EP1590376A2 - Combinaison de catalyseurs, polymeres isotactiques, procede de production de polymeres isotactiques lineaires et utilisation de ces polymeres - Google Patents

Combinaison de catalyseurs, polymeres isotactiques, procede de production de polymeres isotactiques lineaires et utilisation de ces polymeres

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Publication number
EP1590376A2
EP1590376A2 EP04705387A EP04705387A EP1590376A2 EP 1590376 A2 EP1590376 A2 EP 1590376A2 EP 04705387 A EP04705387 A EP 04705387A EP 04705387 A EP04705387 A EP 04705387A EP 1590376 A2 EP1590376 A2 EP 1590376A2
Authority
EP
European Patent Office
Prior art keywords
general formula
catalyst combination
alkyl
aryl
linear
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP04705387A
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German (de)
English (en)
Inventor
Bernhard Rieger
Sandra Deisenhofer
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Sued Chemie AG
Original Assignee
Inventis Technologies GmbH
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Inventis Technologies GmbH filed Critical Inventis Technologies GmbH
Publication of EP1590376A2 publication Critical patent/EP1590376A2/fr
Withdrawn legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F110/04—Monomers containing three or four carbon atoms
    • C08F110/06—Propene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F10/04—Monomers containing three or four carbon atoms
    • C08F10/06—Propene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • 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
    • C08F4/65908—Component covered by group C08F4/64 containing a transition metal-carbon bond in combination with an ionising compound other than alumoxane, e.g. (C6F5)4B-X+
    • 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
    • C08F4/65912—Component covered by group C08F4/64 containing a transition metal-carbon bond in combination with an organoaluminium compound
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S526/00—Synthetic resins or natural rubbers -- part of the class 520 series
    • Y10S526/943—Polymerization with metallocene catalysts

