WO2016204469A1 - Procédé de fabrication d'un catalyseur métallocène supporté - Google Patents

Procédé de fabrication d'un catalyseur métallocène supporté Download PDF

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WO2016204469A1
WO2016204469A1 PCT/KR2016/006264 KR2016006264W WO2016204469A1 WO 2016204469 A1 WO2016204469 A1 WO 2016204469A1 KR 2016006264 W KR2016006264 W KR 2016006264W WO 2016204469 A1 WO2016204469 A1 WO 2016204469A1
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group
formula
molecular weight
alkyl
metallocene
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PCT/KR2016/006264
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English (en)
Korean (ko)
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유영석
조경진
권혁주
최이영
이기수
송은경
김우리
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주식회사 엘지화학
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Priority claimed from KR1020160029835A external-priority patent/KR101850985B1/ko
Application filed by 주식회사 엘지화학 filed Critical 주식회사 엘지화학
Priority to EP16811882.6A priority Critical patent/EP3255066B1/fr
Priority to JP2017546872A priority patent/JP6450467B2/ja
Priority to CN201680021196.XA priority patent/CN107531828B/zh
Priority to US15/566,098 priority patent/US10501563B2/en
Publication of WO2016204469A1 publication Critical patent/WO2016204469A1/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
    • 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
    • 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
    • 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
    • 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
    • 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 method for preparing a metallocene supported catalyst which can more effectively prepare polyolefins which can be preferably used for blow molding, as the polymer elasticity increases and the swell (swel l) has a molecular weight distribution.
  • metallocene catalysts using Group 4 transition metals are easier to control the molecular weight and molecular weight distribution of polyolefins than conventional Ziegler-Natta catalysts, and can control the comonomer distribution of polymers, resulting in improved mechanical properties and processability. And so on.
  • polyolefins prepared using metallocene catalysts have a problem of poor workability due to narrow molecular weight distribution.
  • Tebbe reagent a complex of titanocene (Tebno reagent) and alkylaluminum (Alkylaluminium) called Tebbe reagent and has played a role in increasing the molecular weight.
  • Tebbe reagent The main characteristic of the Tebbe reagent is that the Tebbe reagent is activated by a base to form titaniumalkyl idene, which is related to the double bond. , Metathesis, etc.), but the role of Tebe reagents in ethylene polymerization without the addition of lewis bases is not known.
  • the Petasis group succeeded in ring-closing metathesis by simply adding heat to Tebe reagents. Accordingly, it is presumed that Tebbe reagent forms titaniumalkyl idene by polymerization temperature when it participates in polymerization, resulting in polymerization using alkylidene-specific reactions.
  • the technology and development can be more effectively produced the polyolefin which can satisfy mechanical properties and processability at the same time and can be preferably used for blow molding. This is constantly required.
  • the present invention provides a method for preparing a metallocene-supported catalyst which can more effectively prepare a polyolefin which can be preferably used for blow molding, as the polymer elasticity increases and the molecular weight distribution of the swell is improved. will be.
  • the present invention is prepared in the presence of a metallocene supported catalyst prepared from the production method, it can satisfy mechanical properties and processability at the same time to provide a polyolefin which can be preferably used for blow molding. '
  • the present invention is to prepare a molecular weight regulator composition by mixing a cyclopentadienyl metal compound of Formula 1 and an organoaluminum compound of Formula 2 for 50 to 108 hours at room temperature; And supporting at least one metallocene compound represented by one of the following Chemical Formulas 3 to 6 and the molecular weight modifier composition on a carrier; and a supported metallocene catalyst.
  • Cp 1 and Cp 2 are each independently a ligand including a cyclopentadienyl group, an indenyl group, or a fluorenyl group;
  • R 1 and R 2 are each independently a substituent of Cp 1 and Cp 2 , hydrogen, alkyl of 1 to 20 carbon atoms, alkenyl of 1 to 20 carbon atoms, alkylaryl of 7 to 20 carbon atoms, arylalkyl of 7 to 20 carbon atoms, Aryl having 6 to 20 carbon atoms, heteroalkyl having 1 to 20 carbon atoms, heteroalkenyl having 2 to 20 carbon atoms, heteroalkylaryl having 6 to 20 carbon atoms, heteroarylaryl having 6 to 20 carbon atoms or heteroaryl having 5 to 20 carbon atoms, ;
  • M 1 is a Group 4 transition metal element;
  • X is halogen,
  • R 3 , R 4 and R 5 in Formula 2 are each independently an alkyl group having 4 to 20 carbon atoms or halogen, at least one of R 3 , R 4 and R 5 is an alkyl group having 4 to 20 carbon atoms,
  • M 1 is a Group 4 transition metal
  • Cp 5 and Cp 6 are the same as or different from each other, and each independently Cyclopentadienyl, indenyl, 4,5,6,7-tetrahydro-1-indenyl, and fluorenyl radicals, and any one selected from the group consisting of hydrocarbons having 1 to 20 carbon atoms, ;
  • R a and R b are the same as or different from each other, and 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 7 and Cp 8 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-indenyl and fluorenyl radicals They may be substituted with a hydrocarbon having 1 to 20 carbon atoms;
  • R c and R d are the same as or different from each other, and each independently hydrogen, C1 to C20 alkyl, C1 to C10 alkoxy, C2 to C20 alkoxyalkyl, C6 to C20 aryl, C6 to C10 aryloxy, C2 C20 to C40 alkenyl, C7 to C40 alkylaryl, C7 to C40 arylalkyl, C8 to C40 arylalkenyl, or C2 to C10 alkynyl;
