WO2020091177A1 - Nouveau composé de métal de transition et procédé de préparation de polypropylène l'utilisant - Google Patents

Nouveau composé de métal de transition et procédé de préparation de polypropylène l'utilisant Download PDF

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WO2020091177A1
WO2020091177A1 PCT/KR2019/007152 KR2019007152W WO2020091177A1 WO 2020091177 A1 WO2020091177 A1 WO 2020091177A1 KR 2019007152 W KR2019007152 W KR 2019007152W WO 2020091177 A1 WO2020091177 A1 WO 2020091177A1
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Prior art keywords
transition metal
group
metal compound
formula
alkyl
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PCT/KR2019/007152
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English (en)
Korean (ko)
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김병석
이인선
김석환
이혜경
전상진
김세영
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주식회사 엘지화학
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Priority claimed from KR1020190069233A external-priority patent/KR102431269B1/ko
Application filed by 주식회사 엘지화학 filed Critical 주식회사 엘지화학
Priority to EP19879818.3A priority Critical patent/EP3786195B1/fr
Priority to US17/251,026 priority patent/US11370851B2/en
Priority to CN201980034296.XA priority patent/CN112154163B/zh
Publication of WO2020091177A1 publication Critical patent/WO2020091177A1/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
    • C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F110/04—Monomers containing three or four carbon atoms
    • C08F110/06—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
    • C08F4/659—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 novel transition metal compound and a method for producing polypropylene using the same.
  • the olefin polymerization catalyst system can be classified into a Ziegler-Natta catalyst system and a metallocene catalyst system, and these two highly active catalyst systems have been developed to suit each characteristic. Since the Ziegler Natta catalyst is a multi-activation catalyst with multiple active sites, the molecular weight distribution of polymers produced using this is characterized by a wide molecular weight distribution, and the composition distribution of the comonomer is not uniform. There is a problem that there is a limit to securing desired properties.
  • the metallocene catalyst is composed of a cocatalyst combination of a main catalyst mainly composed of a transition metal compound and an organometallic compound mainly composed of aluminum.
  • Metallocene catalysts are homogeneous complex catalysts and are single-site catalysts. Accordingly, the polymer produced using the metallocene catalyst has a narrow molecular weight distribution and a uniform composition distribution of the comonomer. In addition, it is possible to change the stereoregularity, copolymerization properties, molecular weight, crystallinity, etc. of the polymer produced through modification of the ligand structure and the polymerization conditions in the metallocene catalyst.
  • V0C volatile organic compounds
  • a transition metal compound represented by Chemical Formula 1 is provided:
  • Urine is carbon (or silicon ());
  • 01-20 is substituted with alkyl, or 01-20 alkyl or unsubstituted 0 6-20 2020/091177 1 »(: 1 ⁇ 1 ⁇ 2019/007152
  • ⁇ And are each independently 01-20 alkyl
  • X 1 and X 2 are each independently halogen.
  • a catalyst composition comprising the transition metal compound.
  • the catalyst composition comprising the step of polymerizing a propylene monomer by introducing hydrogen, provides a method for producing homo polypropylene.
  • the transition metal compound according to the invention is 361 years 0 02 - get the "structure of Symmetr ic, shows excellent catalytic activity when used as a polymerization catalyst for the production of polypropylene, it is possible to also improve the impact strength of the polypropylene is prepared .
  • the transition metal compound can reduce 170 (:) generated in the production process of polypropylene.
  • transition metal compound according to a specific embodiment of the invention, it 2020/091177 1 »(: 1 ⁇ 1 ⁇ 2019/007152
  • transition metal compound according to an embodiment of the present invention is represented by the following Chemical Formula 1:
  • ⁇ And parent 4 are each independently 01-20 alkyl
  • X 1 and X 2 are each independently halogen.
  • halogen is fluorine (, chlorine ( ⁇ ), bromine () or iodine (I) 2020/091177 1 »(: 1 ⁇ 1 ⁇ 2019/007152
  • the 01-20 alkyl group may be a straight chain, branched or cyclic alkyl group. Specifically, 0 1-20 alkyl group is 0 1-15 straight chain alkyl group; 0 1-10 straight chain alkyl group; 0 1-5 straight chain alkyl group; 03 -20 branched or cyclic alkyl group; 03 -15 branched or cyclic alkyl group; Or 0 3-10 branched or cyclic alkyl.
  • (: 1_20 alkyl group is methyl group, ethyl group, 11-propyl group, -Profile group, 11-butyl group, 0-butyl group, 16_butyl group, 11-pentyl group, 11 ⁇ 20-pentyl group or cyclonuclear group.
  • 0 2-20 alkenyl group may be a straight chain alkenyl, branched or cyclic Al. Specifically, 0 2-20 0 2-20 straight-chain alkenyl group an alkenyl group, an 0 2-10 straight chain alkenyl, straight chain alkenyl groups 02-5, 0 3-20 branched alkenyl, branched alkenyl groups 03 -15 , 0 3-10 branched alkenyl group, 3 ⁇ 4- 20 cyclic alkenyl group or (: 5-10 cyclic alkenyl group. More specifically, the alkenyl group of C2-20 may be an ethenyl group, a propenyl group, a butenyl group, a pentenyl group, or a cyclonuclear group.
