로필렌의 제조 방법

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US5032562A (en) 1989-12-27 1991-07-16 Mobil Oil Corporation Catalyst composition and process for polymerizing polymers having multimodal molecular weight distribution
WO1996016069A1 (fr) * 1994-11-22 1996-05-30 Fina Research S.A. Metallocenes pontes utiles dans des systemes de catalyseurs destines a la polymerisation d'olefines
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
KR200312308Y1 (ko) 2003-02-06 2003-05-09 주식회사 제일 유브이 유턴형 컨베이어 자외선 경화기
WO2014169017A1 (fr) * 2013-04-11 2014-10-16 Exxonmobil Chemical Patents Inc. Procédé de fabrication de polyoléfines à l'aide de catalyseurs de polymérisation métallocène et copolymères obtenus par ce procédé
KR20160101062A (ko) * 2014-02-13 2016-08-24 미쓰이 가가쿠 가부시키가이샤 에틸렌/α-올레핀 공중합체의 제조 방법
KR20160103042A (ko) * 2014-02-13 2016-08-31 미쓰이 가가쿠 가부시키가이샤 에틸렌·α-올레핀·비공액 폴리엔 공중합체 및 그의 용도, 및 그의 제조 방법

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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
WO1996016069A1 (fr) * 1994-11-22 1996-05-30 Fina Research S.A. Metallocenes pontes utiles dans des systemes de catalyseurs destines a la polymerisation d'olefines
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
KR200312308Y1 (ko) 2003-02-06 2003-05-09 주식회사 제일 유브이 유턴형 컨베이어 자외선 경화기
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