  • Z 2 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 alkyl Liden, 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 Cp3 ⁇ 4 c ring with the Cp 4 R d ring or crosslinks one Cp 4 R d ring with M 2 or Is a combination of;
  • n 1 or 0;
  • M 3 is a Group 4 transition metal
  • Cp 9 is any one selected from the group consisting of cyclopentadienyl, indenyl, 4,5,6,7-tetrahydro-1-indenyl and fluorenyl radicals, which may be substituted with hydrocarbons having 1 to 20 carbon atoms Can be;
  • 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-C40 arylalkyl, C8-C40 arylalkenyl, or C2-C10 alkynyl;
  • Z 3 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 Or a substituted or unsubstituted amino group, C2 to C20 alkylalkoxy, or C7 to C40 arylalkoxy;
  • B 2 ' is one or more or a combination of carbon, germanium, silicon, phosphorus or nitrogen atom containing radicals which crosslink the Cp 5 R e ring and J;
  • J is any one selected from the group consisting of NR f , 0, PR f and S, wherein R f is C1 to C20 alkyl, aryl, substituted alkyl or substituted aryl, [Formula 6]
  • 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 C20 alkoxyalkyl group, C3 to C20 heterocycloalkyl group, or C5 to C20 heteroaryl group;
  • D is — 0—, -S-, -N (R)-or -SKRKR ')-, wherein R and R' are the same as or different from each other, and each independently hydrogen, halogen, an alkyl group of C1 to C20, C2 To C20 alkenyl group, or C6 to C20 aryl group;
  • L is a C1 to C10 straight or branched chain alkylene group
  • B 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 C20 alkyl group, C2 to C20 alkenyl group, C6 to C20 aryl group, nitro group, amido group, C1 to C20 alkylsilyl group , A C1 to C20 alkoxy group, or a C1 to C20 sulfonate group;
  • C 1 and C 2 are the same as or different from each other, and each independently
  • R1 to R17 and R1 'to R9' 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 alkyl Silyl 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 or more adjacent to each other of R10 to R17 may be connected to each other to form a substituted or unsubstituted aliphatic or aromatic ring.
  • the present invention also provides a method for producing a polyolefin, which comprises polymerizing an olefin monomer in the presence of a metallocene supported catalyst.
  • the present invention also provides a polyolefin produced according to the above production method.
  • a method for preparing a metallocene supported catalyst, a metallocene supported catalyst prepared therefrom, a method for preparing polyolefin using the same, and a polyolefin prepared therefrom will be described.
  • a metallocene supported catalyst is prepared by supporting a specific molecular weight modifier composition with a metallocene compound on a carrier.
  • the method for preparing the metallocene supported catalyst may include mixing a cyclopentadienyl metal compound of Formula 1 and an organoaluminum compound of Formula 2 to stir at room temperature for 50 to 108 hours to prepare a molecular weight modifier composition; And supporting at least one metallocene compound represented by one of Chemical Formulas 3 to 6 and the molecular weight modifier composition on a carrier.
  • M 1 is a Group 4 transition metal
  • Cp 5 and Cp 6 are the same as or different from each other, and are 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 a hydrocarbon of 1 to 20 carbon atoms;
  • R a and R b are the same as or different from each other, and 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 Or 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 7 and Cp 8 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-indenyl and fluorenyl radicals They may be substituted with a hydrocarbon having 1 to 20 carbon atoms;
  • R c and R d are the same as or different from each other, and each independently hydrogen, C1 to C20 alkyl, C1 to C10 alkoxy, C2 to C20 alkoxyalkyl, C6 to C20 aryl, C6 to C10 aryloxy, C2 C20 to C40 alkenyl, C7 to C40 alkylaryl, C7 to C40 arylalkyl, C8 to C40 arylalkenyl, or C2 to C10 alkynyl;
  • Z 2 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 Or 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 Cp3 ⁇ 4 c ring with the Cp 4 R d ring or crosslinks one Cp 4 R d ring with M 2 or Is a combination of;
  • n 1 or 0;
  • M 3 is a Group 4 transition metal
  • Cp 9 is any one selected from the group consisting of cyclopentadienyl, indenyl, 4, 5, 6, 7-tetrahydro-1-indenyl and fluorenyl radicals, which are substituted with hydrocarbons having 1 to 20 carbon atoms Can be;
  • R e is hydrogen, alkyl of C1 to C20, alkoxy of C1 to C10, alkoxyalkyl of C2 to C20, aryl of C6 to C20, aryloxy of C6 to C10, 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 arylalkyl, C6 to C20 aryl, substituted or unsubstituted C1 to C20 alkylidene Or a substituted or unsubstituted amino group, C2 to C20 alkylalkoxy, or C7 to C40 arylalkoxy;
  • B 2 is at least one or a combination of carbon, germanium, silicon, phosphorus or nitrogen atom containing radicals which crosslink the Cp3 ⁇ 4 e ring and J;
  • J is any one selected from the group consisting of NR f , 0, 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 alkoxyalkyl group, C3 to C20 heterocycloalkyl group, or C5 to C20 hetero Aryl 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 are each independently hydrogen, halogen, C1 to An alkyl group of C20, an alkenyl group of C2 to C20, or an aryl group of C6 to C20;
  • L is a C1 to C10 straight or branched chain alkylene group
  • B is carbon, silicon or germanium
  • Q is hydrogen, halogen, C1 to C20 alkyl group, C2 to C20
  • 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 C20 alkyl group, C2 to C20 alkenyl group, C6 to C20 aryl group, nitro group, amido group, C1 to C20 alkylsilyl group , A C1 to C20 alkoxy group, or a C1 to C20 sulfonate group;
  • C 1 and C 2 are the same as or different from each other, and are each independently represented by one of the following Formulas 7a, 7b, or 7c, except that C 1 and C 2 are both Formula 7c;
  • R1 to R17 and R1 'to R9' 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 and 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 or more adjacent to each other of R10 to R17 are connected to each other to form a substituted or unsubstituted aliphatic or aromatic ring.