  • 0 6-30 aryl may mean an aromatic hydrocarbon between mono-, bi- or tri. Specifically, 0 6-30 aryl may be a phenyl group, a naphthyl group or an anthracenyl group.
  • 0 7-30 Alkylaryl may mean a substituent in which one or more hydrogens of aryl are substituted by alkyl.
  • 0 7-30 alkylaryl is methylphenyl, ethylphenyl, propylphenyl, -Propylphenyl, 11-butylphenyl, It may be a butyl phenyl or cyclohexyl phenyl.
  • 0 7-30 aryl may be the hydrogen of one or more alkyl substituents, by means a substituted aryl group.
  • 0 7-30 arylalkyl may be a benzyl group, phenylpropyl or phenyl nucleus.
  • the transition metal compound of Formula 1 in the polymerization of polypropylene While having a structure, it is possible to realize all the characteristics of each ligand of both indene structures.
  • the transition metal compound of Chemical Formula 1 is a bridge group connecting two indene structural ligands, and includes a divalent functional group A substituted with alkyl groups (R 3 and R 4 ) having 1 or more carbon atoms. Accordingly, the atomic size is increased, the available angle is increased, and it is possible to exhibit better catalytic activity due to easy access to monomers during polymer production.
  • one of the two indene structural ligands is substituted with R 1 at position 3, and the other ligand is replaced with methyl and R 2 at positions 2 and 4, respectively.
  • Two ligand structures are different and have an asymmetric structure. Accordingly, when manufacturing the polypropylene polymer, it is possible to exhibit an effect of lowering the melting point by controlling the tact ici ty in the molecular structure.
  • the polymer to be prepared may exhibit a narrower molecular weight distribution.
  • Substituent R 1 at position 3 is specifically, C ⁇ o or C 3-1 () alkyl; Or Ci- 20 or C 6 ⁇ aryl substituted or unsubstituted with Ci- 2 o alkyl.
  • the substituent is C 3-i o or C 4-i o straight-chain alkyl such as n-butyl and n-heptyl; Cs-io pulverized alkyl such as isopropyl, t-butyl, etc .; Phenyl; Or t- butylphenyl C 3, such as-may be a phenyl substituted by 6 branched alkyl, it can exhibit a high catalytic activity than the above-described functional group.
  • position 2 is methyl
  • Position 4 may be substituted with a functional group R 2 , specifically C 6-20 aryl substituted with Ci- 20 alkyl.
  • R 2 in formula (I) may be a phenyl group substituted with a C 3-6 branched alkyl, such as tert- butylphenyl, and the substitution position of C 3 -6 branched alkyl group on the phenyl group, R 2 It may be the 4th position corresponding to the position and the para position.
  • the transition metal compound of Chemical Formula 1 may include a Group 4 transition metal such as zirconium (Zr) or hafnium (Hf) as the center metal (M). 2020/091177 1 »(: 1/10 ⁇ 019/007152
  • the transition metal compound contains zirconium ( ⁇ ) as the center metal, it has a higher affinity because it has more orbitals capable of accepting electrons, as compared to the case of other group 4 transition metals such as It can be combined with a monomer, and as a result, it can exhibit a better catalytic activity improvement effect.
  • X 1 and X 2 may be each independently chloro.
  • the show may be more specifically silicon (), and the substituents ⁇ and for the show are the same as each other in terms of improving the solubility by increasing solubility, and may be alkyl. Specifically, 0 1-4 straight-chain alkyl, and more specifically, each may be a methyl group.
  • the same alkyl group as each other as a substituent for the show of the bridge group it is excellent in solubility in preparing the supported catalyst, and can exhibit improved loading reactivity.
  • transition metal compound of Formula 1 include compounds having the following structure:
  • the transition metal compound of Chemical Formula 1 may be prepared by reacting a ligand compound of Chemical Formula 2 with a group 4 transition metal-containing halide:
  • Reaction Scheme 1 shows a ligand compound used in the preparation of the transition metal compound according to an embodiment of the present invention, and a process for preparing the transition metal compound using the ligand compound.
  • Scheme 1 below is only an example for illustrating the present invention, and the present invention is not limited thereto.
  • the first indene compound (I) in which position 3 is substituted with a functional group of parent 1 is butyl lithium (11 in 1 ! Ni), in the presence of an alkyl lithium, such as dimethyldichlorosilane, reacting with a bridge group providing compound (II), to prepare a bridge group bonded indene compound (III);
  • the bridged bond-indene compound (III) is substituted with methyl and urine 2 at positions 2 and 4, respectively, in the presence of alkyl lithium such as butylium (11 to 11 teeth) and (: ⁇ ) Reacting with the diindene compound (IV) to prepare the ligand compound (2) of Formula 2; and reacting the ligand compound (2) with a halide containing a Group 4 transition metal such as 3 ⁇ 4 (: 1 4 )
  • the step of preparing the transition metal compound (1) of Formula 1 may be prepared by a manufacturing method comprising a.
