WO2016186295A1 - Système catalyseur hybride supporté, et procédé de préparation de polyoléfine l'utilisant - Google Patents

Système catalyseur hybride supporté, et procédé de préparation de polyoléfine l'utilisant Download PDF

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WO2016186295A1
WO2016186295A1 PCT/KR2016/000880 KR2016000880W WO2016186295A1 WO 2016186295 A1 WO2016186295 A1 WO 2016186295A1 KR 2016000880 W KR2016000880 W KR 2016000880W WO 2016186295 A1 WO2016186295 A1 WO 2016186295A1
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group
carbon atoms
formula
aryl
alkyl
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PCT/KR2016/000880
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English (en)
Korean (ko)
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이승미
이용호
박진영
이기수
신은지
사석필
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주식회사 엘지화학
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Priority claimed from KR1020160009561A external-priority patent/KR20160134464A/ko
Application filed by 주식회사 엘지화학 filed Critical 주식회사 엘지화학
Priority to CN201680014797.8A priority Critical patent/CN107406535B/zh
Priority to JP2017543375A priority patent/JP6511152B2/ja
Priority to EP16796622.5A priority patent/EP3243848B1/fr
Priority to US15/552,136 priority patent/US10189920B2/en
Publication of WO2016186295A1 publication Critical patent/WO2016186295A1/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
    • C08F4/02—Carriers therefor
    • 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
    • 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
    • C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double 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
    • C08F4/69—Chromium, molybdenum, tungsten or compounds thereof

Definitions

  • Linear alpha-efin is an important material used in comonomers, cleaners, lubricants, plasticizers, etc. It is widely used commercially, especially 1-nuxene and 1-octene in the production of linear low density polyethylene (LLDPE) It is often used as a comonomer to control the density of
  • LLDPE Linear Low-Density Polyethylene
  • comonomers such as 1-nuxene and 1-octene
  • alpha-olefins have different types of market and market size
  • the technology for selectively producing a specific olefin is important commercially.
  • ethylene igomerization or 1-nucleene or ethylene oligomerization is used.
  • chrome catalyst technology Much research is being done on chrome catalyst technology to produce 1-octene with high selectivity.
  • Conventional commercial manufacturing methods for producing 1-nuxene or 1-octene include SHOP process of Shell Chemical and Ziegler Process of Chevron Philips. It is possible to produce a wide range of alpha-olefins with C4-C20 carbon atoms.
  • the above method synthesizes alpha-olefins of various lengths simultaneously according to the Schultz-Flory distribution. There was a need to go through the separation process.
  • an object of the present invention is to provide a catalyst system capable of simultaneously performing oligomerization and copolymerization of olefin monomers in a single reactor with high efficiency and a method of preparing polyolefin using the same without the need to perform a separate process for preparing alpha-olefins. It is.
  • At least two groups represented by the following formula (1) in the molecule at least one of the groups represented by the formula (1) is a chromium (Cr) coordination bond to the atom (P),
  • a group (L) which connects each of the two or more groups with 4 to 8 carbon atoms, respectively, an aliphatic group having 2 to 20 carbon atoms, a heteroaliphatic group having 2 to 20 carbon atoms, an alicyclic group having 2 to 20 carbon atoms, and carbon atoms Heteroaliphatic group of 2 to 20, or the aliphatic group, heteroaliphatic group, alicyclic group, And at least one organic cream compound having a group having two or more heteroalicyclic groups bound thereto; and
  • a common supported catalyst system in which at least one metallocene compound is supported on a carrier.
  • R 4 are each independently 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 aryl alkyl group having 7 to 20 carbon atoms, or an alkylaryl group having 7 to 20 carbon atoms, or 7 to 20 carbon atoms. It is a 20 alkoxy aryl group.
  • a method for producing a polyolefin comprising the step of polymerizing an olefin monomer in the presence of the common supported catalyst system.
  • the elimination and copolymerization of the olephine monomers can be carried out at the same time with high efficiency in a single reaction vessel without the need to perform a separate process for producing the alpha-olefin.
  • the cost of manufacturing or purchasing the comonomer, a raw material, can be reduced, resulting in lower production costs for the final product.
  • the alpha-olefin comonomers produced primarily in the common supported catalyst system of the present invention are present in the supported catalyst system or in a short distance from the supported catalyst system, thereby increasing the accessibility of the metallocene compound as a (co) polymerization catalyst. High conversion rate has improved co-polymerization efficiency.
  • At least two groups represented by the following formula (1) in the molecule at least one of the groups represented by the formula (1) is a chromium (Cr) coordination bond to the atom (P),
  • At least one metallocene compound is supported on a carrier supported catalyst system.
  • Ri to R 4 are each independently 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 aryl alkyl group having 7 to 20 carbon atoms, or an alkylaryl group having 7 to 20 carbon atoms, or 7 carbon atoms To alkoxyaryl group of 20.