  • Cp 1 and Cp 2 are each independently a ligand including a cyclopentadienyl group, indenyl group, or fluorenyl group;
  • R 1 and R 2 are each independently a substituent of Cp 1 and Cp 2 , hydrogen, alkyl of 1 to 20 carbon atoms, alkenyl of 1 to 20 carbon atoms, alkylaryl of 7 to 20 carbon atoms, arylalkyl of 7 to 20 carbon atoms, Aryl having 6 to 20 carbon atoms, heteroalkyl having 1 to 20 carbon atoms, heteroalkenyl having 2 to 20 carbon atoms, heteroalkylaryl having 6 to 20 carbon atoms, heteroarylaryl having 6 to 20 carbon atoms or heteroaryl having 5 to 20 carbon atoms, ;
  • M 1 is a Group 4 transition metal element;
  • X is halogen.
  • R 1 and R 2 may be each independently selected from the group consisting of hydrogen, methyl, ethyl, butyl, and t-butoxy nucleus.
  • M 1 is a Group 4 transition metal element, preferably may be selected from the group consisting of titanium, zirconium and hafnium.
  • X is a halogen, preferably may be selected from the group consisting of F, (: 1, Br and I.
  • R 3 , R 4 and R 5 in Formula 2 are each independently an alkyl group having 4 to 20 carbon atoms or a halogen, and at least one of R 3 , R 4 and R 5 is an alkyl group having 4 to 20 carbon atoms.
  • R 3 , R 4 and R 5 may each independently be an isobutyl group.
  • the metal alkyl idenes made from metals have different partial charges between the metals and the alkyl groups, so that the alkyl idenes with partial negative charges are combined with the met l locenes of the forward transition metals with l ewi s acidic c than aluminum alkyls. It is expected to increase the molecular weight while having intermediates in the form and to enable the production of polyolefins having large molecular weights and wider distributions.
  • a metallocene supported catalyst may be prepared by reacting a specific molecular weight modifier composition with a metallocene compound as described above as described in Scheme 1 and supported on a carrier.
  • Helero extends the meaning of molecular weight control action by the hydrogen reactivity change of the existing Tebbe type reagent, the precursor and titanocene (Ti tanocene)
  • This technique is used to control the molecular weight by directing the reaction and controlling the reaction of hydrogen by using a small amount of Ti tanocene. This results in instability, ie, the use of a minimum molecular weight modifier to enable efficient molecular weight control.
  • the molecular weight regulator composition is 0.1 to 1.0 equivalent (eq.), Preferably 0.1 to 1 to the cyclopentadienyl metal compound of Formula 1 and the organoaluminum compound of Formula 2 Mixing in 0.5 equivalents, it can be produced by stirring at room temperature, for example 50 to 108 hours, preferably 62 to 90 hours at 22.5 to 25 I.
  • the molecular weight modifier composition is a mixture of the cyclopentadienyl metal compound of Formula 1 and the organoaluminum compound of Formula 2, or a reaction product thereof, for example, formed by reacting a compound of Formula 1 and Formula 2 Organometallic complexes.
  • the molecular weight regulator including a specific substituent in the cyclopentadienyl group of the formula (1) and the organic functional group of the formula (2) shows a significantly improved solubility compared to the conventional, uniformly catalyst with excellent precursor properties (homogenei ty) with the catalyst precursor
  • the composition can be formed to exhibit excellent polymerization performance.
  • the metallocene supported catalyst of the present invention has a molecular weight distribution in which the swell (swel l) is improved by increasing the molecular weight and polymer elasticity, it can exhibit excellent mechanical properties and processability, blow The polyolefin which can be preferably used for molding etc. can be manufactured more effectively.
  • the molecular weight modifier generated by reacting the cyclopentadienyl metal compound of Formula 1 and the organoaluminum compound of Formula 2 may be represented by the following Formula 8, Formula 9, Formula 10, or Formula 11.
  • Organo lithium and organo magnesium have a mechanism that acts as a strong base that has nothing to do with ti tanocene carbine.
  • the present invention focuses on the chemical reaction that Ti tanocene combined with organoaluminum can be formed by thermal decomposition of Ti tanium carbene, which can result from the carbene, and is most important in the formation of polymers.
  • the molecular weight modifier composition includes the compounds of Formulas 1 and 2 in the form of a mixture that does not react with each other, or a reaction product of the compounds of Formulas 1 and 2, for example, a metal of these compounds.
  • the elements may be included in the form of organometallic complexes in which X and / or R 1 , R 2 and R 3 are bonded to each other. In this case, together with the organometallic complex, some of the unreacted compounds of Formula 1 and / or Formula 2 may further be included.
  • the molecular weight modifier assists the activity of the metallocene catalyst, allowing polymerization to proceed with great activity even in the presence of a relatively small amount of metallocene catalyst, Increased elasticity allows the production of polyolefins having a molecular weight distribution with better swels.