  • reaction in each step may be performed by applying known reactions.
  • reaction in each step may be performed by applying known reactions.
  • the transition metal compound of Formula 1 is Due to its structure, it is three-dimensionally regular and has a narrow molecular weight distribution, showing excellent impact strength. 2020/091177 1 »(: 1 ⁇ 1 ⁇ 2019/007152
  • Polypropylene can be produced.
  • the transition metal compound may reduce the amount of 170: generated in the polymer manufacturing process.
  • a catalyst composition comprising the above-described transition metal compound is provided.
  • the catalyst composition includes the transition metal compound of Formula 1 as a single catalyst. Accordingly, compared with the case of mixing and using two or more types of catalysts, the molecular weight distribution of the polymer to be produced is significantly narrowed, so that the strength characteristics can be improved.
  • the transition metal compound may be used as a single component or may be used in the form of a supported catalyst supported on a carrier.
  • the transition metal compound is used in the form of a supported catalyst, it is possible to further improve the morphology and physical properties of the produced polypropylene, and can also be suitably used for slurry polymerization, bulk polymerization, and gas phase polymerization processes.
  • a carrier having a hydroxy group, a silanol group, or a siloxane group having high reactivity on the surface may be used, and for this purpose, the surface may be modified by calcination ( ⁇ 1 (: ⁇ 3 011)), or dried. It can be used in "the moisture is removed.
  • silica produced by calcining silica gel, silica dried at high temperature, silica-alumina, and silica-magnesia can be used, and these are typically 2 0, 3 ⁇ 4 ⁇ 3 , ⁇ and 3 ⁇ 4 ⁇ 0 ⁇ 3 ) 2, etc. It may contain oxide, carbonate, sulfate, and nitrate components.
  • the temperature may be 200 to 600, and 250 to 600 Can be.
  • the calcination or drying temperature for the carrier is 200 If it is as low as below, there is a possibility that the moisture remaining on the carrier is too large and the surface moisture and the co-catalyst may react, and the co-catalyst loading rate may be relatively high due to the hydroxyl group present in excess. A positive cocatalyst is required.
  • the drying or calcination temperature is too high, in excess of 6001 :, the surface area decreases as the pores on the surface of the carrier are merged, and a lot of hydroxyl groups or silanol groups disappear on the surface. May decrease. 2020/091177 1 »(: 1 ⁇ 1 ⁇ 2019/007152
  • the amount of hydroxy groups on the surface of the carrier can be controlled by the method and conditions of the carrier or drying conditions, such as temperature, time, vacuum or spray drying. If the amount of the hydroxy group is too low, there are fewer reaction sites with the cocatalyst, and if it is too large, it may be due to moisture other than the hydroxy group present on the surface of the carrier particle. In one example, the amount of hydroxy groups on the surface of the carrier may be 0. 1 to 10_01 ⁇ or 0.5 to 5 0111101 / dragon.
  • the transition metal compound is included in the catalyst composition in the form of a supported catalyst, the transition metal compound is per carrier weight, for example, based on 1 for silica, 10 11 11101 or more, or 30 Or more, and may be supported in a content range of 100 11101 or less, or 80 ⁇ 1 ⁇ ) 1 or less.
  • the transition metal compound shows an appropriate supported catalytic activity, which can be advantageous in terms of maintaining the activity of the catalyst and economical efficiency.
  • the catalyst composition may further include a cocatalyst in terms of improving high activity and process stability, in addition to the transition metal compound and carrier.
  • the cocatalyst may include one or more of the compounds represented by the following Chemical Formula 3, Chemical Formula 4 or Chemical Formula 5.
  • 2 may be the same or different from each other, and each independently halogen; 0 1-20 hydrocarbon group; Or a halogen substituted -20 hydrocarbon;
  • the seedling is a neutral or cationic Lewis base
  • ⁇ is a group 13 element
  • each independently one or more hydrogen atoms are halogen, -2 () hydrocarbon, alkoxy or phenoxy substituted or unsubstituted, (: 6-2 () aryl group or -2 ( ) .
  • Examples of the compound represented by Formula 3 include methyl aluminoxane, ethyl aluminoxane, isobutyl aluminoxane, or alkyl aluminoxane-based compounds such as butyl aluminoxane, any one or a mixture of two or more of which Can be used.
  • examples of the compound represented by Chemical Formula 4 include trimethyl aluminum, triethyl aluminum, triisobutyl aluminum, tripropyl aluminum, tributyl aluminum, dimethylchloro aluminum, triisopropyl aluminum, tri _ aluminum, tricyclopentyl aluminum, Tripentyl aluminum, triisopentyl aluminum, trinuclear aluminum, trioctyl aluminum, ethyl dimethyl aluminum, methyl diethyl aluminum, triphenyl aluminum, tri-tolyl aluminum, dimethyl aluminum methoxide, dimethyl aluminum ethoxide, trimethyl boron, tri Ethyl boron, triisobutyl boron, tripropyl boron, tributyl boron, and the like, and more specifically, may be selected from trimetal aluminum, triethyl aluminum, and triisobutyl aluminum.