  • the term 'common supported catalyst system' refers to an organic cream compound metallocene compound and a carrier; or alternatively, an organic cream compound, a metallocene compound, a cocatalyst and a carrier are added at the same time or in any order, thereby increasing activity.
  • the catalyst supported catalyst system can be added to the reaction system in the presence or absence of solvent and monomers.
  • oligomerization used in the present invention means that the olefinic monomer is polymerized. Depending on the number of olefinic monomers to be polymerized, it is called trimerization and tetramerization, which are collectively referred to as multimerization or oligomerization.
  • oligomerization in the present invention means, but is not limited to, the selective preparation of 1-nuxene and / or 1-octene which are the main comonomers of LLDPE from ethylene.
  • the catalyst used for lepin oligomerization reaction includes a ligand and a transition metal coordinating to the ligand, wherein As a result, the structure of the active catalyst may be changed, and thus, the selectivity and activity of the alpha-olefin may be different.
  • the organic chromium compound according to the embodiment of the present invention includes a ligand compound which is not previously known, and by appropriately adjusting the substituent introduced into the ligand compound, it is possible to easily control the electronic and three-dimensional environment around the transition metal (Cr). It was confirmed that oligomerization of olefins was possible with high catalytic activity and selectivity.
  • PNP functional groups diphosphinoamine functional groups represented by 1, and one or more of these PNP functional groups contain a complex compound in which a cr (Cr) coordination bond to a factor (P) That is, the organochrome compound according to one embodiment of the present invention is a compound in which chromium forms a coordinating bond to any one or more PNP functional groups in a ligand compound including two or more PNP functional groups in a molecule.
  • Such organic cream compounds may serve to perform oligomerization of olefinic monomers with excellent catalytic activity in the supported catalyst system of the present invention.
  • Ri to R 4 are each independently 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 aryl alkyl group having 7 to 20 carbon atoms, or an alkylaryl group having 7 to 20 carbon atoms, or 7 carbon atoms To alkoxyaryl group of 20. More specifically, specific examples of the ligand compound including one or more PNP functional groups represented by the following Chemical Formula 1 include the following compounds, but the present invention is not limited thereto.
  • the ligand compound may be synthesized in the same manner as in the following reaction formula 1, but the present invention is not limited thereto.
  • the method for preparing the ligand compound will be described in more detail than in the following Examples.
  • Ri to R 4 and L are the same as those defined in Formula 1 above, and X is halogen.
  • the specific ligand compound may include all possible optical isomers.
  • the organochrome compound of the present invention may be a chromium complex compound obtained by reacting the ligand compound with a chromium source.
  • chromium source forming the ligand compound with the ligand compound include chloroacetate, acetylacetonate, chromium trichloride tristetrahydrofuran, chromium (lll) -2-ethylnucleoacetate, chromium Tris (2,2,6,6-tetramethyl-3,5-heptanedionate),
  • Chromium may be one or more selected from the group consisting of benzoylacetonate, crumb (III) nucleofluoro-2,4-pentanedionate and crumb (NI) acetate hydroxide.
  • the PNP functional group of Formula 1 is connected to 4 to 8 carbon atoms, and the group (L) connecting the PNP functional group is an aliphatic group having 2 to 20 carbon atoms, a heteroaliphatic group having 2 to 20 carbon atoms, and having 2 to 20 carbon atoms. Alicyclic group, heterocyclic group having 2 to 20 carbon atoms, or the aliphatic group, heteroaliphatic group, cycloaliphatic group, and heteroalicyclic group.
  • the ligand compound and the transition metal (The organic cream compound, which is a complex of Cr) coordination complex, interacts easily with PNP-Cr depending on the electronic and three-dimensional environment around the transition metal, showing high oligomerization activity, and especially for 1-nuxene and 1-octene. High selectivity can be indicated.
  • the organic chromium compound may be applied to a common supported catalyst system to exhibit high oligomerization reaction activity, and in particular, may exhibit high selectivity for 1-nuxene, 1-octene and the like. Therefore, 1-nucleene, 1-octene, etc. produced therefrom High quality polyolefin can be produced by incorporation into high efficiency comonomer from polyolefin polymerization reaction.
  • the aryl group is preferably an aromatic ring having 6 to 20 carbon atoms, specifically, phenyl, naphthyl, anthracenyl, pyridyl, dimethylanilinyl, anisolyl, and the like. It doesn't work.
  • an alkylaryl group means a C6-C20 aryl group in which one or more linear or branched alkyl groups are substituted
  • the arylalkyl group means a straight-chain or branched alkyl group in which one or more C6-C20 aryl groups are substituted at least one.
  • the alkoxy aryl group means an aryl group having 6 to 20 carbon atoms in which at least one alkoxy group is substituted.
  • a hetero element means N, 0, F, S, P, and a heteroaryl group means an aryl group containing one or more hetero elements.