  • cyclopentadienyl metal compound of Formula 3 examples include biscyclopentadienyl titanium dichloride, biscyclopentadienyl zirconium dichloride, biscyclopentadienyl hafnium dichloride, and bis indenyl.
  • Titanium dichloride or bisflorenyltitanium dichloride bis (2-ethylcyclopenta-2, 4-diene-1-yl) titanium dichloride, bis (2-butylcyclopenta-2, 4-diene-1-yl Titanium dichloride, bis (2- (6-t-subsidiary-nuclear) cyclopenta-2, 3-diene-1-yl) titanium dichloride, bis (2-ethylcyclopenta-2, 4-diene- 1-day) zirconium Dichloride, bis (2-ethylcyclopenta-2, 4-dieen-1-yl) hafnium dichloride, and the like.
  • organoaluminum compound of Formula 4 examples include triisobutyl aluminum, trinuclear aluminum, trioctyl aluminum, diisobutyl aluminum chloride, dinuxyl aluminum chloride, isobutyl aluminum dichloride, and the like.
  • the compound of Formula 1 and the compound of Formula 2 are each a metal element (M) contained in the formula (3), aluminum (A1) contained in the formula (4) as a molar ratio, about 1: 0.01 to 1: 100 Or in a molar ratio of about 1: 0.5 to 1: 10.
  • the molecular weight modifier may be used in an amount of about 0.01 to 10 parts by weight, or about 0.01 to 1 part by weight based on 100 parts by weight of the catalyst precursor.
  • the molecular weight modifier is about 1 to 85 mol, preferably about 3 to 70 mol, more preferably about 5 to 55 mol%, black 10 to 50 mol% based on the total amount of the catalyst precursor Can be used.
  • the effect and effect of the addition of the molecular weight modifier are optimized, and the polymer melt index is low, the molecular weight distribution is wide, the molecular weight is large, and the stress cracking resistance is improved more than the density or polymer melt index. Polyolefin can be obtained.
  • the present invention when an excessive amount of organoaluminum is present in the reaction vessel, it reacts with the metallocene catalyst as in general alkylaluminum, causing deactivation while causing deactivation. Accordingly, the present invention has the advantage of not inhibiting the activity of the existing metallocene precursor itself by reacting the catalytic amount of the molecular weight regulator with the maximum efficiency compared to the precursor. In addition, the present invention can effectively control the molecular weight of a single or common supported catalyst while using a small amount of the molecular weight regulator corresponding to the amount of catalyst of the metallocene precursor supported when preparing the metallocene supported catalyst.
  • the present invention has the advantage of finely adjusting the polymer structure according to the amount of the molecular weight regulator while maintaining the polymerization conditions without activity degradation.
  • the metallocene supported catalyst is to be used in the form of a supported catalyst in which the metallocene compound and the molecular weight modifier composition is supported on a carrier.
  • the metallocene catalyst may be used together by common hybridization of two different subphase metallocene compounds, or may include only one metallocene compound.
  • the metallocene compound represented by Chemical Formula 3 may be, for example, a compound represented by one of the following structural formulas, but is not limited thereto.
  • the compound represented by Chemical Formula 4 may be, for example, a compound represented by the following structural formula, but is limited thereto.
  • the compound represented by Formula 5 may be, for example, a compound represented by the following structural formula, but is not limited thereto.
  • Group 4 transition metal (M) may include titanium, zirconium, hafnium, and the like, but is not limited thereto.
  • R1 to R17 and R1 to R9 of Chemical Formulas 7a, 7b, and 7c are each independently hydrogen, methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, tert-butyl group, pentyl group, nucleosil group, heptyl group, octyl group, phenyl group, halogen group, trimethylsilyl group, triethylsilyl group, tripropylsilyl group, tributylsilyl group, triisopropylsilyl group, It is more preferable that it is a trimethylsilyl methyl group, a meso group, or an ethoxy group, but it is not limited only to this.
  • L is more preferably a C4 to C8 linear or branched alkylene group, but is not limited thereto.
  • the alkylene group may be unsubstituted or substituted with an alkyl group of C1 to C20, an alkenyl group of C2 to C20, or an aryl group of C6 to C20.
  • A is hydrogen, methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, tert-butyl group, methoxymethyl group, tert-subspecific methyl group, 1-specific It is preferably an ethyl group, 1-methyl-1-methoxyethyl group, tetrahydropyranyl group, or tetrahydrofuranyl group, but is not limited thereto.
  • B is preferably silicon, but is not limited thereto.
  • the metallocene compound of Formula 6 may be a non-covalent electron pair which forms a structure in which an indeno indol derivative and / or a fluorene derivative are crosslinked by a bridge, and may act as a Lewis base to the ligand structure.
  • the Lewis acid property of the carrier it has a high polymerization activity even when supported on the surface.
  • the activity is high, and due to the proper steric hindrance and the electronic effect of the ligand, the reaction is not only low but also maintains high activity even in the presence of hydrogen. .
  • the beta-hydrogen of the polymer chain in which the nitrogen atom of the intenoindole derivative is grown is stabilized by hydrogen bonding, thereby inhibiting the beta-hydrogen el itninat ion, thereby adding an ultra high molecular weight olefin polymer.
  • a specific example of the structure represented by Chemical Formula 7a may include a structure represented by one of the following structural formulas, but is not limited thereto.