  • examples of the compound represented by the formula (5) is triethyl ammonium tetraphenyl boron, tributyl ammonium tetraphenyl boron, 2020/091177 1 »(: 1 ⁇ 1 ⁇ 2019/007152
  • Trimethylammonium tetra (trifluoromethylphenyl) aluminum Trimethylammonium tetra (trifluoromethylphenyl) aluminum.
  • the above mixture can be used.
  • the cocatalyst is a compound represented by Chemical Formula 3, more specifically 0 1 such as methylaluminoxane.
  • -20 may be an alkyl aluminoxane-based compound.
  • the alkyl aluminoxane-based compound acts as a scavenger (613 ⁇ 4 d) of hydroxyl groups present on the surface of the carrier to catalyze 2020/091177 1 »(: 1 ⁇ 1 ⁇ 2019/007152
  • the cocatalyst may be supported in an amount of 8 ⁇ 01 or more, or 1011 ⁇ 01 or more, and 25 ⁇ 01 or less, or 20 ⁇ 01 or less based on the weight of carrier, for example, for silica 1.
  • carrier for example, for silica 1.
  • the catalyst composition may further include an antistatic agent.
  • an antistatic agent specifically, an ethoxylated alkylamine represented by the following Chemical Formula 6 may be used, and in addition, any component known as an antistatic agent may be used without limitation.
  • the catalyst composition includes an antistatic agent, the generation of static electricity is suppressed in the polypropylene polymerization process, so that physical properties of the produced polypropylene can be further improved.
  • silver may be 8-30 alkyl, and when ⁇ contains an alkyl group having a carbon number in the above range, it may exhibit a fine powder reducing effect through an excellent antistatic action without causing unpleasant odor.
  • the ethoxylated alkyl amines or seedlings 7 in the formula (6) is a straight chain alkyl of 3 ⁇ 4- 22, or (in: 12 to 18 straight chain alkyl, or (: 13-15 straight-chain alkyl of one One of these compounds alone or a mixture of two or more may be used.
  • commercially available company 111ra 163 manufactured by 0 ⁇ may be used.
  • an antistatic agent when further included, it may be included for 1 to 13 ⁇ 4, more specifically for 1 to 5 based on the carrier 101 ⁇ 2.
  • the catalyst composition when the catalyst composition includes both the above-described carrier, cocatalyst, and antistatic agent, the catalyst composition may include supporting a cocatalyst compound on a carrier, and supporting the transition metal compound on the carrier; And injecting an antistatic agent in a slurry state and heat-treating the carrier on which the cocatalyst and the transition metal compound are supported; and may be prepared by a manufacturing method.
  • the supported catalyst having a structure determined according to the loading order is 2020/091177 1 »(: 1 ⁇ 1 ⁇ 2019/007152
  • the catalyst composition may be used in a slurry (h) state in a solvent or in a diluted state depending on a polymerization method, or may be used in the form of a mud catalyst mixed with a mixture of oil and grease.
  • the solvent is an aliphatic hydrocarbon solvent having 5 to 12 carbon atoms suitable for the polymerization process of propylene monomers, such as pentane, nucleic acid, heptane, nonane, decane, and Isomers and aromatic hydrocarbon solvents such as toluene and benzene, or hydrocarbon solvents substituted with chlorine atoms such as dichloromethane and chlorobenzene, and any one or a mixture of two or more thereof may be used.
  • the catalyst composition may further include the above-described solvent, and a small amount of alkyl aluminum may be removed from the solvent before use to remove a small amount of water or air that can act as a catalyst poison.
  • the catalyst composition may be used in the form of a mud catalyst mixed with a mixture of oil and grease.
  • the amount of the volatile organic compound contained in the produced homo polypropylene can be further reduced compared to the case where it is dissolved or diluted in a solvent, and as a result, the odor resulting from the volatile organic compound is also reduced. I can do it.
  • the catalyst composition having the above configuration can reduce the amount of mc generated during the production of homopolypropylene, and increase the impact strength.
  • a method for producing homo polypropylene using a catalyst composition comprising the transition metal compound of Chemical Formula 1, and a polypropylene prepared accordingly are provided.
  • the production method of the polypropylene includes the step of polymerizing a propylene monomer by introducing hydrogen in the presence of the catalyst composition comprising the transition metal compound of Formula 1 above.
  • the polymerization process is performed by contacting the catalyst composition and propylene under hydrogen gas. 2020/091177 1 »(: 1 ⁇ 1 ⁇ 2019/007152
  • the hydrogen gas may be introduced in an amount of 50 to 700 ⁇ m based on the total weight of the propylene monomer.
  • the hydrogen gas is 70 ⁇ ! n or more, or 103 ⁇ 4)! L or more, and may be added in a content of 50 ⁇ ⁇ 1 or less, or 303 ⁇ 4) ⁇ 1 or less.
  • the polymerization process may be performed by a continuous polymerization process, for example, a variety of polymerization processes known as polymerization reactions of olefin monomers such as a continuous solution polymerization process, a bulk polymerization process, a suspension polymerization process, a slurry polymerization process or an emulsion polymerization process.