  • Halogen also means fluorine (F), chlorine (CI), brine (Br), and iodine.
  • the organic chromium compound of one embodiment of the present invention includes two or more, preferably two groups represented by the formula (1), these are groups (L) connecting 4 to 8 carbon atoms, 2 to An aliphatic group of 20, a heteroaliphatic group of 2 to 20 carbon atoms, an alicyclic group of 2 to 20 carbon atoms, a heteroalicyclic group of 2 to 20 carbon atoms, or the aliphatic group, a heteroaliphatic group, an alicyclic group, and a heteroalicyclic group Groups can be linked to two or more combined groups.
  • groups (L) connecting 4 to 8 carbon atoms 2 to An aliphatic group of 20, a heteroaliphatic group of 2 to 20 carbon atoms, an alicyclic group of 2 to 20 carbon atoms, a heteroalicyclic group of 2 to 20 carbon atoms, or the aliphatic group, a heteroaliphatic group, an alicyclic group, and a heteroalicyclic group Groups can be linked to two or
  • linking groups ( ⁇ ) are as follows:
  • * is a moiety bonded to N in Formula 1
  • R ' is independently hydrogen or alkyl of 1 to 5 carbon atoms
  • p is an integer of 1 to 6
  • q is an integer of 1 to 5
  • a plurality of R's bonded to one ring may be the same or different from each other.
  • the organic cream compound including the group represented by Formula 1 may be a catalyst precursor capable of performing oligomerization reaction of an olefin by coordinating a PNP functional group with chromium.
  • the organochromium compound of the above embodiment forms at least one PNP functional group at a suitable position, thereby forming a crack complex, and thus, an example will be described later to increase catalyst activity and selectivity resulting from the interaction between the two groups. It was confirmed at.
  • Formulas 1 to R4 may be the same as each other, preferably phenyl.
  • both of the groups represented by the formula (1) is a coordination bond in the two groups represented by the formula (1) It can be represented as 1-1:
  • ⁇ to Y 3 are each independently halogen, hydrogen, a hydrocarbyl group having 1 to 10 carbon atoms, or a heterohydrocarbyl group having 1 to 10 carbon atoms.
  • L is a group connecting 4 to 8 carbon atoms between nitrogen ( ⁇ ) atoms, an aliphatic group of 2 to 20 carbon atoms, a heteroaliphatic group of 2 to 20 carbon atoms, an alicyclic group of 2 to 20 carbon atoms, carbon number 2 to 20 heteroalicyclic group, or the aliphatic group, heteroaliphatic group, alicyclic group, and heteroalicyclic group is a group of two or more bonded,
  • Ri to F are each independently 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 aryl alkyl group having 7 to 20 carbon atoms, or an alkylaryl group having 7 to 20 carbon atoms, or 7 to 20 carbon atoms 20 alkoxyaryl groups;
  • ⁇ to ⁇ 3 are each independently halogen, hydrogen, a hydrocarbyl group having 1 to 10 carbon atoms, or a heterohydrocarbyl group having 1 to 10 carbon atoms.
  • Formula 1-1 to R 4 may be the same as each other, preferably phenyl.
  • Y 2 and Y 3 of Formula 1-1 may each independently be a halogen, hydrogen, hydrocarbyl group or heterohydrocarbyl group.
  • ⁇ , ⁇ 2 and ⁇ 3 are each independently an acetylacetonate group (cetylacetone), an acetate group (acetate), a tetrahydrofuran group (tetrahydrofuran), 2-ethyl hexanoate group (2-ethyl hexanonate), butyrate group butyrate, pentanoate, laurate, or stearate.
  • the specific organochromium compound may include all possible optical isomers.
  • the organic chromium compound includes two groups represented by Chemical Formula 1, and only one of two groups represented by Chemical Formula 1 forms a coordination bond. If present, it may be represented by Formula 1-2:
  • the organic chromium compound of the present invention may be one of the ligand group of Formula 1 is formed with the coordination bond and the remaining part of the free ligand (free Ngand) without forming the coordination bond with the creme.
  • the PNP functional group that forms a coordinative bond with chromium exhibits an oligomerization activity with respect to the olepin-based monomer, but the phosphorus (P) atom portion of the free glass coordination bond does not form a carrier or cocatalyst in the common supported catalyst system.
  • Lewis acid-base bonds can be achieved. Therefore, the supporting capacity of the PNP-Cr catalyst can be enhanced to increase the supporting efficiency and thus the activity of the supported catalyst system and the efficiency of the limerization process. Can be higher than
  • An organochromium compound including a free ligand, such as Formula 1-2 may be obtained by reacting a molar number of crack source less than the number of moles of PNP functional groups present in the ligand compound of Formula 1. For example, less than 1 mole, for example, about 0.2 to about 0.8 mole, preferably about 0.4 to about 0.6 mole of chromium source, per 1 mole of the PNP functional group present in the ligand compound represented by Formula 1 Organic cream compounds with at least some free glass can be produced. It may be desirable to include chromium sources in this range in terms of achieving both catalytic activity and supporting efficiency improvements simultaneously.