Definitions

  • the present invention relates to a new catalyst combination and plastomeric polymers and a process for the production of linear isotactic polymers with plastomeric properties and their use.
  • DE 198 16 154 discloses highly active zirconocene dichlorides, with which isolated stereo errors can be incorporated along an isotactic chain depending on the monomer concentration.
  • These asymmetric catalysts have alkyl or alkoxy substituents in 5, 6 positions of the indenyl group pe and lead to an improved activity and thus to very high molecular weights.
  • These 5, 6-substituted metallocene catalysts cause high concentrations of isolated stereo errors, which leads to soft polypropylenes of low crystallinity and excellent elastomeric properties.
  • a catalyst combination for the production of linear isotactic polymers which has an activator and a metal complex of the general formula I
  • R x -R 4 linear or branched Ci to C 10 alkyl, 5- to 7-membered cycloalkyl, which in turn can carry one or more Ci to Cio alkyl residues as a substituent, C 6 ⁇ to C ⁇ 8 aryl or arylalkyl or alkylaryl, where RVR 2 , R 3 / R 4 can be partially or simultaneously incorporated into 5- to 7-membered fused cycloalkyl or aryl rings, which in turn can contain heteroatom units (eg 0, S, NR) -;
  • R 6 -R 9 is hydrogen, linear or branched Ci to Cio alkyl or hydrogen, linear or branched Ci to C 10 alkyl, 5- to 7-membered cycloalkyl, which in turn is one or more Ci to Cg alkyl radicals Can carry substituent, C 6 - to C 8 aryl or arylalkyl or alkylaryl, with the proviso that the radicals R 6 / R 7 or R 8 / R 9 are incorporated into 5- to 7-membered fused cycloalkyl or aryl rings, these may be substituted, interrupted by heteroatoms and / or connected to a further cycloalkyl and / or aryl ring;
  • R ⁇ o_ R n is hydrogen, C - to C 8 -alkyl, 4- to 7-membered cycloalkyl, aryl, where R 10 , R 11 together with E can form a 4-7-membered cycloalkyl or aryl;
  • R 12 Ci to C 8 alkyl, aryl, Ca. - to C 8 -oxyalkyl, CI to C 3 -trialkylsiloxy;
  • X is hydrogen, halogen or C to C 8 alkyl, aryl, benzyl;
  • the metal complexes according to the invention are thus distinguished by the fact that they are asymmetrical and have a special substitution in the radicals R 6 -R 9 .
  • the ring with the substituents R _.- R is preferably a fluorenyl ring system, which can also be substituted.
  • the metal complex of the general formula I is preferably a compound of the general formula II.
  • E 2 can be the same or be different.
  • An equally preferred catalyst combination is based on a compound of the general formula III.
  • the catalyst combination preferably contains a compound of the general formula IV as a metal complex
  • the catalyst combination can have a compound of the general formula V as a metal complex.
  • the radicals R x to R 4 and R 10 to R i2 and E and MX 2 have the meaning given in the general formula I.
  • the activator is preferably an open-chain or cyclic alumoxane compound of the general formula VI or VII
  • R 13 denotes a C 1 -C 4 -alkyl group and n denotes a number between 5 and 30.
  • cationic activators of the general formula VIII to XI may be included in 'the catalyst combination.
  • R 14 denotes a C 1 -C 4 -alkyl group or an aryl group and R 15 denotes a perfluorinated alkyl or aryl radical.
  • the activators mentioned above can both available individually as well as in combination.
  • the metal complex and the activator according to general form VI to XI are preferably present in amounts such that the atomic ratio between aluminum from the alumoxane and / or boron (res. Aluminum) from the cationic activator and the transition metal from the metal complex is in the range from 1: 1 to 10 6 : 1.
  • a method for the production of linear isotactic polymers is also provided.
  • inventive procedural for preparing the linear, isotactic polymers prepared from at least one monomer of a C 2 - are constructed to C 2 o-olefin, a C 2 - to C 2 o ⁇ olefin in the presence of a catalyst combination reacted as described above.
  • a polymer is obtained whose tacticity is greater than 60% [mmmm] pentad concentration.
  • the polymerization reaction is preferably carried out in the gas phase, in suspensions or in supercritical monomers, in particular in solvents which are inert under the polymerization conditions.
  • solvents which are preferred as inert solvents are: contain no reactive molecules. Examples of these are benzene, toluene, xylene, ethylbenzene or alkanes such as propane, n-butane, i-butane, pentane, hexane, heptane or mixtures thereof.
  • the polymerization can be carried out under conditions known per se. It is advantageous here if the pressure is from 1 to 100 bar, preferably from 3 to 20 bar and in particular from 5 to 15 bar. Suitable temperatures are those in the range from -50 to 200 ° C., preferably 10 to 150 ° C. and in particular 20 to 40 ° C.
  • the method comprises, as described above, the reaction of a C 2 - to C 2 o-olefin and, if appropriate, further monomers, and a catalyst combination of at least one activator of the general formula VI to XI in the presence of at least one metal complex of the general formula I to V.
  • the activator is preferably an open-chain or cyclic alumoxane compound of the general formula VI or VII.
  • R 13 denotes a C 1 -C 4 -alkyl group and n denotes a number between 5 and 30.
  • Cationic activators of the general formulas VIII to XI can also be present in the catalyst combination.
  • R 14 denotes a Ci to C 4 -Alyl group or a AArryyllggrruuppppie and R 15 is a perfluorinated alkyl or aryl radical.
  • 03/082466 AI (e.g. from claim 11) described.
  • the disclosure content is therefore expressly referred to.
  • the activators mentioned above can be present either individually or in combination.
  • the metal complex and the activator according to the general formulas VI to XI are preferably present in amounts such that the atomic ratio between aluminum from the alumoxane and / or boron or aluminum from the cationic activator and the transition metal from the metal complex is in the range from 1: 1 to 10 6 : 1.
  • the invention further relates to a novel isotactic polymer with plastomeric properties (claims 17 to 24).
