WO2018117403A1 - Catalyseur métallocène supporté hybride et procédé de préparation d'une polyoléfine faisant appel à celui-ci - Google Patents

Catalyseur métallocène supporté hybride et procédé de préparation d'une polyoléfine faisant appel à celui-ci Download PDF

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WO2018117403A1
WO2018117403A1 PCT/KR2017/012420 KR2017012420W WO2018117403A1 WO 2018117403 A1 WO2018117403 A1 WO 2018117403A1 KR 2017012420 W KR2017012420 W KR 2017012420W WO 2018117403 A1 WO2018117403 A1 WO 2018117403A1
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group
formula
carbon atoms
compound
alkyl group
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PCT/KR2017/012420
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Korean (ko)
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김선미
최이영
이기수
홍복기
이승민
선순호
박진영
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주식회사 엘지화학
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Priority claimed from KR1020170145519A external-priority patent/KR102073253B1/ko
Application filed by 주식회사 엘지화학 filed Critical 주식회사 엘지화학
Priority to CN201780004061.7A priority Critical patent/CN108473613B/zh
Priority to EP17861201.6A priority patent/EP3363820B1/fr
Priority to US15/773,748 priority patent/US10544247B2/en
Publication of WO2018117403A1 publication Critical patent/WO2018117403A1/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
    • 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
    • C08F4/65904—Component covered by group C08F4/64 containing a transition metal-carbon bond in combination with another component of 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
    • 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
    • C08F4/65922—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 containing at least two cyclopentadienyl rings, fused or not
    • C08F4/65925—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 containing at least two cyclopentadienyl rings, fused or not two cyclopentadienyl rings being mutually non-bridged
    • 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
    • C08F4/65922—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 containing at least two cyclopentadienyl rings, fused or not
    • C08F4/65927—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 containing at least two cyclopentadienyl rings, fused or not two cyclopentadienyl rings being mutually bridged
    • 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
    • C08F4/65916—Component covered by group C08F4/64 containing a transition metal-carbon bond supported on a carrier, e.g. silica, MgCl2, polymer

Definitions

  • the present invention relates to a common supported metallocene catalyst and a method for preparing polyolefin using the same.
  • 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.
  • Ziegler-Natta catalysts have been widely applied to the existing commercial processes since the invention in the 50s, but since the active site is a multi-site catalyst (mul-si te cata lyst) with multiple active sites, the broad molecular weight distribution of the polymer is Toxing, The composition distribution of comonomer is not uniform ⁇ There is a problem that the limit to secure the 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 which has a narrow molecular weight distribution according to the characteristics of a single active site and a homogeneous composition of the comonomer, and a stereoregularity, copolymerization characteristic, and molecular weight of the polymer according to the ligand structure modification and the change of polymerization conditions of the catalyst. , Has the property of changing the crystallinity and the like.
  • 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. This is supported by a single support of a titanium (Ti) -based Ziegler-Natta catalyst that produces high molecular weight and a zirconium (Zr) -based metallocene catalyst that produces low molecular weight. As a method of producing a bimodal di str ibut i on polymer, the supporting process is complicated and the morphology of the polymer is deteriorated due to the promoter.
  • Ti titanium
  • Zr zirconium
  • 5, 525, 678 describes a method of using a catalyst system for olefin polymerization in which a high molecular weight polymer and a low molecular weight polymer can be simultaneously polymerized by simultaneously supporting a metallocene compound and a nonmetallocene compound on a carrier. 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 the 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 preparation of the 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 of controlling the molecular weight distribution by supporting a double-nucleated 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 released from the carrier component of the finished catalyst, causing fouling. .
  • the present invention is to provide a common supported metallocene catalyst capable of producing a polyolefin having excellent processability and showing a mul t imodal molecular weight distribution.
  • the first metallocene compound represented by the formula (1) A second metallocene compound represented by Formula 2, wherein one of Formula 2 and C 2 is Formula 3a; To be represented by the formula (2), in the formula (2) one of the C, and C 2 to the metallocene compound of the third metal formula 3b; Cocatalyst compounds; And a common supported metallocene catalyst comprising a carrier.
  • the present invention also provides a method for producing polyolefin, comprising the step of polymerizing the olefin monomer in the presence of the common supported metallocene catalyst.