  • the common supported catalyst system of the present invention is at least one metallocene compound Include.
  • Alpha-olefin comonomers such as 1-nuxene or 1-octene produced by oligomerization of the olefinic monomers by the organic chromium compound are catalyzed by the metallocene compound supported on the supported catalyst system of the present invention. Copolymerizes with other olefinic monomers to produce polyolefins.
  • the alpha-olefin comonomers produced first by the organic cream compound are present in the supported catalyst system or in a short distance from the supported catalyst system, and thus have high accessibility with the metallocene compound which is a polyolefin (co) polymer catalyst. High comonomer conversion rates.
  • the metallocene compound may be at least one selected from the compounds represented by the following Chemical Formulas 3 to 6:
  • M 1 is a Group 4 transition metal
  • Cp 1 and Cp 2 are the same as or different from each other, and each independently selected from the group consisting of cyclopentadienyl, intenyl, 4,5,6,7-tetrahydro-1-indenyl, and fluorenyl radicals One, they may be substituted with hydrocarbons of 1 to 20 carbon atoms;
  • R a and R b are the same or different and are each independently hydrogen, C1 to C20 alkyl, C1 to C10 alkoxy, C2 to C20 alkoxyalkyl, C6 to C20 aryl, C6 to C10 aryloxy, C2 Alkenyl to C20, alkylaryl of C7 to C40, arylalkyl of C7 to C40, arylalkenyl of C8 to C40, or alkynyl of C2 to C10;
  • Z 1 is a halogen atom, C1 to C20 alkyl, C2 to C10 alkenyl, C7 to C40 alkylaryl, C7 to C40 arylalkyl, C6 to C20 aryl, substituted or unsubstituted C1 to C20 alkylidene A substituted or unsubstituted amino group, C2 to C20 alkylalkoxy, or C7 to C40 arylalkoxy;
  • n 1 or 0;
  • M 2 is a Group 4 transition metal
  • Cp 3 and Cp 4 are the same as or different from each other, and are each independently selected from the group consisting of cyclopentadienyl, indenyl, 4,5,6,7-tetrahydro-1-intenyl and fluorenyl radicals Which may be substituted with hydrocarbons having 1 to 20 carbon atoms;
  • R c and R d are the same or different and are each independently hydrogen, C1 to C20 alkyl, C1 to C10 alkoxy, C2 to C20 alkoxyalkyl, C6 to C20 aryl, C6 to C10 aryloxy, C2 Alkenyl to C20, alkylaryl of C7 to C40, arylalkyl of C7 to C40, arylalkenyl of C8 to C40, or alkynyl of C2 to C10;
  • Z 2 is a halogen atom, C 1 to C 20 alkyl, C 2 to C 10 alkenyl, C 7 to C 40 alkylaryl, C 7 to C 40 arylalkyl, C 6 to C 20 aryl, substituted or unsubstituted C 1 to C 20 alkylidene A substituted or unsubstituted amino group, C2 to C20 alkylalkoxy, or C7 to C40 arylalkoxy;
  • B 1 is one or more of a carbon, germanium, silicon, phosphorus or nitrogen atom containing radical which crosslinks the Cp 3 R c ring and the Cp 4 R d ring or crosslinks one Cp 4 R d ring with M 2 Or a combination thereof;
  • n 1 or 0;
  • M 3 is a Group 4 transition metal
  • Cp 5 is any one selected from the group consisting of cyclopentadienyl, indenyl, 4,5,6,7-tetrahydro-l-indenyl and fluorenyl radicals, which can be substituted with 1 to 20 hydrocarbons And;
  • R e is hydrogen, C1 to C20 alkyl, C1 to C10 alkoxy, C2 to C20 alkoxyalkyl, C6 to C20 aryl, C6 to C10 aryloxy, C2 to C20 alkenyl, C7 to C40 alkylaryl C7 to C40 arylalkyl, C8 to C40 arylalkenyl, or C2 to C10 alkynyl;
  • Z 3 is a halogen atom, C1 to C20 alkyl, C2 to C10 alkenyl, C7 to C40 alkylaryl, C7 to C40 aryl ' alkyl, C6 to C20 aryl, substituted or unsubstituted C1 to C20 alkyl A lidene, a substituted or unsubstituted amino group, C 2 to C 20 alkylalkoxy, or C 7 to C 40 arylalkoxy;
  • B 2 is at least one of carbon, germanium, silicon, phosphorus or nitrogen atom-containing radicals or a combination thereof that crosslinks the Cp 5 R e ring and J;
  • J is any one selected from the group consisting of NR f , O, PR f and S, wherein R f is C1 to C20 alkyl, aryl, substituted alkyl or substituted aryl.