  • a continuous bulk-slurry polymerization process may be preferable in terms of obtaining a uniform molecular weight distribution and commercial production of the product.
  • the polymerization reaction above it can be carried out at a temperature of 1101: or less or 1001: or less, and further controlling pressure conditions, Or more, or 30 13 ⁇ 4 ⁇ : or more, 100 13 ⁇ 4 "011 2 or less, or
  • a trialkyl aluminum such as triethyl aluminum may be selectively added during the reaction.
  • alkyl is as defined above, specifically, is alkyl, and more specifically, it may be a straight or branched chain alkyl of -6 such as detyl, ethyl, isobutyl, and the like.
  • trialkyl aluminum is the total amount of the propylene monomer With respect to the weight of 300 ppm or more, or 400 ppm or more, it may be added in a content of 600 ppm or less, or 450 ppm or less, and in the presence of trialkyl aluminum in this content range, homo polypropylene having excellent strength characteristics is superior to polymerization. It can be easily manufactured.
  • Homo polypropylene according to an embodiment of the invention produced by the above-described manufacturing method may exhibit increased strength characteristics with excellent workability.
  • the homo polypropylene can exhibit excellent processability by exhibiting a low melting temperature (Tm) of 145 ° C or less, and accordingly, it is possible to lower the processing temperature during the processing process using the homo polypropylene, thereby reducing the effect of energy slicing 1 . It can be obtained and blending is easy.
  • the melting temperature or melting point can be determined immediately using a differential scanning calorimeter (DSC). Specifically, after increasing the temperature of the homo polypropylene to 200 ° C,
  • the temperature was lowered to 30 ° C, and the temperature was increased again to measure the temperature at the top of the DSC (Di f ferent i al Scanning Calorimeter, TA) curve as the melting point. can do.
  • the speed of the temperature rise and fall is 10 ° C / min, respectively, the melting point is the result measured in the second temperature rise section.
  • the homo polypropylene produced by the above production method has a high weight average molecular weight of 340,000 g / mol or more and a melt index of 7 g / 10 min or less (2.16 kg at 23 CTC according to ASTM D1238) under the conditions of inputting 100 ppm of hydrogen gas during polymerization. (Measured by load).
  • a high weight average molecular weight 340,000 g / mol or more
  • a melt index of 7 g / 10 min or less 2.16 kg at 23 CTC according to ASTM D1238)
  • the homo polypropylene produced by the above-described manufacturing method shows a narrow molecular weight distribution of 2.7 or less together with the above-mentioned melting temperature, melting index and weight average molecular weight. As a result, excellent stiffness and impact strength characteristics can be exhibited.
  • the weight average molecular weight (Mw) and molecular weight distribution (MWD) of the homo polypropylene can be measured using gel permeation chromatography (GPC), and MWD is the weight average molecular weight (Mw) and number. After measuring the average molecular weight (Mn), it can be determined by the ratio of the weight average molecular weight to the number average molecular weight (Mw / Mn).
  • the evaluation temperature is 160 ° C
  • 1,2,4 -trichlorobenzene is used as a solvent
  • the flow rate is lmL / min.
  • the sample is prepared at a concentration of lOmg / lOmL, and then supplied in an amount of 200 uL.
  • the values of Mw and Mn are derived using an assay curve formed using polystyrene standards.
  • the molecular weight of the polystyrene standard U / mol was 2,000 / 10,000 / 30,000 / 70,000 / 200, 000/700, 000 / 2,000,000 / 4,000, 000/10, 000, 00 ⁇ .
  • the homo polypropylene according to an embodiment of the present invention exhibits excellent melt processability when molding into various products such as various molded articles, as it has a low melting temperature and a melt index, and a narrow molecular weight distribution and a high weight average molecular weight. It can also exhibit improved mechanical properties such as high impact strength.
  • a molded article comprising the above-mentioned homo polypropylene is provided.
  • the product can be prepared according to conventional methods, except for using the homo polypropylene of one embodiment described above.
  • preferred embodiments are presented to help understanding of the present invention. However, the following examples are only for illustrating the present invention, and the contents of the present invention are not limited by the following examples.
  • Step 1 Preparation of dimethylsilanediyl (3 -phenyl-1H-indene-1yl) (2 -methyl- 4- (4-tert-butylphenyl) -1H-indene)
  • Step 2 Preparation of dimethylsilanediyl (3 -phenyl-1H-indene-1yl) (2 -methyl- 4- (4-tert-butylphenyl) -1H-indene-1yl) zirconium dichloride
  • the ligand prepared above was dissolved in a mixed solution of toluene / diethyl ether (2/1 volume ratio, 0.53M) and n-BuLi (2.05eq) was added at -25 ° C. 2020/091177 1 »(: 1/10 ⁇ 019/007152
  • step 1 of Preparation Example 1-1 except that 3- 0 -propyl-vs_indene is used instead of 3 -phenyl-111-indene, the same method as in Preparation Example 1-1 is performed, Dimethylsilanediyl of the above structure (3- 0 -propyl- 1) (2 -methyl- 4- (4 hema 6 -butylphenyl)--inden-1 -yl) zirconium dichloride was prepared.