  • Common supported metallocene catalysts may be provided comprising a carrier:
  • At least one of Ri to R 8 is (CH 2 ) n -0R (wherein R is a straight or branched chain alkyl group having 1 to 6 carbon atoms, n is an integer of 2 to 10), and the others are the same as each other, or Different from each other independently hydrogen, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkylaryl group having 7 to 20 carbon atoms, or an arylalkyl group having 7 to 20 carbon atoms,
  • Xi and 3 ⁇ 4 are the same as or different from each other, and each independently a halogen, or an alkyl group having 1 to 20 carbon atoms,
  • M 2 is a Group 4 transition metal
  • 3 ⁇ 4 are the same as or different from each other, and are each independently a halogen or an alkyl group having 1 to 20 carbon atoms,
  • B is carbon, silicon or germanium
  • At least one of Qi and Q 2 is — (C3 ⁇ 4) m — (where R 'is a straight or branched chain alkyl group having 1 to 6 carbon atoms and m is an integer from 2 to 10.), and the remainder is hydrogen A halogen, an alkyl group of 1 to 20 carbon atoms, an alkenyl group of 2 to 20 carbon atoms, an aryl group of 6 to 20 carbon atoms, an alkylaryl group of 7 to 20 carbon atoms, or an arylalkyl group of 7 to 20 carbon atoms,
  • C 2 is represented by the following Chemical Formula 3a or 3b, and the other is represented by the following Chemical Formula 3c,
  • 3 ⁇ 4 to R 27 are the same as or different from each other, and each independently, hydrogen, an alkyl group of C1 to C20, an alken.yl group of C2 to C20, an alkoxy group of C1 to C20, an alkylsilyl group of C1 to C20, and C1 to C20 A silylalkyl group, a C6 to C20 aryl group, a C7 to C20 alkylaryl group, or a C7 to C20 arylalkyl group.
  • the substituents of Chemical Formulas 1, 2, 3a, 3b, and 3c will be described in more detail.
  • the alkyl group of ⁇ : ⁇ to C20 includes a linear or branched alkyl group, and specifically, methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, tert-butyl group, pentyl group, nuclear group, hep And the like, but not limited thereto.
  • the alkenyl group of C2 to C20 includes a straight or branched alkenyl group, and specifically, may include an allyl group, ethenyl group, propenyl group, butenyl group, pentenyl group, and the like, but is not limited thereto.
  • the C6 to C20 aryl group includes a monocyclic or condensed aryl group, and specifically includes a phenyl group, a biphenyl group, a naphthyl group, a phenanthrenyl group, a fluorenyl group, and the like, but is not limited thereto.
  • alkoxy group for C 1 to C 20 examples include a hydroxy group, an hydroxy group, a phenyloxy group, a cyclonuxyloxy group, and the like, but are not limited thereto.
  • the Group 4 transition metal examples include titanium, zirconium, hafnium, and the like, but are not limited thereto.
  • the first metallocene compound represented by Formula 1 is-(C3 ⁇ 4) n-0R in the substituent of cyclopentadiene (Cp), wherein R is a linear or branched alkyl group having 1 to 6 carbon atoms, and n is 2 to
  • Cp cyclopentadiene
  • J which is an integer of 10
  • a low molecular weight polyolefin can be produced when the polyolefin using the comonomer is produced, showing a lower conversion to the comonomer compared to other Cp-based catalysts not containing the substituent.
  • The-(CH 2 ) n-0R group in the substituent is stable because it can form a covalent bond through close interaction with the silanol group on the silica surface used as a support. Supported polymerization is possible.
  • At least one of Ri and R 5 is preferably-(CH 2 ) n -0R, and more preferably n is 2 to 4.
  • alpha -olefin comonomers such that-(CH 2 ) n — OR functionality is 1-butene, or 1-hexene.
  • n has a short alkyl chain of 4 or less, the copolymerization with respect to the alpha olepin comonomer is lowered while maintaining the overall polymerization activity, thereby making it possible to prepare a polyolefin having a controlled copolymerization without degrading other physical properties. Because there is.
  • first metallocene compound represented by Chemical Formula 1 may include a compound represented by the following structural formulas, but the present invention is not limited thereto.
  • the second metallocene compound represented by Chemical Formula 2 and one of Chemical Formula 2 and one of C 2 is asymmetrical by the bridge between the indeno indol derivative and the indene derivative. And a non-covalent electron pair that can act as a Lewis base to the ligand structure, thus exhibiting high polymerization activity.