  • A is hydrogen, halogen, C1 to C20 alkyl group, C2 to C20 alkenyl group C6 to C20 aryl group, C7 to C20 alkylaryl group, C7 to C20 arylalkyl group, C1 to C20 alkoxy group, C2 to C20 An alkoxyalkyl group, a C3 to C20 heterocycloalkyl group, or a C5 to C20 heteroaryl group;
  • D is -0-, -S-, -N (R)-or -Si (R) (R, wherein R and R 'are the same as or different from each other, and each independently hydrogen, halogen, alkyl group of C1 to C20 A C2 to C20 alkenyl group, or a C6 to C20 aryl group;
  • E is a C1 to C10 straight or branched chain alkylene group
  • B 3 is carbon, silicon or germanium;
  • Q is hydrogen, halogen, C1 to C20 alkyl group, C2 to C20 alkenyl group, C6 to C20 aryl group, C7 to C20 alkylaryl group, or C7 to C20 arylalkyl group;
  • M is a Group 4 transition metal
  • X 1 and X 2 are the same as or different from each other, and each independently halogen, C1 to
  • An alkyl group of C20 an alkenyl group of C2 to C20, an aryl group of C6 to C20, a nitro group, an amido group, an alkylsilyl group of C1 to C20, an alkoxy group of C1 to C20, or a sulfonate group of C1 to C20;
  • C 1 and C 2 are the same as or different from each other, and are each independently represented by one of the following Chemical Formulas 7a, 7b, or 7c, except that C 1 and C 2 are both of Chemical Formula 7c;
  • R9 to R25 and R9 'to R17' are the same as or different from each other, and each independently hydrogen, halogen, C1 to C20 alkyl group, C2 to C20 alkenyl group, C1 to C20 alkylsilyl group, C1 to C20 silylalkyl group , C1 to C20 alkoxysilyl group, C1 to C20 alkoxy group, C6 to C20 aryl group, C7 to C20 alkylaryl group, or C7 to C20 arylalkyl group, two adjacent to R18 to R25
  • the foregoing can be linked to each other to form a substituted or unsubstituted aliphatic or aromatic ring.
  • the C1 to C20 alkyl group 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, heptyl group, jade Tilts, etc., but this is not limited.
  • 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.
  • the C5 to C20 heteroaryl group includes a monocyclic or condensed ring heteroaryl group, carbazolyl group, pyridyl group, quinoline group, isoquinoline group, thiophenyl group, furanyl group, imidazole group, oxazolyl group, thiazolyl group , Triazine group, tetrahydropyranyl group, tetrahydrofuranyl group and the like, but are not limited thereto.
  • alkoxy group for C1 to C20 examples include a hydroxy group, a special group, a phenyloxy group, and a cyclonuclear oxy group, but are not limited thereto.
  • the Group 4 transition metals include, but are not limited to, titanium, zirconium, and hafnium.
  • R9 to R25 and R9 'to R17' are each independently hydrogen, methyl, ethyl, propyl, isopropyl, or n-butyl.
  • E of Formula 6 is more preferably a straight chain or branched alkylene group of C4 to C8, but is not limited thereto.
  • the alkylene group is an alkyl group of C1 to C20, an alkenyl group of C2 to C20, Or an aryl group of C6 to C20.
  • a in Formula 6 is hydrogen, methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, tert-butyl group, methoxymethyl group, tert- butylmethyl group, 1- ethoxyethyl group, 1-methyl It is preferable that the -1-methoxyethyl group, tetrahydropyranyl group, or tetrahydrofuranyl group is used, but not limited thereto. And, it is preferable that B 3 of Formula 6 is silicon, but is not limited thereto.
  • the metallocene compound represented by Chemical Formula 6 in the metallocene compound mainly contributes to making a high molecular weight copolymer having a high SCB (short chain branch) content, and the metallocene compound represented by Formula 3 is mainly a low SCB.
  • the content may contribute to making a low molecular weight copolymer.
  • the metallocene compound represented by Formula 4 or 5 may also contribute to making a low molecular weight copolymer having a moderate SCB content.
  • the metallocene compound represented by Chemical Formula 6 forms an ligand structure in which an indeno indole derivative and a fluorene derivative are crosslinked by a bridge compound, and has a non-covalent electron pair capable of acting as a Lewis base to the ligand structure, thereby forming a Lewis of the carrier. It is supported on the surface having acidic properties and shows high polymerization activity even when supported. In addition, due to the electronically rich indeno indole and / or fluorene group, the activity is high, and due to the proper steric hindrance and the electronic effect of the ligand, the hydrogen response is low and high activity is maintained even in the presence of hydrogen.
  • ultra-high molecular weight olefin polymers can be polymerized by stabilizing beta-hydrogen of the polymer chain in which nitrogen atoms of indenoindole derivatives are grown by hydrogen bonding.