  • Chemical Formula 7b may include a structure represented by one of the following structural formulas, but is not limited thereto.
  • Chemical Formula 7c may include a structure represented by one of the following structural formulas, but is not limited thereto.
  • metallocene compound represented by Chemical Formula 6 may include a compound represented by one of the following structural formulas, but only
  • the metallocene compound and the molecular weight modifier composition as described above are used in the form of a supported catalyst supported on a carrier.
  • the supporting step may be performed by mixing the carrier, the metallocene catalyst and the molecular weight modifier composition at a temperature of 30 to 100 ° C., preferably 35 to 90 t, or 40 to 80 ° C. at 1 hr to 12 hr, Preferably it can be carried out by stirring for 1 hr to 4 hr.
  • the metallocene supported catalyst may be in the form of a supported metallocene catalyst in which a metallocene compound and a promoter are supported on a carrier.
  • a metallocene compound and a promoter may be different from each other.
  • It may be a common supported metallocene catalyst comprising a.
  • the carrier may be silica, silica-alumina, silica-magnesia, or the like, and may be any carrier known to support other metallocene catalysts.
  • a carrier may be used in a dry state at a high temperature, the drying temperature may be, for example, about 180 to 800 ° C. If the drying temperature is too low, excess separation on the carrier may react with the promoter to degrade the performance. If the drying temperature is too high, the hydroxyl group content is too low on the surface of the carrier to reduce the reaction space with the promoter. can do.
  • the carrier may be one carrying an aluminum-containing first cocatalyst of the formula (12).
  • R 18 is each independently a halogen, a halogen substituted or unsubstituted hydrocarbyl group having 1 to 20 carbon atoms, n is an integer of 2 or more.
  • the molecular weight modifier composition may be supported immediately after the metallocene compound is supported on the carrier on which the first cocatalyst is supported.
  • the organo aluminum and precursors are first reacted with MA0 and then supported on silica.
  • Ti tani cene Ti tani cene
  • Tibec reagent Tibec reagent
  • the stability of the supported catalyst resulting from the heterogeneity of the MA0 solution according to the reactivity between the precursor and MA0, and the conventional Tebe reagent reaction are about 2 to 4 days in the present invention, for example, 3 Problems with reproducibility of catalyst properties can arise from shorter reaction times compared to days.
  • the present invention is a method in which the molecular weight regulator is added immediately after the metallocene compound catalyst precursor is added to silica loaded with a C 1 promoter such as MA0 to ensure uniformity of silica-MA0 itself,
  • the regulator can also sufficiently increase the molecular weight even with a catalytic amount compared to the precursor.
  • the present invention can prevent the occurrence of a problem of inhibiting the intrinsic activity of the precursor in a small amount of the molecular weight regulator.
  • the common supported metallocene catalyst it may further include a borate-based crab 2 co-catalyst of the formula (13):
  • T + is a + monovalent polyatomic ion
  • B is boron in the +3 oxidation state
  • Q is independently a hydride group, a dialkylamido group, a halide group, an alkoxide group, an aryl oxide group, Selected from the group consisting of hydrocarbyl groups, halocarbyl groups and halo-substituted hydrocarbyl groups, wherein Q has up to 20 carbons, but at less than one position Q is a halide group.
  • the first cocatalyst of Chemical Formula 12 may be an alkylaluminoxane compound having a repeating unit bonded in a linear, circular or reticulated form, and specific examples of the first cocatalyst include methylaluminoxane (MA0) and ethylalumina. Noxyl acid, isobutyl aluminoxane or butyl aluminoxane.
  • the C2 promoter of Formula 13 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 , ⁇ , ⁇ -dimethylanilinium tetraphenylborate , ⁇ , ⁇ -diethylanilinium tetraphenylborate , ⁇ dimethyl (2,4,6-trimethylanilinium) tetraphenyl Borate, trimethylammonium tetrakis (pentafluorophenyl) borate, methylditetradecylammonium tetrakis (
  • the carrier may be made of one metal.
  • the Rosene compound and the Crab 1 promoter are sequentially supported, the second metallocene compound and the Crab 2 promoter can be sequentially supported. In between these supporting steps, a washing step using a solvent may be further performed.
  • the production of a polyolefin comprising the step of polymerizing the olethene-based monomer in the presence of a metallocene-supported catalyst carrying a specific molecular weight modifier with a metallocene compound on the carrier A method is provided.
  • the polymerizing of the olefin monomer may be performed by mixing at least one metallocene compound represented by one of Chemical Formulas 3 to 6 with a cyclopentadienyl metal compound of Chemical Formula 1 and an organoaluminum compound of Chemical Formula 2 below.
  • a metallocene supported catalyst obtained by supporting together a molecular weight modifier composition obtained by stirring at 22.5 to 25 ° C. for 50 to 108 hours, preferably 62 to 90 hours.
  • a metallocene supported catalyst obtained by supporting together a molecular weight modifier composition obtained by stirring at 22.5 to 25 ° C. for 50 to 108 hours, preferably 62 to 90 hours.
  • a polyolefin may be prepared by polymerizing any olefin monomer.
  • the olefin monomer that can be used at this time include ethylene, propylene, 1-butene, 1-nuxene, 1-octene, 1-pentene, 4-methyl-1-pentene, 1-nucleene, 1-heptene, 1-decene , 1-Undecene, 1-dodecene, norbornene, ethylidenenorbornene, styrene, alpha -methylstyrene and 3- Chloromethyl styrene and the like.