  • Step 1 of Preparation Example 1-1 except for using 3-11-propyl-in-inden instead of 3 -phenyl-111-indene, in the same manner as in Preparation Example 1-1, Dimethylsilanediyl (3-11 -propyl- 111-inden-1 -yl) (2 -methyl- 4- (4a6 _butylphenyl) -in_indene-1yl) zirconium dichloride was prepared.
  • Step 1 Preparation of dimethylsilanediyl (vs-inden-1-yl) (2-methyl- 4- (4a6-butylphenyl) _in_inden)
  • Methyl- 4- (4a6 _ butylphenyl) indene (2-1 (-4- (4-1;-8 3 ⁇ 4) 1 11 ( 16116) (1 6 (!)
  • Toluene / ⁇ mixed solution (5 / After dissolving in 1 volume ratio, 0.73 ⁇ 41), 11-61111 (1.05 6 (!)) was slowly added dropwise to -251: and stirred at room temperature for 3 hours.
  • the ligand prepared above was dissolved in a mixed solution of toluene / diethyl ether (2/1 volume ratio, 0.53 cc), and then 11-11 teeth (2.05 roots) were added at -251: and stirred at room temperature for 5 hours.
  • a slurry prepared by mixing ⁇ (: 1 4 (1 6 (!) In toluene (0.17 3 ⁇ 40) in a separate flask was added at -25, and stirred at room temperature overnight.
  • the solvent was vacuum dried, 1X1 was re-injected, and after removing the needle (: 1) through a filter, the filtrate was vacuum dried, and 1X1 / nucleic acid was added to recrystallize at room temperature. Thereafter, the resulting solid was filtered and dried in vacuo to obtain the titled transition metal compound in the solid phase.
  • Step 2 Preparation of dimethylsilanediyl (4- (4-tert-butylphenyl) -1H-indene-1yl) (2-methyl- 4- (4-tert-butylphenyl) -1H-indene) 2020/091177 1 »(: 1 ⁇ 1 ⁇ 2019/007152
  • Step 3 Dimethylsilanediyl (4- (4a6 _butylphenyl) -in-inden-1-yl) (2 -methyl- 4- (4 6-butylphenyl)-: in-inden-1-yl ) Preparation of zirconium dichloride
  • the ligand prepared above was dissolved in a toluene / diethyl ether mixed solution (2/1 volume ratio, 0.533 ⁇ 40, and then _25 (2.05 6 (! Rules were added and stirred at room temperature for 5 hours.
  • the solvent was vacuum dried, 1X1 was re-introduced, and after removing the knee through a filter, the filtrate was vacuum dried, and 1X1 / nucleic acid was added to recrystallize at room temperature. Then, the resulting solid was filtered and dried in vacuo to obtain the titled transition metal compound in the solid phase.
  • Step 1 Preparation of 7- (4'-tert-butylphenyl) -2 -methyl- 1-indanon
  • Step 3 Dimethylsilanediyl (2.3 -dimethyl-1H-inden-1-yl) (2 -methyl-4- (4- 2020/091177 1 »(: 1 ⁇ 1 ⁇ 2019/007152! :-Butylphenyl) -in-inden)
  • Step 4 Dimethylsilane diyl (2, 3-dimethyl-in-inden-1-yl) (2-methyl- 4- (4-la!:-Butylphenyl) -in_inden-1-yl) zirconium di Preparation of chloride
  • the ligand prepared above was dissolved in a toluene / diethyl ether mixed solution (2/1 volume ratio, 0.533 ⁇ 40, and then added at -251: gani (about 2.05)) and stirred at room temperature for 5 hours.
  • a toluene / diethyl ether mixed solution (2/1 volume ratio, 0.533 ⁇ 40, and then added at -251: gani (about 2.05)) and stirred at room temperature for 5 hours.
  • gani about 2.05
  • the solvent was vacuum dried, 1X1 was re-injected, and after removing the needle (: 1 through the filter, the filtrate was vacuum dried and recrystallized at room temperature by adding £ 01 / nucleic acid. Thereafter, the resulting solid was filtered and dried in vacuo to obtain the titled transition metal compound in the solid phase.
  • Step 3 of Comparative Production Example 1-4 except that 2, 3 -dimethyl-4- (4-butylphenyl) -in_indene was used instead of 2, 3 -dimethyl-in-indene.
  • dimethylsilanediyl (2,3-dimethyl- 4- (4ara ⁇ butylphenyl) -111-indene-1 -yl) (2 -methyl- 4- (4A-Butylphenyl) _ Dae-Inden-1-yl) Zirconium dichloride was prepared.
  • Step 1 Preparation of dimethylsilanediyl bis (3-propyl-1H-indene) (Dimethylsi lanediyl bi s (3-propyl-lH-indene)
  • n-BuLi (1.05 eq) was slowly added dropwise at -25 ° C, and then 3 at room temperature. Stir for hours. Subsequently, CuCN (2 mol%) was added, stirred for 30 minutes, and then dichlorodimethyl Si lane (0.5 eq) was added at -10 ° C, followed by stirring overnight at room temperature. Then, after work-up with water and dried, a ligand was obtained.