  • by including at least two or more different metallocene compounds selected from the above formulas 3 to 6 is a high molecular weight olefin-based copolymer, and at the same time has a wide molecular weight distribution and excellent physical properties
  • metallocene compound represented by Formula 5 may be, for example, a compound represented by a structural formula, but is not limited thereto.
  • the common supported catalyst system is one in which at least one of the above-described metallocene compounds and at least one of the organic chromium compounds are supported on the carrier.
  • the common supported catalyst system may further include one or more of an aluminum-containing agent of the formula (8), and a borate-based second catalyst of the formula (9).
  • R 26 are the same as or different from each other, and are each independently a halogen radical, a hydrocarbyl radical having 1 to 20 carbon atoms, or a carbon atom substituted with halogen Hydrocarbyl radical of 20 to 20, k is an integer of 2 or more,
  • T + is a polyvalent ion of +1
  • B is boron in +3 oxidation state
  • G is independently a hydride group, dialkyl amido group, halide group, alkoxide group, aryl oxide group, hydrocarbyl group, halo car It is selected from the group consisting of bil group and halo-substituted hydrocarbyl group, wherein G has up to 20 carbons, but at less than one position, G is a halide group.
  • the polymerization activity can be improved while the molecular weight distribution of the finally produced polyolefin becomes more uniform.
  • the first cocatalyst of Chemical Formula 8 may be an alkylaluminoxane compound having a repeating unit bonded in a linear, circular or reticular form, and specific examples of the first cocatalyst include methylaluminoxane (MAO) and ethylaluminoxane. , Isobutyl aluminoxane or butyl aluminoxane.
  • MAO methylaluminoxane
  • ethylaluminoxane ethylaluminoxane
  • Isobutyl aluminoxane or butyl aluminoxane Isobutyl aluminoxane or butyl aluminoxane.
  • the second cocatalyst of Chemical Formula 9 may be a borate-based compound in the form of trisubstituted ammonium salt, dialkyl ammonium salt, or trisubstituted phosphonium salt.
  • Specific examples of the second cocatalyst include trimetalammonium tetra Phenylborate, methyldioctadecylammonium tetraphenylborate, triethylammonium tetraphenylborate, tripropylammonium tetraphenylborate, tri (n-butyl) ammonium tetraphenylborate, methyltetracyclocyclodecylammonium tetraphenylborate, N, ⁇ -dimethylaninium tetraphenylborate, ⁇ , ⁇ -diethylaninium tetraphenylborate, ⁇ , ⁇ -dimethyl (2,4,6-trimethyl
  • the molar ratio of the organic cream compound to the metallocene compound is about 10: 1 based on the transition metal. It may be about 1:10, preferably about 1: 5 to about 5: 1, but the present invention is not limited thereto, and the poly ratio to be produced may be controlled in various molar ratios according to lepin.
  • the mass ratio of the total transition metal to the carrier included in the metallocene compound and the organic chromium compound may be 1:10 to 1: 1,000.
  • the mass ratio of the promoter compound carrier may be 1: 1 to 1: 100.
  • the carrier may be a carrier containing a hydroxy group on the surface, and preferably a carrier having a highly reactive hydroxyl group and a siloxane group which are dried to remove moisture on the surface. Can be used.
  • silica, silica-alumina, and silica-magnesia dried at high temperatures may be used, which are typically oxides, carbonates, sulfates, and the like, such as Na 2 O, K 2 CO 3, BaSO 4 , and Mg (NO 3 ) 2 . May contain nitrates.
  • the drying temperature of the carrier is preferably about 200 to 800 ° C, more preferably about 300 to 600 ° C, and most preferably about 300 to 400 ° C. Moisture when the carrier has a drying temperature of less than about 200 ° C If there is too much water on the surface, the cocatalyst reacts, and if it exceeds about 800 ° C, the pores on the surface of the carrier are combined to reduce the surface area, and also the surface of the hydroxy group disappears and only siloxane groups remain. It is not preferable because the reaction space is reduced.
  • the amount of hydroxyl groups on the surface of the carrier is preferably about 0.1 to 10 mm / g, more preferably about 0.5 to 1 mm / g.
  • the amount of the hydroxyl groups on the surface of the carrier is a method and conditions for preparing the carrier or drying conditions. For example, it can be adjusted by temperature, time, vacuum or spray drying.
  • the amount of the hydroxy group is less than about 0.1 mmol / g, the reaction site with the promoter is small. If the amount of the hydroxy group is greater than about 10 mmol / g, it may be due to moisture other than the hydroxyl group present on the surface of the carrier particle. Not desirable
  • a catalyst system comprising the organic chromium compound, the metallocene compound, and the cocatalyst
  • the components of the catalyst system are active at the same time or in any order, added together in the presence or absence of monomers in any suitable solvent to make the catalyst active.