  • the electronically rich indenoindole derivatives have a beta-hydrogen of a polymer chain in which nitrogen atoms grow, By stabilizing by inhibiting beta-hydrogen el iminat i on it can polymerize a high molecular weight polyolefin compared to the first metallocene compound.
  • the second metallocene compound exhibits high copolymerization activity and low hydrogen reactivity as it contains indene derivatives having relatively little steric hindrance; greater than the molecular weight of polarulepine prepared using the first metallocene compound;
  • the high molecular weight polyolefin which is smaller than the molecular weight of the polyolefin manufactured using the 3rd metallocene compound mentioned later can be superposed
  • R 10 of Formula 3a is C1 to C20 alkyl group, C2 to C20 alkenyl group, C1 to C20 alkoxy group, C1 to C20 alkylsilyl group, C1 to C20 silyl It is preferable that they are an alkyl group, C6-C20 aryl group, C7-C20 alkylaryl group, or C7-C20 arylalkyl group.
  • R 10 substituent
  • any one or more of R 24 and 7 in the general formula (3c) is C1 to C20 alkyl group, C2 to C20 alkenyl group, C1 to C20 Alkoxy group, C1 to C20 alkylsilyl group, C1 to C20 silylalkyl group, C6 to C20 aryl group, C7 to C20 It is preferable that it is an alkylaryl group or the C7-C20 arylalkyl group, A methyl group, an ethyl group, a propyl group, an isopropyl group, n-butyl group, tert- butyl group, a pentyl group, a nuclear group, a heptyl group, an octyl group phenyl group More preferably, a halogen group, trimethylsilyl group, triethylsilyl group, tripropy
  • the second metallocene compound may include a compound represented by the following structural formulas, but the present invention is not limited thereto.
  • the third metallocene compound represented by Chemical Formula 2, and one of Chemical Formula 2 and C 2 is Chemical Formula 3b, wherein the indeno indole derivative and the cyclopentadiene (Cp) derivative are asymmetric by the bridge. It forms a crosslinked structure, and exhibits high polymerization activity by having a lone pair of electrons which can act as a Lewis base in the ligand structure.
  • the electronically rich indeno indole derivatives stabilize beta-hydrogen in the polymer chain in which nitrogen atoms are grown by hydrogen bonding, thereby inhibiting beta-hydrogen el iminat i on to polymerize high molecular weight polyolefins compared to the first metallocene compound. can do.
  • the third metallocene compound includes cyclopentadiene (Cp) derivative # having less steric hindrance than the indene derivative, the third metallocene compound exhibits high copolymerization activity and low hydrogen reactivity, thereby using the first and second metallocene compounds.
  • Higher molecular weight polyolefin can be polymerized with higher activity than the prepared polyolefin.
  • the third metallocene compound may include a compound represented by the following structural formula, but the present invention is not limited thereto.
  • the common metallocene catalyst of the embodiment includes the first to third metallocene compounds, and exhibits a broad molecular weight distribution of mult imoda l, which is excellent in processability and particularly in physical properties.
  • Polyolefin can be produced excellent in environmental stress cracking resistance.
  • the mixing molar ratio of the first metallocene compound, the second metallocene compound, and the third metallocene compound may be about 1: 0.1 to 5: 0.1 to 5, more preferably About 1: 0.2-5: 0.5-2.
  • the common supported metallocene catalyst of the embodiment as a co-catalyst supported on a carrier for activating the metallocene compound, it is an organometallic compound containing a Group 13 metal, under a general metallocene catalyst It will not be specifically limited if it can be used when superposing
  • the promoter compound is an aluminum-containing agent of the formula
  • It may include one or more of the cocatalyst, and a second borate-based cocatalyst of the formula (5).
  • T + is a +1 polyvalent ion
  • B is boron in +3 oxidation state
  • G is independently a hydride group, a dialkyl amido group, and a halide group.
  • the first cocatalyst of Chemical Formula 4 may be an alkylaluminoxane compound having a repeating unit bonded in a linear, circular, or reticular form.
  • Specific examples of the first cocatalyst include methylaluminoxane (MA0) and ethylalumina. Noxic acid, isobutyl aluminoxane, or butyl aluminoxane etc. are mentioned.