  • An essential element of the new isotactic polymers according to the invention is that they have a tacticity have greater than 60% [mmmm] pentad concentrations. At the same time, these polymers according to the invention have a molecular weight of up to 5,000,000 g / mol at a TG of -50 to 30 ° C.
  • the polymers according to the invention are thus the first ultra-high molecular weight polyolefins which can have a molecular weight of up to 5,000,000 g / mol. It is preferred that the tacticity is in the range from greater than 60% to 98%.
  • the molecular weight is preferably in the range from 1,000,000 to 3,000,000 g / mol, particularly preferably in the range from 1.3 to 2,000,000 g / mol.
  • these novel plastomeric polymers can preferably be prepared using a catalyst combination as described above.
  • the polymers according to the invention can be composed of all C2 to C 2 o-olefins.
  • Preferred olefins are C 3 -C 20 -alk-1-ene.
  • Examples include propene, 1-butene, 2-butene, 1-pentene, 1-hexene, 1-octene, 1-nonene, 1-decene, 1-dodecene, 1-hexadecene, 1-octadecene or 1-eicotene.
  • olefin a C 5 ⁇ can to C 2 o _ Cycloolef-in are eligible.
  • Examples of cycloolefins are cyclopentene, cyclohexene, norbornene and its derivatives. It is particularly preferred if polypropylene is used as the olefin.
  • the isotactic polymers according to the invention can of course also as copolymers composed of Polyproplyen and a C 4 - to C 2 o ⁇ 01efin and / or a cycloolefin be constructed.
  • the isotactic polymer according to the invention can also be a terpolymer composed of propylene, a C 2 -C 20 -olefin and a cycloolefin.
  • all additives known from the prior art can be contained. Examples include fillers, plasticizers and nucleating agents.
  • the linear isotactic polymer according to the invention can, of course, in and of itself, as known from polymer chemistry, also be provided as granules, so that it can be processed without problems.
  • Possible areas of application of the isotactic polymers described here are films, threads, molded parts, etc.
  • the diastereomeric alcohol (16.6 g, 65.4 mmol) was dissolved in 100 ml of toluene and 1.0 g of p-toluene sulfonic acid was added. The solution was heated under reflux using a water separator until no more water was formed. The reaction mixture was neutralized by washing with aqueous KOH and dried over Na 2 S0. After evaporation of the solvent, 2-methyl-1H-benzo [jb] indeno [4, 5-d] thiophene (3) was obtained as a crystalline solid (14.9 g, 63.1 mmol, 97%).
  • Fig. 1 shows the frontal view (Fig. La) and the side view (Fig. Lb).
  • the frontal view shows that the position of the ethylene bridge at C3 of the MBIT unit and the connection of the benzothiophene fragment to C8 and C15 of the central indene ring lead to a rear orientation of these
  • the side view of the complex (7a) shows some peculiarities of the architecture of the complex.
  • the Cp Flu -Zr-Cp MBIT angles are 128.0 ° for ⁇ and 62.9 ° for ⁇ .
  • the corresponding angles can be seen in FIG. 2.
  • the angle ⁇ Flu is 189.5 ° and differs from the results of the bridged indenyl and fluorenyl complexes known from the prior art, for which values of less than 180 ° were typically observed.
  • the resulting improved accessibility of the zirconium center is obviously one reason for the higher activity of the complex (7a).
  • the mean distance between Zr (IV) and fluorenyl carbon atoms of (7a) (2.574 (4) ⁇ ) is significantly longer than the distance between Zr (IV) and the carbon atoms of the MBIT unit (2.530 (4) ⁇ ) , which leads to an asymmetrical arrangement of the Zr (IV) center between the two Cp planes.
  • zirconices (7a), (8) / MAO proved to be suitable catalysts for the polymerization of propylene.
  • Table 3 shows the dependencies of the new heterocenes in relation to the monomers and the temperature. The compounds of types (7a), (7c) and (8) were used as monomers.
  • the synthesis of the compounds according to the invention is based on 2-methylindan-1-one and the desired 2-methylindene is obtained in a yield of over 60% in a three-step process.
  • m- Xylene (1) reacted with methacrylic acid chloride.
  • the purified indanone (2) is obtained in a yield of 66% after purification by distillation and Friedel-Craft alkylation.
  • the reduction of indanone (2) is carried out with NaBH 4 .
  • the indene (3) is obtained as a viscous liquid.
  • the two isomers (5) and (6) are obtained in a subsequent reaction in a yield of 45%.
  • the desired isomer 5 can then be isolated by crystallization from toluene / hexane in a ratio of 1: 2.
  • the conversion of the ligand (5) into the desired hafnium complex can be carried out by deprotonation with n-BuLi in a mixture of toluene / dioxane at -78 ° C. and with stirring for 2 hours at room temperature r. A subsequent addition of HfCl 4 in solution is required here. The reaction is carried out by stirring at room temperature for 20 hours. The hafnium complex (7) can then be isolated in a yield of 45%. The precipitated yellow complex is isolated from toluene solution and extracted with cold toluene. The toluene is then removed as quickly as possible and the yellow powder is dried under vacuum.
  • the hafnium complex (7) prepared according to Example 1 above is used to polymerize propylene in various solvents. leads .
  • the polymerization reaction in toluene is carried out in one
  • a polymerization reaction was carried out in liquid propylene.
  • the temperature of a 500 ml autoclave was set to -10 ° and the reactor was filled with propylene.
  • the desired polymerization temperature of the catalyst and the cocatalyst were then added as described above.
  • the polymerization reaction was also quenched with methanol and the resulting one
  • FIGS. 5 to 7 The corresponding measurement results are compiled in FIGS. 5 to 7 (tables 5 to 7).
  • the influence of temperature on the polymerization conditions can be seen from Table 5 in FIG. FIG. 5 shows sustainably that the catalyst combination according to the invention can be used to obtain polymers which not only have an extremely high molecular weight of up to 800,000, but which also have a very high tacticity with respect to the mmmm pentad.
  • the hafnium complex (7) in particular has outstanding properties with regard to the polymerization.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)