  • Suitable solvents include, but are not limited to, heptane, toluene, cyclonucleic acid, methylcyclonucleic acid, 1-nuxene, diethyl ether, tetrahydrofuran, acetonitrile, dichloromethane, chloroform, chlorobenzene, methanol, acetone, and the like.
  • the common supported catalyst system according to the present invention may be prepared by, for example, supporting a cocatalyst compound on a carrier, supporting a metallocene compound on the carrier, and supporting an organic chromium compound on the carrier. .
  • the order of the step of supporting the metallocene compound and the step of supporting the organic chromium compound may be changed as necessary. That is, the metallocene compound is first supported on the carrier. Thereafter, the supported organic catalyst compound may be further supported to produce a supported catalyst, or the organic chromium compound may be supported on a carrier first, and then the supported metallocene compound may be further supported to prepare a supported catalyst.
  • a method for producing a polyolefin including the step of polymerizing an olefin monomer in the presence of the above-described common supported catalyst system.
  • Ethylene may be preferably used as the olefin monomer.
  • the preparation of the polyolefin according to the present invention can be carried out preferably using ethylene as the olefin monomer, using one continuous slurry polymerization reactor, a loop slurry reactor, a gas phase reactor or a solution reactor.
  • the common supported catalyst system is an aliphatic hydrocarbon solvent having 5 to 12 carbon atoms, for example, pentane, nucleic acid, heptane, nonane, decane, and isomers thereof, such as aromatic hydrocarbon solvents such as benzene, dichloromethane and chlorobenzene. It may be dissolved or diluted in a hydrocarbon solvent substituted with a chlorine atom, and then injected into a reaction system.
  • the solvent used herein is preferably used by removing a small amount of water or air that acts as a catalyst poison by treating a small amount of alkyl aluminum, and may be carried out by further use of a promoter.
  • the step of polymerizing the lepin monomer may be carried out at a temperature of about 5 ° C. to about 20 ° C., preferably at a temperature of about 30 ° C. to about 150 ° C.
  • the step of polymerizing the olefinic monomer is at a pressure of about 1 bar to about 300 bar, Preferably it can be carried out at a pressure of about 2 bar to about 150 bar.
  • the polymerization can be carried out by supplying the lepin-based monomer in the presence of hydrogen gas.
  • the hydrogen gas serves to suppress the rapid reaction of the metallocene compound of the initial polymerization to produce a higher amount of high molecular weight polyolefin. Therefore, by using such a hydrogen gas, a higher molecular weight and Polyolefins with a broad molecular weight distribution can be obtained effectively.
  • the hydrogen gas may be introduced such that the molar ratio of hydrogen gas: an olefinic monomer is about 1: 100 to 1: 1,000.
  • the amount of the hydrogen gas is too small, the catalytic activity is not sufficiently realized, so that the desired molecular weight and molecular weight distribution can be obtained.
  • the production of polyolefins may be difficult to obtain, and the addition of excessive amounts of hydrogen gas may not provide sufficient catalytic activity.
  • each of the organic chromium compound and the metallocene compound supported on the common supported catalyst system and the olefinic monomers in contact with each other are multiplied (oligomerization). Reaction) and polymerization reaction of the olefinic monomer.
  • the oligomerization reaction and polymerization reaction are not limited to sequentially occurring, and each metallocene compound or organic cream compound supported on the common supported catalyst system and an olefin resin monomer are used. At the same time, they may occur sequentially or randomly, depending on their contact with.
  • alpha-olefins such as propylene, 1-butene, 1-octene, and 1-nuxene produced by the contact between the organic chromium compound and the olefinic monomer are present in or near the supported catalyst system. Therefore, the alpha-olefin produced by the organic cream compound supported on the common supported catalyst system is highly in contact with the metallocene compound, and is much higher than in the general olefin copolymerization reaction in which the alpha-olefin is introduced into the reaction system separately from the catalyst system. do.
  • TiCI 3 (THF) 3 (10 mm) was quickly added to the dilithium salt of -78 ° C ligand synthesized in THF solution from (Dimethyl (tetramethylCpH) t-Butylaminosilane).
  • the semi-aqueous solution was slowly stirred at -78 ° C for room temperature for 12 hours.
  • an equivalent amount of PbCI 2 (10 mmol) was added to the semi-aqueous solution at room temperature, followed by stirring for 12 hours. After stirring for 12 hours, the blue vagina obtained a black solution.
  • nucleic acid was added to filter the product.
  • the desired ([methyl (6-t-buthoxyhexyl) silyl (n5-tetramethylCp) (t-Butylamido)] TiCI 2 ) from 1 H-NMR was (tBu-O- (CH 2 ) 6 ) (CH 3 ) Si (C 5 (CH 3 ) 4 ) (tBu-N) TiCI 2 .
  • Example 2 The polymer obtained therefrom was filtered to remove most of the polymerization solvent and then dried for 4 hours in an 80 ° C vacuum oven.