  • the second cocatalyst of Formula 5 may be a borate-based compound in the form of a trisubstituted ammonium salt, or a dialkyl ammonium salt, a trisubstituted phosphonium salt.
  • Such a second cocatalyst include trimetalammonium tetraphenylborate, methyldioctadecylammonium tetraphenylborate, triethylammonium tetraphenylborate, tripropylammonium tetraphenylborate, tri (n-butyl) ammonium tetraphenylborate , Methyltetracyclooctadecylammonium tetraphenylborate, ⁇ , ⁇ —dimethylaninium tetraphenylborate, ⁇ , ⁇ -diethylaninynium tetraphenylborate, ⁇ , ⁇ -dimentyl (2,4,6-trimethylaniyl (Nium) tetraphenylborate, trimethylammonium tetrakis (pentafluorophenyl) borate, Methylditetradec
  • Triethylammonium tetrakis (2,3,4,6-tetrafluorophenyl) borate Tripropylammonium tetrakis (2,3,4,6-tetrafluorophenyl) borate, tri ( ⁇ -butyl) ammonium tetrakis (2,3.4,6-, tetrafluorophenyl) borate, dimethyl (t-butyl ) Ammonium Tetrakis (2,3,4,6-Tetrafluorophenyl) borate, N : N dimethyl dimethylaninium tetrakis (2,3,4,6 ⁇ tetrafluorophenyl) borate, ⁇ , ⁇ - ⁇ Diethylaninium tetrakis (2.3,4,6-tetrafluorophenyl) borate or ⁇ , ⁇ -dimethyl— (2,4,6 ⁇ trimethylaninynium) tetrakis- (2,3,4,6-te
  • the weight ratio of the total transition metal to the carrier included in the first metallocene compound, a metallocene compound and a metallocene compound with the third metal to second metal is from 1: 10 to 1: Can be 1,000.
  • the carrier and the metallocene compound are included in the mass ratio, an optimal shape can be exhibited.
  • the mass ratio of the promoter compound to the carrier may be 1: 1 to 1: 100.
  • a carrier containing a hydroxy group on the surface may be used, and preferably, a highly reactive hydroxy group and a siloxane group which are dried to remove moisture on the surface
  • the carrier which has is used may be used.
  • silica, silica-alumina, silica-magnesia, etc., dried at a high temperature may be used, and these are typically oxides, carbonates, such as Na 2 O, K 2 C0 3 , BaS0 4 , and Mg (N0 3 ) 2 . Sulfate, and nitrate components.
  • the drying temperature of the carrier is preferably 200 to 800 ° C, more preferably 300 to 600 ° C, most preferably 300 to 40 CTC. Drying Temperature of the Carrier ⁇ If it is less than 200 ° C, the moisture and cocatalyst on the surface will react too much, and if it exceeds 800 ° C, the pores on the surface of the carrier will merge and the surface area will decrease. It is not preferable because many hydroxyl groups are lost and only siloxane groups are left, resulting in a decrease in reaction space with the promoter.
  • the amount of hydroxy groups on the surface of the carrier is preferably from 0.1 to 10 mmol / g, more preferably from 0.5 to 5 mmol / g.
  • the amount of hydroxyl groups on the surface of the carrier can be controlled by the method and conditions for preparing the carrier or by drying conditions such as temperature, time, vacuum or spray drying.
  • the amount of the hydroxy group is less than 0.01 mmol / g, the reaction site with the promoter is small. If the amount of the hydroxyl group is more than 10 ⁇ L / g, the hydroxy group present on the surface of the carrier particle may be due to moisture. It is not desirable because there is.
  • the common supported metallocene catalyst of the above embodiment can be used by itself for the polymerization of olefinic monomers.
  • the common supported metallocene catalyst may be prepared and used as a prepolymerized catalyst in contact with an olefinic monomer.
  • the catalyst may be separately used, such as ethylene, propylene, 1-butene, 1-nuxene, 1-octene, and the like. It can also be prepared and used as a prepolymerized catalyst by contacting with the pin monomer.
  • the hybrid supported metallocene catalyst of the embodiment the step of supporting the promoter on the carrier; Supporting the first to third metallocene compounds on the carrier on which the promoter is supported; It may be prepared by a manufacturing method comprising a.
  • the first to third metallocene compounds may be supported one by one, or two or three may be supported together.