  • Step 2 Preparation of dimethylsilanediyl bis (3-propyl-inden-1-yl) zirconium dichloride (Dimethylsi lanediyl bi s- (3-propyl-inden-l-yl) zirconium dichlor ide)
  • ligand was dissolved in Toluene / Ether (2/1, 0.53M) and n_ BuLi (2.05 eq) was added at -25 ° C, followed by stirring at room temperature for 5 hours.
  • ZrCU (1 eq) was added to Toluene (0.17 M) into the flask, and the mixture was stirred overnight at room temperature.
  • the solvent is vacuum dried and DCM is re-injected to remove LiCl through f i ter, etc.
  • the filtrate is vacuum dried, and DCM / Hexane is added to recrystallize at room temperature. Then, the resulting solid was f i l ter and dried in vacuo to obtain a solid metallocene compound.
  • n-BuLi (1.05 eq) was slowly added dropwise at -25 ° C, and then 3 hours at room temperature. While stirring. Subsequently, Di chloro dimethyl Si lane (1.05 eq) was added at -10 ° C, followed by stirring overnight at room temperature. After 2-Me-l-H-Indene (1 eq) was dissolved in Toluene / THF (5/1, 0.7M) in another reactor, n-BuLi (1.05 eq) was slowly added dropwise at -25 ° C, and then at room temperature. It was stirred for 3 hours. after
  • Step 2 Dimethylsilanediyl (3-butyl-1H-indene-1yl) (2-methyl-1H-indene-1yl) zirconium dichloride (Dimethylsi lanediyl (3-buty 1-1H to i nden- l ⁇ y 1) Preparation of (2-methyl-lH-inde-l-yl) zirconium di chloride)
  • ligand was dissolved in Toluene / Ether (2/1, 0.53M) and n_ BuLi (2.05 eq) was added at _25 ° C, followed by stirring at room temperature for 5 hours.
  • ZrC14 (1 eq) was added to Toluene (0.17 M) in a flask, and then stirred at room temperature overnight.
  • Step 1 of Preparation Example 1-1 3-:!-Butyl-in-indene was used instead of 3 -phenyl-111-indene and 2 -methyl-4- (4a6 _butylphenyl) indene was used.
  • Dimethylsilanediyl (3-butyl-111-inden-1-yl) (2) was carried out in the same manner as in Production Example 1-1, except that 2-methyl- 4-phenylindene was used.
  • -Methyl- 4-phenyl-in-inden-1-yl) zirconium dichloride was prepared.
  • nucleic acid 400 400 mL was added, stirred for 1 minute, left for 15 minutes to decant the solvent using cannula, and an antistatic agent (Atmer 163ä, 3 g manufactured by CR0DA) was dissolved in nucleic acid 400 and transferred to the reactor using cannula.
  • the mixture was stirred for 20 minutes at room temperature and transferred to a glass filter to remove the solvent, primary drying under vacuum at room temperature for 5 hours, and secondary drying under vacuum for 4 hours at 45 ° C to obtain a supported catalyst.
  • a metallocene supported catalyst was carried out in the same manner as in Production Example 2-1, except that each of the transition metal compounds prepared in 2 to 1-5 or Comparative Production Examples 1-1 to 1-8 was used respectively.
  • Example 1 instead of the metallocene-supported catalyst of Production Example 2-1, the metallocene-supported catalysts of Production Examples 2-2 to 2-5 or Comparative Production Examples 2-1 to 2-8 were used. Homopolypropylene was prepared by performing the same method as in Example 1 except for the above. Test Example 1
  • MI Melt Index
  • Weight average molecular weight g / mol and molecular weight distribution (MWD, polydi spers ty ty index): The weight average molecular weight (Mw) and the number average molecular weight (Mn) were measured using gel permeation chromatography (GPC), respectively. Then, the molecular weight distribution was calculated by the ratio of Mw / Mn. Specifically, Polymer Laboratories PLgel 2020/091177 1 »(: 1 ⁇ 1 ⁇ 2019/007152
  • Measurements were made using a ⁇ 220 instrument using a 300_ length column in-house. At this time, the evaluation temperature is 160 ° (:, 1,2, 4 -trichlorobenzene was used as a solvent, the flow rate was 11/11. Samples were prepared at a concentration of 101 Pa / 10, and then supplied in an amount of 200. The values of and were derived using an assay curve formed using polystyrene standards. The molecular weight of the polystyrene standard (yong / 11101) was 9 of 2,000 / 10,000 / 30,000 / 70,000 / 200,000 / 700,000 / 2,000,000 / 4,000,000 / 10,000, 000.
  • the supported catalysts of Preparation Examples 2-1 to 2-5 containing the transition metal compound according to the present invention exhibited a high catalytic activity of 14 PP / g or more, from which the polymer was prepared using the transition metal compound. 2020/091177 1 »(: 1 ⁇ 1 ⁇ 2019/007152
  • the homo polypropylene of Examples 1 to 5 showed a high of 340,000 for / 11101 or higher and a low of 7 for / 101 11 for injection of hydrogen gas during the polymerization reaction. From this, it can be seen that a wide range of ⁇ 3 (16 production) is possible by controlling the amount of hydrogen gas input during the polymerization reaction.