  • Example 2 The polymer obtained therefrom was filtered to remove most of the polymerization solvent and then dried for 4 hours in an 80 ° C vacuum oven.
  • Example 1 polyolefin polymerization was carried out in the same manner as in Example 1 except that the common supported catalyst of Preparation Example 2 was used.
  • Example 3 Example 3
  • Example 1 polyolefin polymerization was carried out in the same manner as in Example 1, except that the supported catalyst of Preparation Example 2 was used, and hydrogen was added at 0.03% relative to ethylene. Comparative Example 1
  • Example 1 polyolefin polymerization was carried out in the same manner as in Example 1, except that the support catalyst of Comparative Preparation Example 1 was used, and 13.5 g of 1-nuexene was added.
  • the supported catalyst, polymerization conditions, polymerization activity, molecular weight and molecular weight distribution of the obtained polymers used in Examples and Comparative Examples are shown in Table 1 below.
  • the content of the alpha olefin in the polyolefin was confirmed by calculating the molar ratio of the branch chain of each sample after normalizing the integration value of the main chain to 1000 in the 1 H NMR spectrum. More specifically, when the analytical value having different structure ends is obtained from the co-polymerized polyolefin, the rest of the co-polymerized polyolefin is estimated except for the end of the structure having a double bond (that is, the alpha-olefin not used for the co-polymerization). The chain to 1000 Placed and calculated as the ratio of relative ends. At this time, it is assumed that structures having a double bond at the terminal are produced in the same molar ratio with the same molecular weight. Referring to Table 1, Comparative Example 1 was confirmed that there is no copolymer phosphorus by copolymerizing only ethylene without a comonomer using only a supported catalyst on which a metallocene compound is supported.
  • Comparative Example 2 was polymerized by using only a metallocene supported catalyst and adding 1-nuxene as a comonomer, and as a result, it was confirmed that 1-nuxene copolymerized polyolefin was produced. Although 13.5 g was added, it was confirmed that about 13.0 g of 1-nucleene remained in the filtrate after synthesis, and an equivalent amount of 1-nuxene remained in the copolymerization.

Abstract

La présente invention concerne un système catalyseur hybride supporté, et un procédé de préparation d'une polyoléfine l'utilisant. Selon la présente invention, le système catalyseur hybride supporté peut simultanément conduire l'oligomérisation et la polymérisation de monomères d'oléfine présentant une efficacité élevée dans un réacteur unique sans conduire séparément de procédé de préparation d'α-oléfines. Par conséquent, les coûts de production d'un produit final peuvent être réduits dans la mesure où le coût de préparation ou d'achat d'un comonomère, qui est un matériau coûteux, est réduit.
PCT/KR2016/000880 2015-05-15 2016-01-27 Système catalyseur hybride supporté, et procédé de préparation de polyoléfine l'utilisant WO2016186295A1 (fr)

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CN201680014797.8A CN107406535B (zh) 2015-05-15 2016-01-27 复合负载型催化剂体系及使用其制备聚烯烃的方法
JP2017543375A JP6511152B2 (ja) 2015-05-15 2016-01-27 混成担持触媒系、およびこれを用いたポリオレフィンの製造方法
EP16796622.5A EP3243848B1 (fr) 2015-05-15 2016-01-27 Système catalyseur hybride supporté, et procédé de préparation de polyoléfine l'utilisant
US15/552,136 US10189920B2 (en) 2015-05-15 2016-01-27 Hybrid supported catalyst system and method of preparing polyolefin using the same

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WO2021210755A1 (fr) 2020-04-16 2021-10-21 주식회사 엘지화학 Copolymère d'éthylène/alpha-oléfine ayant une excellente isolation électrique
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WO2021210756A1 (fr) 2020-04-16 2021-10-21 주식회사 엘지화학 Composition de film d'encapsulation comprenant un copolymère d'éthylène/alpha-oléfine et film d'encapsulation la comprenant
WO2021210749A1 (fr) 2020-04-16 2021-10-21 주식회사 엘지화학 Composition de film d'encapsulation comprenant un copolymère d'éthylène/alpha-oléfine et film d'encapsulation la comprenant

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WO2021210755A1 (fr) 2020-04-16 2021-10-21 주식회사 엘지화학 Copolymère d'éthylène/alpha-oléfine ayant une excellente isolation électrique
WO2021210748A1 (fr) 2020-04-16 2021-10-21 주식회사 엘지화학 Copolymère d'éthylène/alpha-oléfine ayant une excellente isolation électrique
WO2021210756A1 (fr) 2020-04-16 2021-10-21 주식회사 엘지화학 Composition de film d'encapsulation comprenant un copolymère d'éthylène/alpha-oléfine et film d'encapsulation la comprenant
WO2021210749A1 (fr) 2020-04-16 2021-10-21 주식회사 엘지화학 Composition de film d'encapsulation comprenant un copolymère d'éthylène/alpha-oléfine et film d'encapsulation la comprenant
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