  • polyethylene is produced using ethylene, or together with ethylene, propylene, 1-butene, 1-nuxene, 1-octene, 1-pentene, 4-methyl-1-pentene, 1
  • An ethylene-alpha olefin copolymer may be prepared by copolymerizing alpha olefins such as -nuxene, 1-heptene, 1-decene, 1-undecene or 1-dodecene.
  • the comonomer such as alpha olefin may be copolymerized by being used in an amount of about 30% by weight or less, or about 0 to 20% by weight, or about 0.01 to 15% by weight based on the total amount of the olefin monomer. have.
  • this amount of alpha olefins are copolymerized, the final polyolefins produced can exhibit excellent stress cracking resistance within a density range suitable for blow molding.
  • the density of the polymer may be decreased, leading to a decrease in flexural strength.
  • the polymerization method of the above-described embodiment may be carried out in a slurry phase in an aliphatic hydrocarbon solvent such as nucleic acid, butane or pentane, for example.
  • an aliphatic hydrocarbon solvent such as nucleic acid, butane or pentane, for example.
  • the metallocene catalyst including the molecular weight modifier exhibits excellent solubility in such a solvent, they can be stably supplied to the dissolution and reaction system so that the polymerization process can proceed effectively, and poly having a large molecular weight and a wider molecular weight distribution can be obtained. Lepin can be produced effectively.
  • the polymerization of the olefinic monomers may be performed by reacting at a temperature of about 25 to about 500 ° C. and about 1 to about 100 kgf / cm 2 for about 1 to about 24 hours. Specifically, the polymerization of the olefin monomer may be carried out at a temperature of about 25 to about 500 ° C, preferably about 25 to about 200 ° C, more preferably about 50 to about 100 ° C.
  • the reaction pressure may also be carried out at about 1 to about 100 kgf / cm 2 , preferably at about 1 to about 50 kgf / cm 2 , more preferably at about 5 to about 40 kgf / cm 2 .
  • the catalytic activity calculated from the ratio of the weight (g) of the polymer produced per unit weight content (g) of the catalyst used in the process for producing the polyolefin based on the unit time (h) is not less than 1.0 kg / gCat-hr or 1.0 to 15 0 kg / gCat ⁇ hr, preferably 10.0 kg / gCat ⁇ hr or more, and more preferably 8.0 kg / gCat ⁇ hr or more.
  • the present invention can effectively control the molecular weight of a single or common supported catalyst while using a small amount of the molecular weight regulator corresponding to the amount of catalyst of the metallocene precursor supported when preparing the metallocene supported catalyst.
  • Existing conventional techniques have been shown to simply increase the molecular weight, but the present invention has the advantage of finely adjusting the polymer structure according to the amount of the molecular weight regulator while maintaining the polymerization conditions without activity degradation.
  • a polyolefin prepared according to the production method of the above-described embodiment.
  • Such a polyolefin may be preferably used for blow molding, injection molding, etc., as it has a molecular weight distribution in which a large molecular weight and a polymer elasticity increase to improve swell.
  • the polyolefin according to the present invention may have a large molecular weight of about 100,000 to 2,000,000 or about 110,000 to 1,500,000, about 120,000 to 700,000, about 150,000 to 550,000, about 200,000 to 450,000 by the action of the above-described molecular weight modifier, etc.
  • the elasticity can be increased to have a molecular weight distribution that improves the swell.
  • the polyolefins may have a greater molecular weight of at least about 250,000, or at least about 280,000, at least about 300,000, at least about 330,000.
  • the melt index (Ml 21.6 kg) of the polyolefin prepared through the slurry polymerization process or the like is 15.0 g / 10 m in or less, or 0.01 to 15 g / 10 min, preferably 10 g / 10 min or less, and more preferably 1 g /. can be iOmin or less. Due to such a large molecular weight and high polymer elasticity increases the molecular weight distribution of the swell (swell), can exhibit excellent mechanical properties and processability at the same time.
  • Such polyolefin may be used for blow molding, and may be used for injection molding, film, pipe or beam cap, and the like.
  • a polyolefin which can be preferably used for blow molding or injection molding is more effectively produced.
  • a method for producing a metallocene supported catalyst is provided.
  • the melt index is low, the molecular weight distribution is wide, and the high notch creep test (FNCT) is higher than the density or melt index, so that it is suitable for blow molding or injection molding.
  • FNCT high notch creep test
  • Particularly suitable polyolefins can be produced very effectively.
  • FIG. 1 is a graph showing the molecular weight distribution of a polymer for a polymerization reaction using a metallocene supported catalyst prepared according to Examples 10-12 and Comparative Example 4 (Brown: Test Example 10, Red: Test Example 11, Purple: Test Example 12, Blue: Comparative Test Example 4).
  • Figure 2 is a graph showing the molecular weight distribution of the polymer for the polymerization reaction using the metallocene supported catalyst prepared according to Comparative Example 3, Example 8 (red: test example 8, green: Comparative Test Example 3).
  • Figure 3 is a graph showing the molecular weight distribution of the polymer for the polymerization reaction using the metallocene supported catalyst prepared according to Comparative Example 2, Example 5 (red: Test Example 5, Blue: Comparative Test Example 2).
  • the reaction product was dried in vacuo to remove all volatiles, followed by addition of nucleic acid (hexane) to the remaining oily liquid material, followed by filtration using a schlenk glass filter.
  • the filtered solution was dried in vacuo to remove the nucleic acid, which was then added again to induce precipitation at low temperature (-20 ° C.).