Abstract

La présente invention concerne une combinaison de catalyseurs servant à produire des polymères isotactiques linéaires, cette combinaison contenant un complexe métallique asymétrique et un activateur.
EP04705387A 2003-01-28 2004-01-27 Combinaison de catalyseurs, polymeres isotactiques, procede de production de polymeres isotactiques lineaires et utilisation de ces polymeres Withdrawn EP1590376A2 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE10303225A DE10303225A1 (de) 2003-01-28 2003-01-28 Katalysatorkombination, isotaktische Polymere sowie ein Verfahren zur Herstellung von linearen isotaktischen Polymeren und dessen Verwendung
DE10303225 2003-01-28
PCT/EP2004/000694 WO2004067581A2 (fr) 2003-01-28 2004-01-27 Combinaison de catalyseurs, polymeres isotactiques, procede de production de polymeres isotactiques lineaires et utilisation de ces polymeres

Publications (1)

Publication Number Publication Date
EP1590376A2 true EP1590376A2 (fr) 2005-11-02

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ID=32667893

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Application Number Title Priority Date Filing Date
EP04705387A Withdrawn EP1590376A2 (fr) 2003-01-28 2004-01-27 Combinaison de catalyseurs, polymeres isotactiques, procede de production de polymeres isotactiques lineaires et utilisation de ces polymeres

Country Status (8)

Country Link
US (1) US7381679B2 (fr)
EP (1) EP1590376A2 (fr)
JP (1) JP2006517991A (fr)
CN (2) CN100457784C (fr)
CA (1) CA2514645A1 (fr)
DE (1) DE10303225A1 (fr)
NO (1) NO20053659L (fr)
WO (1) WO2004067581A2 (fr)

Families Citing this family (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2016171807A1 (fr) 2015-04-20 2016-10-27 Exxonmobil Chemical Patents Inc. Composition catalyseur comprenant un support fluoré et ses procédés d'utilisation
KR101917911B1 (ko) * 2015-07-02 2018-11-12 주식회사 엘지화학 전이금속 화합물 및 이를 포함하는 촉매 조성물
KR101910701B1 (ko) * 2015-07-02 2018-10-22 주식회사 엘지화학 전이금속 화합물 및 이를 포함하는 촉매 조성물
US9803037B1 (en) * 2016-05-03 2017-10-31 Exxonmobil Chemical Patents Inc. Tetrahydro-as-indacenyl catalyst composition, catalyst system, and processes for use thereof
KR101920401B1 (ko) * 2016-12-06 2019-02-08 한화케미칼 주식회사 올레핀 중합 촉매용 전이금속 화합물, 이를 포함하는 올레핀 중합 촉매 및 이를 이용하여 중합된 폴리올레핀
US10703838B2 (en) 2017-10-31 2020-07-07 Exxonmobil Chemical Patents Inc. Mixed catalyst systems with four metallocenes on a single support
SG11202008735RA (en) * 2018-03-19 2020-10-29 Exxonmobil Chemical Patents Inc Processes for producing high propylene content pedm using tetrahydroindacenyl catalyst systems
US10899853B2 (en) 2018-03-19 2021-01-26 Exxonmobil Chemical Patents Inc. Processes for producing high propylene content PEDM using tetrahydroindacenyl catalyst systems
KR102558310B1 (ko) * 2018-12-12 2023-07-24 주식회사 엘지화학 전이금속 화합물, 이를 포함하는 촉매 조성물 및 이를 이용한 중합체의 제조방법

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JP3405784B2 (ja) * 1993-09-28 2003-05-12 昭和電工株式会社 ポリオレフィンの製造方法
JP3408594B2 (ja) * 1993-10-22 2003-05-19 昭和電工株式会社 ポリオレフィンの製造方法
DE19816154A1 (de) * 1998-04-09 1999-10-21 Bernhard Rieger Lineare isotaktische Polymere, Verfahren zu ihrer Herstellung und deren Verwendung sowie eine Katalysatorkombination
WO2001047939A1 (fr) * 1999-12-28 2001-07-05 Basell Technology Company B.V. Composes de metallocene heterocycliques et leur utilisation dans des systemes catalytiques pour produire des polymeres d'olefines
ES2326537T3 (es) * 2000-01-18 2009-10-14 Basell Polyolefine Gmbh Ligando para un catalizador metaloceno para fabricar polimeros basados en propileno y metodo de obtencion del mismo.

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Also Published As

Publication number Publication date
CN100457784C (zh) 2009-02-04
HK1090935A1 (zh) 2007-01-05
CN101029102A (zh) 2007-09-05
WO2004067581A3 (fr) 2004-12-09
US7381679B2 (en) 2008-06-03
WO2004067581A2 (fr) 2004-08-12
NO20053659D0 (no) 2005-07-27
US20070015657A1 (en) 2007-01-18
CA2514645A1 (fr) 2004-08-12
NO20053659L (no) 2005-10-28
JP2006517991A (ja) 2006-08-03
DE10303225A1 (de) 2004-08-05
CN1753914A (zh) 2006-03-29

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