  • the supporting order is not limited, but by first supporting the third metallocene catalyst having a relatively poor morphology, it is possible to improve the shape of the common supported metallocene catalyst, so as to the third metal After supporting the catalyst, the second metallocene catalyst and the first metallocene catalyst may be sequentially supported.
  • the supporting conditions are not particularly limited and may be performed in a range well known to those skilled in the art.
  • the support temperature is possible in the range of 30 ° C to 150 ° C, preferably from room temperature to 100 ° C, more preferably From room temperature to 80 ° C.
  • the supporting time is the metallocene ⁇ to be supported. It may be appropriately adjusted according to the amount of the compound.
  • the supported catalyst can be used as it is by removing the solvent by distillation under reduced pressure by filtration or by distillation under reduced pressure.
  • Preparation of a supported catalyst can be carried out in a solvent or in the absence of: A.
  • available solvents include aliphatic hydrocarbon solvents such as nucleic acids or pentane, aromatic hydrocarbon solvents such as toluene or benzene, and hydrocarbon solvents substituted with chlorine atoms such as dichloromethane.
  • organic solvents such as ether solvents such as diethyl ether or THF, acetone, ethyl acetate, and the like, and nucleic acid, heptane, toluene, or dichloromethane are preferred.
  • a method for producing a polyolefin including the step of polymerizing the olefin monomer in the presence of the common supported metallocene catalyst.
  • the olefin monomer is ethylene, propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-nuxene, 1-heptene, 1-octene, 1-decene, 1-undecene, 1- Dodecene, 1-tetradecene, 1—nuxadecene, 1-aitocene, norbornene, norbonadiene, ethylidene nobodene, phenyl nobodene, vinyl nobodene, dicyclopentadiene, 1, 4-butadiene , 1 , 5-pentadiene. 1,6 ⁇ nucleodiene. Styrene, alpha-methylstyrene,.
  • It may be at least one selected from the group consisting of divinylbenzene and 3—chloromethylstyrene.
  • a continuous solution polymerization process For the polymerization reaction of the olefin resin, a continuous solution polymerization process, bulk polymerization process, suspension polymerization process.
  • Various polymerization processes known as polymerization reaction of olefin monomers such as slurry polymerization process or emulsion polymerization process, may be employed. Such polymerization reaction may be carried out at a temperature of about 25 to 500 ° C, or about 25 to 200 ° C. or about 50 to 150 ° C, and under a pressure of about 1 to 100 bar or about 10 to 80 bar.
  • the common supported metallocene catalyst may be used dissolved or diluted in a solvent such as pentane, nucleic acid, heptane, nonane, decane, toluene, benzene, dichloromethane, chlorobenzene, and the like.
  • a solvent such as pentane, nucleic acid, heptane, nonane, decane, toluene, benzene, dichloromethane, chlorobenzene, and the like.
  • a solvent such as pentane, nucleic acid, heptane, nonane, decane, toluene, benzene, dichloromethane, chlorobenzene, and the like.
  • the polyolefin prepared by the above production method may be a polyolefin having a multimodal molecular weight distribution.
  • the polyolefin prepared had a weight average molecular weight (Mw) of 100,000. To 300,000 g / mol. More preferably, the increase is. The average molecular weight is.
  • the molecular weight distribution (PDI) of the prepared polyolefin may be 5 or more. More preferably, the molecular weight distribution is 8 or more, 9 or more, or 10 or more, 20 or less, 18 or less, or 17 or less.
  • the polyolefin may be an ethylene / alpha—lepin copolymer.
  • the ethylene / alpha-olefin copolymer has a density of 0.948 to 0.960 g / cm 3 , or 0.950 to 0.955 g / cm 3 . Density of Ethylene / Alpha-Lepin Copolymer
  • the integral value of the region where log Mw is 5.0 to 5.5 is 10 to 20% of the total X-axis integral value. , Preferably 10 to 18%, more preferably 10 to 16%.
  • Mw means weight average molecular weight
  • w means weight fraction.
  • a log Mw of 5.0 to 5.5 is a region where physical properties and processability of the product provided by injection of the ethylene / alpha-olefin copolymer are confirmed.
  • region whose log Mw is 5.0-5.5 with respect to the X-axis integral value is a numerical value which shows the tie molecular fraction of the high molecular weight in the said ethylene / alpha-olefin copolymer. Accordingly, when the ratio of the integral of the log Mw of 5.0 to 5.5 is less than 10% of the total integral value of the X axis, the ethylene / alpha-olefin copolymer has a relatively low level of environmental stress cracking resistance. (ESCR).