  • homo polypropylenes of Examples 1 to 5 can be expected to exhibit excellent stiffness and impact strength characteristics by exhibiting a narrow _ of 2.7 or less in addition to the above-described physical properties.
  • the polymer of Comparative Example 1 prepared using the catalyst of Comparative Preparation Examples 2-1 in which the first ligand structure of the transition metal compound is unsubstituted uses a transition metal compound in which one or more hydrogens in the first ligand are substituted.
  • the substitution in the first ligand affects the physical properties of the polymer, especially and.
  • the polymer of Comparative Example 3 prepared using the transition metal compound in which the 2nd position was further substituted in addition to the 4th position, compared to Comparative Example 2, significantly decreased, Although it increased, 3 ⁇ 4 increased significantly and 3 ⁇ 4 ⁇ ) also increased.
  • the polymers of Comparative Examples 4 and 5 prepared by using the transition metal compound in which position 2 is further substituted or position 2 and 4 are further substituted in addition to position 3 , Compared with the example, the MI increased, the Mw decreased, the MWD increased significantly, and the MWD increased more particularly when the 4th position was further substituted.
  • the polymer of Comparative Example 6 prepared using a transition metal compound in which the positions 3 of both the first and second ligand structures in the transition metal compound are identically substituted with an isopropyl group has a low Tm due to a decrease in Tact i ci ty. Although shown, Mw was greatly reduced and MWD and MI were greatly increased. From this, it can be expected that the polymer of Comparative Example 6 has a reduced impact strength characteristic.
  • the polymer of Comparative Example 8 prepared by using a transition metal compound substituted only with phenyl at the 4th position also had reduced activity and decreased Mw compared to Example 2. This difference is because, in the case of Example 2, the catalytic activity was significantly increased due to the sufficient provision of an induct ive ef fect due to the t-butylphenyl group present at position 4 in the second ligand structure in the transition metal compound.
  • the MI, Mw, and _ of the polymer vary depending on the bonding position and type of the substituents in the first and second ligands, and further comprising the first and second ligands of the indene structure.
  • the effect of the present invention that is, the polymer It can be seen that the properties of low Tm and MI, high Mw and narrow MWD at can be realized simultaneously.

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  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
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  • Materials Engineering (AREA)
  • Crystallography & Structural Chemistry (AREA)
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Abstract

La présente invention concerne un nouveau composé de métal de transition ayant une excellente activité catalytique et étant utile pour produire un polypropylène ayant une résistance au choc élevée, et un procédé de préparation de polypropylène l'utilisant.
PCT/KR2019/007152 2018-11-02 2019-06-13 Nouveau composé de métal de transition et procédé de préparation de polypropylène l'utilisant WO2020091177A1 (fr)

Priority Applications (3)

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EP19879818.3A EP3786195B1 (fr) 2018-11-02 2019-06-13 Nouveau composé de métal de transition et procédé de préparation de polypropylène l'utilisant
US17/251,026 US11370851B2 (en) 2018-11-02 2019-06-13 Transition metal compound and method for preparing polypropylene using the same
CN201980034296.XA CN112154163B (zh) 2018-11-02 2019-06-13 过渡金属化合物及使用其制备聚丙烯的方法

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KR10-2018-0133858 2018-11-02
KR20180133858 2018-11-02
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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP5052068B2 (ja) * 2006-08-11 2012-10-17 三井化学株式会社 包装材料用プロピレン系樹脂組成物およびその用途
EP2933277A1 (fr) * 2014-04-17 2015-10-21 Borealis AG Nouveau système de catalyseur pour la production de copolymères de polyéthylène dans un processus de polymérisation en solution à température élevée
JP2016160294A (ja) * 2015-02-27 2016-09-05 日本ポリプロ株式会社 繊維強化ポリプロピレン系樹脂組成物
KR20170008987A (ko) * 2015-07-15 2017-01-25 한화케미칼 주식회사 메탈로센 화합물 및 이의 제조방법
KR20170099691A (ko) * 2016-02-24 2017-09-01 주식회사 엘지화학 혼성 담지 메탈로센 촉매 및 이를 이용한 폴리올레핀의 제조 방법

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP5052068B2 (ja) * 2006-08-11 2012-10-17 三井化学株式会社 包装材料用プロピレン系樹脂組成物およびその用途
EP2933277A1 (fr) * 2014-04-17 2015-10-21 Borealis AG Nouveau système de catalyseur pour la production de copolymères de polyéthylène dans un processus de polymérisation en solution à température élevée
JP2016160294A (ja) * 2015-02-27 2016-09-05 日本ポリプロ株式会社 繊維強化ポリプロピレン系樹脂組成物
KR20170008987A (ko) * 2015-07-15 2017-01-25 한화케미칼 주식회사 메탈로센 화합물 및 이의 제조방법
KR20170099691A (ko) * 2016-02-24 2017-09-01 주식회사 엘지화학 혼성 담지 메탈로센 촉매 및 이를 이용한 폴리올레핀의 제조 방법

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