  • the precipitate obtained was filtered at low temperature to give a white solid [t-Bu-0 (CH 2 ) 6 -C 5 H 4 ] 2 ZrCl 2 compound in a yield of 92>.
  • the measured KEL and 13 C NMR data of [t-Bu_ 0 (C3 ⁇ 4) 6 -C 5 H 4 ] 2 ZrCl 2 obtained were as follows.
  • the reaction mixture was stirred for 12 hours while slowly bringing the temperature to room temperature.
  • Tetramethylcyclopentadiene 1.2 mole (150 g) and 2.4 L of THF were added to the reactor, and the reactor temperature was changed to -20 ° C.
  • 480 mL of n-BuLi was added to the reactor at a rate of 5, L / min using a feed pump.
  • n—BuLi was added, followed by stirring for 12 hours while slowly raising the temperature to room temperature.
  • an equivalent of methyl (6-t-butoxy nucleosil) dichlorosilane (326 g, 350 mL) was added quickly to the reactor. The reaction mixture was stirred for 12 hours while slowly warming to room temperature.
  • TiCl 3 (THF) 3 n-BuLi and the ligand dimethyl (tetramethyl CpH) t-butylaminosilane (dimethyl (tetramethylCpH) t-butylaminosi lane) in the dilithium salt of -78 ° C ligand synthesized in THF solution 10 ⁇ l ol) was added rapidly. The reaction solution was stirred for 12 hours while slowly releasing to room temperature at -78 ° C.
  • silica (SYL0P0L 948, manufactured by Grace Davison) was dehydrated under vacuum at a temperature of 400 ° C. for 15 hours.
  • the metallocene supported catalyst was prepared in the same manner as in Example 1, except that 160 mg (30 mol%) and 270 mg (50 mol%) of the molecular weight modifier were added. Prepared.
  • Example 4 Preparation of Metallocene Supported Catalyst
  • a metallocene supported catalyst was prepared in the same manner as in Example 1, except that 465 mg (0.1 ⁇ L / gSi) of the catalyst precursor prepared in Synthesis Example 2 was used. .
  • the metallocene supported catalyst was prepared in the same manner as in Example 4, except that the content of the molecular weight modifier was 160 mg (30 mol%) and 270 mg (50 mol%), respectively. Prepared. .
  • Example 7 Preparation of Metallocene Supported Catalyst
  • a metallocene supported catalyst was prepared in the same manner as in Example 1, except that 690 mg (0.1 ⁇ l ol / gSi0 2 ) of the catalyst precursor prepared in Synthesis Example 3 was used. It was. Examples 8 and 9: Preparation of Metallocene Supported Catalysts
  • a metallocene supported catalyst was prepared in the same manner as in Example 7, except that the content of the molecular weight modifier was 160 mg (30 mol) and 270 mg (50 mol%), respectively. It was.
  • Example 10 Preparation of Metallocene Supported Catalysts
  • silica (SYL0P0L 948, manufactured by Grace Davi son) was dehydrated under vacuum at a temperature of 400 ° C. for 15 hours.
  • a 10 wt% methylaluminoxane (MAO) / luene solution was added to 49.7 mL in a glass reactor, and silica (SYL0P0L 948, manufactured by Grace Davi son) was added at 40 ° C. Stirring while stirring at ° C. After lowering the temperature to 80! after dissolving 520 mg (0.075 ⁇ ol / g Si0 2 ) catalyst precursor prepared in Synthesis Example 3 in 20 mL of toluene, 53 mgdO mol3 ⁇ 4 the molecular weight regulator prepared in Synthesis Example 4 Were put together and immediately put into the reaction machine.
  • MAO methylaluminoxane
  • aninium borate N, N-dimethyl ani 1 Indium tetraki s (pentaf luorophenyl) borate, AB
  • 948 mg (l .2 ⁇ ol / gSi0 2 ) was pre-dissolved in 20 mL of toluene, added as a solution and stirred at 40 ° C for 2 hours.
  • the metallocene supported catalyst was prepared in the same manner as in Example 10, except that the content of the molecular weight modifier was 160 mg (30 mol%) and 270 mg (50 mol%), respectively. Prepared. Comparative Example 1: Preparation of Metallocene Supported Catalyst
  • silica (SYL0P0L 948, manufactured by Grace Davi son) was dehydrated under vacuum at a temperature of 400 ° C. for 15 hours.
  • 10 wt% of methylaluminoxane (MAO) / luene solution was added to 49.7 mL, and 9.1 g of silica (SYL0P0L 948, manufactured by Grace Davison) was added at 40 ° C., and the reactor temperature was increased to 80 ° C. Stirring while raising. After lowering the temperature to 80 ° C.
  • MAO methylaluminoxane
  • silica (SYL0P0L 948, manufactured by Grace Davison) was dehydrated under vacuum at a temperature of 400 ° C. for 15 hours.
  • Example 1 Using Parr reaction, 400 mL of nucleic acid was added to an isolated system filled with argon, and then 1 g of trimethylaluminum was dried to dry the reactor and discarded. After 400 mL of nucleic acid was filled in a reaction vessel, 0.5 g of triisobutylaluminum was added thereto.