  • the ratio of the integral value of the region of the log Mw7 ⁇ 5.0 to 5: 5 is greater than 20% with respect to the total X-axis integral value, the molecular weight distribution of the high molecular weight region according to the molecular weight distribution (MWD) Due to the excessive specific gravity, the processability of the ethylene / alpha-olepin copolymer may be greatly reduced.
  • the ethylene / alpha-lefin copolymer may have a spiral flow length (190 ° C, 90 bar) of 13 to 25 cm, more preferably 15 to 20 cm.
  • the spiral flow length (190 ° C, 90 bar) indicates the processability of the ethylene / alpha -olefin copolymer, the larger the value means that the processability is excellent.
  • a larger spiral flow length is not necessarily preferable, and there may be an appropriate range of spiral flow lengths depending on the application.
  • the spiral flow length is applied by applying a specific pressure and temperature to the spiral mold: how polymer is injected and thus melted and injected polymer It can be assessed by measuring if it is pushed out.
  • a specific pressure and temperature to the spiral mold: how polymer is injected and thus melted and injected polymer It can be assessed by measuring if it is pushed out.
  • an injection temperature of 190 ° C, a mold temperature of 50 ° C and the injection pressure can be measured by setting to 90 bar, the ethylene /
  • the spiral flow length of the alpha-olefin co-polymer is 13-25 cm, indicating excellent processability.
  • the ethylene / alpha olefin copolymer is characterized by excellent environmental stress cracking resistance (ESCR, ' envi ronmental st ress crack stance) in addition to the mechanical properties and processability as described above.
  • the processability and environmental resistance crack resistance is a contrary physical properties, if the melt index is increased to increase the workability, the environmental resistance crack resistance is reduced, but the ethylene / of the above embodiment prepared using a specific hybrid supported metallocene catalyst
  • the alpha-olefin copolymer can satisfy both good processability and environmental stress cracking resistance.
  • the ethylene / alpha-olefin copolymer may have an environmental stress crack resistance (ESCR) of 130 hours or more, 140 hours or more, or 150 hours or more, as measured according to ASTM D 1693. If the environmental stress cracking resistance (ESCR) is 130 hours or more, the performance can be stably maintained under the condition of the use of the bottle cap. The higher the environmental stress cracking resistance (ESCR) value is, the better, the upper limit is not limited. For example up to 1,000 hours, or up to 800 hours, or up to about 500 hours.
  • the ethylene / alpha-olepin copolymer exhibits high performance of environmental stress cracking resistance
  • the ethylene / alpha-lepine copolymer can be molded into a food container product such as a borcap to maintain high stability even when used under high temperature and high pressure.
  • the ethylene / alpha -olefin copolymer may have a melt index (Ml, 190 ° C, 2. 16 kg) of 0.7 g / 10 m in or less.
  • the melt index is at least 0.05 g / 10 m in, at least 0.01 g / 10 m in, or at least 0.1 g / lOmin, at most 0.7 g / 10iiiin, at most 0.6 g / 10 m in, or at most 0.5 g /. It may be less than 10m in.
  • the common supported metallocene catalyst according to the present invention When used, it is excellent in workability and has a feature capable of producing a polyolefin having a mult imodal molecular weight distribution. [Specific contents to carry out invention]
  • the reaction mixture changed from pale brown suspension to turbid yellow in suspension form when raised to room temperature. After stirring for one day, both the reaction mixture and the solvent were dried, 200 mL of nucleic acid was added thereto, and the sonic cat ion was allowed to settle. The nucleic acid solution in the upper layer was collected by decant at ion with cannula. This process. The nucleic acid solution obtained twice was dried under vacuum reduced pressure to give bis (3- (4— (tert-butoxy) butyl-2,4—dien-yl) zirconium (IV) chloride, a pale yellow solid. Confirmed- ⁇
  • toluene or ether in the mixture was removed by vacuum depressurization to about 1/5 volume and the volume of nucleic acid was added about 5 times the volume of the remaining solvent.
  • the reason for adding the nucleic acid at this time is to promote crystallization because the synthesized catalyst precursor is insoluble in nucleic acid.