  • the supported catalyst prepared in Example 1 was improved to 10 mg in an argon-filled glove box and placed in a reaction vessel, followed by argon venting, followed by polymerization for 1 hour by making ethylene 30 bar pressure at 78 ° C. Polymerization Test Examples 2-12
  • Test Example 1 Precursor 1/10 * 10.4 128,000 . 2.2 slurry synthesis
  • Test Example 5 30 * 2.3 660,000 2.3 slurry polymerization catalyst precursor 2 / soluble MWE
  • Test Example 8 Catalyst Precursor 3/30 * 2.0 972,000 3.1 Slurry Consolidation
  • the molecular weight distribution graph of the polymer for the polymerization reaction using the metallocene supported catalyst prepared according to Examples 10-12 and Comparative Example 4 is shown in FIG. And (brown: Test Example 10, Red: Test Example 11, Purple: Test Example 12, Blue: Comparative Test Example 4), and a polymerization reaction using a metallocene supported catalyst prepared according to Comparative Example 3 and Example 8.
  • the molecular weight distribution graph of the polymer is shown in Figure 2 (red: Test Example 8, Green: Comparative Test Example 3), Comparative Example 2, of the polymer against the polymerization reaction using the metallocene supported catalyst prepared according to Example 5
  • the molecular weight distribution graph is shown in FIG. 3 (red: test example 5, blue: comparative test example 2).
  • X axis is dlogwf / dlogM
  • y axis is logM
  • the vertical axis is the Intensity axis of the polymer
  • the horizontal axis is the molecular weight axis of the polymer.
  • the present invention is less active fluctuations compared to the prior art, and it can be seen that the molecular weight fluctuations fluctuate depending on the amount of the regulator, thereby enabling fine tuning in preparing the supported catalyst. have.
  • Figure 2 when the input of the existing molecular weight regulator during the polymerization, the activity deterioration is severe and the portion of the increase in molecular weight was not large, but it was confirmed that the increase in molecular weight and activity is maintained to some extent by the supported catalyst.
  • the polymer peaks move toward the polymer and the bimodal opening is narrowed to a single rod according to the change of the molecular weight regulator. This shows that the polymer elasticity, which is important in blow molding, is increased and thus the swell is changed to a model that improves the physical properties, thereby making the polymer of good orientation.
  • the non-reflective regulator may be expressed while entering the reaction step again in the recovery process. In this case, the process may be shaken by an undesired polymerization process, so adding a molecular weight regulator in a reaction vessel is not a commercially appropriate method.
  • the use of a molecular weight regulator during the polymerization process is not good in terms of reaction efficiency, and in the case of an actual mass production plant, reaction is caused by recycling raw materials. Unintentional action on other reaction processes can lead to unwanted polymerization processes. That is, the molecular weight control agent introduced during the polymerization may have instability in the overall polymerization process, but may have a molecular weight control effect at the laboratory level, but may cause process instability in a system of actual mass production scale.
  • the present invention used a molecular weight regulator of the catalytic amount relative to the precursor in order to actively solve this problem and has the advantage of almost no side effects due to the molecular weight regulator in the actual plant application.

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Abstract

La présente invention concerne un procédé de production d'un catalyseur métallocène supporté, apte à préparer de manière plus efficace une polyoléfine qui présente une polydispersité permettant un bon gonflement grâce à une élasticité polymère accrue, et, de ce fait, qui peut de préférence être utilisée pour un moulage par soufflage ou analogue.
PCT/KR2016/006264 2015-06-15 2016-06-13 Procédé de fabrication d'un catalyseur métallocène supporté WO2016204469A1 (fr)

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EP16811882.6A EP3255066B1 (fr) 2015-06-15 2016-06-13 Procédé de fabrication d'un catalyseur métallocène supporté
JP2017546872A JP6450467B2 (ja) 2015-06-15 2016-06-13 メタロセン担持触媒の製造方法
CN201680021196.XA CN107531828B (zh) 2015-06-15 2016-06-13 制备负载型茂金属催化剂的方法
US15/566,098 US10501563B2 (en) 2015-06-15 2016-06-13 Method of preparing supported metallocene catalyst

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20140114310A (ko) * 2014-07-21 2014-09-26 주식회사 엘지화학 폴리올레핀 중합체의 제조방법
KR20150058035A (ko) * 2013-11-18 2015-05-28 주식회사 엘지화학 폴리올레핀의 제조 방법 및 이로부터 제조된 폴리올레핀
KR20150057974A (ko) * 2013-11-18 2015-05-28 주식회사 엘지화학 폴리올레핀의 제조 방법 및 이로부터 제조된 폴리올레핀
KR20150059125A (ko) * 2013-11-21 2015-05-29 주식회사 엘지화학 폴리올레핀의 제조 방법 및 이로부터 제조된 폴리올레핀
KR20150062145A (ko) * 2013-11-28 2015-06-05 주식회사 엘지화학 담지 메탈로센 촉매의 제조방법

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20150058035A (ko) * 2013-11-18 2015-05-28 주식회사 엘지화학 폴리올레핀의 제조 방법 및 이로부터 제조된 폴리올레핀
KR20150057974A (ko) * 2013-11-18 2015-05-28 주식회사 엘지화학 폴리올레핀의 제조 방법 및 이로부터 제조된 폴리올레핀
KR20150059125A (ko) * 2013-11-21 2015-05-29 주식회사 엘지화학 폴리올레핀의 제조 방법 및 이로부터 제조된 폴리올레핀
KR20150062145A (ko) * 2013-11-28 2015-06-05 주식회사 엘지화학 담지 메탈로센 촉매의 제조방법
KR20140114310A (ko) * 2014-07-21 2014-09-26 주식회사 엘지화학 폴리올레핀 중합체의 제조방법

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