  • This hexane slurry was filtered under argon, and after filtration, both the filtered solid and the filtrate were evaporated under vacuum reduced pressure. The remaining filter cake is weighed and sampled in the glove box for synthesis and yield. Purity was confirmed.
  • CDCI3 7.89-6.53 (19H, m), 5.82 (4H, s), 3.19 (2H, s), 2.40 (3H, m), 1.35-1.21 (4H, m), 1.14 (9H, s), 0.97 0.9 (4H, m), —0.34 (3H, t)
  • the metallocene compound of Preparation Example 2 was added to the reaction vessel at a rate of 0.15 kPa ol / gSi3 ⁇ 4, and then stirred at 40 ° C. at 200 rpm for 2 hours.
  • the metallocene metallocene compound of Preparation Example 1 was introduced into the reactor at a ratio of 0.15 kPa ol / gSi0 2 , and then stirred at 40 ° C. at 200 rpm for 2 hours.
  • a hybrid supported metallocene catalyst was prepared in the same manner as in Example 1, except that 0.1 mmol / g Si0 2 was added to the metallocene compound prepared in Preparation Example 1.
  • Example 3
  • Each of the common supported metallocene catalysts prepared in each of the above examples was introduced into a CSTR continuous polymerizer (reactor volume 50 L) to prepare an olefin polymer.
  • comonomer 1-butene was used, and the reactor pressure was maintained at 10 bar and the deposition temperature was maintained at 90 ° C.
  • Mn, Mw, PDI, GPC curve Pre-treat the sample by dissolving it for 160 hours in 1,2,4-Trichlorobenzene containing 0.0125% of BHT using PL-SP260 for 10 hours, using PL-GPC220 The number average molecular weight and the weight average molecular weight were measured at a measurement temperature of 160 ° C. PDI was expressed as the ratio (Mw / Mn) of the weight average molecular weight and the number average molecular weight.
  • the ethylene / alpha -olefin copolymer of the embodiment exhibits a wide molecular weight distribution, as the ratio of the area of the log Mw of 5.0 to 5.5 meets a specific range, the environmental impact crack resistance 150 hours As described above, it can be seen that it exhibits a relatively high spiral flow length and shows excellent processability and significantly improved environmental stress cracking resistance.

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Abstract

La présente invention concerne un catalyseur métallocène supporté hybride et un procédé de préparation d'une polyoléfine faisant appel à celui-ci. Selon la présente invention, le recours à ce catalyseur métallocène supporté hybride permet de préparer une polyoléfine présentant à la fois une excellente résistance aux craquelures sous contraintes dues à l'environnement et une distribution de masse moléculaire multimodale.
PCT/KR2017/012420 2016-12-19 2017-11-03 Catalyseur métallocène supporté hybride et procédé de préparation d'une polyoléfine faisant appel à celui-ci WO2018117403A1 (fr)

Priority Applications (3)

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CN201780004061.7A CN108473613B (zh) 2016-12-19 2017-11-03 负载型混杂茂金属催化剂及使用该催化剂制备聚烯烃的方法
EP17861201.6A EP3363820B1 (fr) 2016-12-19 2017-11-03 Catalyseur métallocène supporté hybride et procédé de préparation d'une polyoléfine faisant appel à celui-ci
US15/773,748 US10544247B2 (en) 2016-12-19 2017-11-03 Supported hybrid metallocene catalyst, and method for preparing polyolefin using the same

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KR20160173802 2016-12-19
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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
KR20030012308A (ko) 2001-07-31 2003-02-12 주식회사 예스아이비 배팅형 복권 시스템 및 배팅 방법
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KR20160123123A (ko) * 2015-04-15 2016-10-25 주식회사 엘지화학 가공성이 우수한 에틸렌/알파-올레핀 공중합체 공중합체

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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
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
KR20150058054A (ko) * 2013-11-18 2015-05-28 주식회사 엘지화학 메탈로센 담지 촉매 및 이를 이용하는 폴리올레핀의 제조방법
KR20150057964A (ko) * 2013-11-18 2015-05-28 주식회사 엘지화학 메탈로센 화합물, 이를 포함하는 촉매 조성물 및 이를 이용하는 올레핀계 중합체의 제조방법
KR20150139462A (ko) * 2014-06-03 2015-12-11 주식회사 엘지화학 폴리올레핀의 제조 방법 및 이로부터 제조된 폴리올레핀
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