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EP1713747A1 - Heterogene chromkatalysatoren - Google Patents

Heterogene chromkatalysatoren

Info

Publication number
EP1713747A1
EP1713747A1 EP05749989A EP05749989A EP1713747A1 EP 1713747 A1 EP1713747 A1 EP 1713747A1 EP 05749989 A EP05749989 A EP 05749989A EP 05749989 A EP05749989 A EP 05749989A EP 1713747 A1 EP1713747 A1 EP 1713747A1
Authority
EP
European Patent Office
Prior art keywords
chromium
catalyst
silica
tridentate ligand
triazacyclohexane
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Withdrawn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
EP05749989A
Other languages
English (en)
French (fr)
Inventor
Philippe Bodart
Cristina Nenu
Bert Weckhuysen
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.)
Total Petrochemicals Research Feluy SA
Original Assignee
Total Petrochemicals Research Feluy SA
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
Priority claimed from EP04100506A external-priority patent/EP1564198A1/de
Application filed by Total Petrochemicals Research Feluy SA filed Critical Total Petrochemicals Research Feluy SA
Priority to EP05749989A priority Critical patent/EP1713747A1/de
Publication of EP1713747A1 publication Critical patent/EP1713747A1/de
Withdrawn legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F11/00—Compounds containing elements of Groups 6 or 16 of the Periodic Table
    • C07F11/005—Compounds containing elements of Groups 6 or 16 of the Periodic Table compounds without a metal-carbon linkage
    • 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
    • C08F110/02—Ethene

Definitions

  • the present invention relates to heterogeneous catalysts for the polymerisation of alpha olefins, particularly for the polymerisation of ethylene to hexene.
  • the present invention further relates to methods for producing th e catalysts and to the use of such catalysts
  • a variety of homogeneous catalysts are known in the literature for the polymerisation of alpha olefins. These systems, as referred here below, are based on chromium complexes comprising a chromium core bound to a ligand that comprises electron donors. Nitrogen is the most common electron donor but phosphorus, oxygen or sulphur have also been used. However, a major drawback of these known homogeneous complexes lies in that at the end of the polymerisation, it is difficult to separate these complexes from the components.
  • Patent WO03/7175 relates to catalyst systems comprising chromium pyrrolide complexes and metal alkyl compound. Said catalyst systems were reported to be active in ethylene trimerization.
  • Patent WO03/084902 relates to homogeneous multi -dentate chromium complexes activated with alkylaluminoxane in order to oligomerize olefins.
  • the chromium systems can have different ligands, such as 1,3,5 triazacyclohexane with different substituents, cyclopentadien yl ligands with different substituents and N-methylimidazole ligands reported by Ruther T. et al., Organometallics 2001 , volume 20, pages 1247 -1250.
  • Patent WO03/076368 discloses a method for the oligomerization of alpha olefins comprising at least 3 carb on atoms wherein the olefin is brought into contact with a catalyst sytem obtained from a chromium source, a 1,3,5 -trialkyl- 1 ,3,5-triazacyclohexane and from at least one activator comprising a boron compound.
  • Patent WO03/076367 discloses a method for the oligomerization of olefins in presence of a homogeneous catalyst based on 1,3,5 triazacyclohexane -CrCI 3 complex with 1,3,5 triazacyclohexane substituted in 1,3,5 positions with cycloalkylalkyl groups.
  • An alkyl aluminium compound or an alkylalumoxane is used as activator.
  • R.D. K ⁇ hn et al. disclose in Chemical Communications, 2000, pages 1927 - 1928 substituted 1,3,5 -triazacyclohexane chromium (III) homogeneous complexes activated with methylalumoxane or N,N-dimethylanilinium tetrakis(pentafluorophenyl) borate and triisobutylaluminium . These complexes are active in the polymerisation of ethylene.
  • the main product is polyethylene, although 1 -hexene and some decenes as co -trimers of 1 -hexene and ethene were also found in the reaction mixture.
  • the Chemical abstract of JP 10 130319 A relates to supported catalysts prepared by reacting in a first step a chromium halide with a cyclic polyamine compound to form a multidentate coordination complexe. Said complexe is reacted in a second step with a silylamide salt such as for example Li bis (trimethylsilyl)amide and further with aluminoxane.
  • This catalyst is active in the polymerization of ethylene with a wide molecular weight distribution.
  • polymerisation means a chemical process that combines two or more monomers to form a polymer.
  • hexene include s 1 -hexene.
  • the present inventors have found a method for producing such heterogeneous chromium catalyst system, said method comprising the steps of: a) providing a silica -containing support, b) treating the silica -containing support with a chromium compound to form a chromium -based silica -containing support, c) activating the chromium -based silica-containing support, d) chemically reducing the activated chromium -based silica-containing support to produce a precursor catalyst, e) reacting the reduced precursor catalyst w ith a tridentate ligand compound to obtain a catalyst and f) optionally activating the catalyst issued from step e) with a cocatalyst.
  • the present inventors have found that the method according to the invention solves the object of the invention.
  • the present invention further provides heterogeneous chromium catalysts.
  • the present invention provides a process for the polymerisation of ethylene and/or alpha olefins, preferably for the polymerisation of ethylene to hexene, by passing the ethylene and /or alpha olefins over the heterogeneous chromium catalyst system of the invention and by further recovering the polymer produced.
  • the inventors have surprisingly found that the heterogeneous chromium catalyst system has an improved activity by catalytic site.
  • the silica-containing support material used in the catalyst of the invention may be composed of 5 to 100 weight percent silica, the remainder if any being selected from aluminium oxide, magnesium oxide, titanium oxide, zirconium oxide, or mixtures thereof.
  • the support is silica.
  • the specific surface area of the silica -containing support is preferably larger than 200 m 2 /g and its pore volume greater than 1 cm 3 /g.
  • the particles size of the silica -containing support preferably ranges from 0.020 to 2 millimetres. More preferably, the silica -containing support is sieved to achieve size fractions between 0.2 and 0.4 millimetres.
  • the required size fraction can be obtained by any method known in the art. As an example, to obtain size fractions between 0.2 and 0.4 millimetres, the silica -containing support is first press into a wafer, then grained and sieved using size sieves with 0.425 mm and 0.212 mm aperture. This may be done either before the treatment of the silica -containing support with the chromium compound or after it.
  • the silica-containing support is then treated with a chromium compound.
  • the chromium compound used in the present invention is preferably chromium trioxide.
  • the resultant catalyst precursor contains between 0.01 and 2 weight percent of chromium, preferably between 0.1 and 1 weight percent of chromium, based on the total weight of the chromium and support. Most preferably, the catalyst contains 1 weight percent of chromium, based on the total weight of the chromiu m and support.
  • the catalyst precursor is then subjected to an activation step in air, at an elevated temperature, for at least 6 hours.
  • the activation temperature preferably ranges from 400 to 900°C. Most preferably, the activation temperature is about 720°C.
  • a chemical reduction process occurs at a temperature of from 200°C to 600°C, preferably at a temperature from 350 to 450°C, and more preferably at a temperature of about 400°C, in either carbon monoxide or hydrogen.
  • the catalyst precursor is treated with a tridentate ligand compound that has been dissolved in a solvent such as chlorinated solvents, one can cite dichloromethane.
  • the tridentate ligand compound is a cyclic tridentate ligand with electron d onating atoms in the cycle, substituted or unsubstituted, more preferably, the tridentate ligand compound is a neutral cyclic tridentate ligand with electron donating atoms in the cycle, substituted or unsubstituted, most preferably the tridentate ligand c ompound is the 1,3,5- triazacyclohexane, wherein each of the nitrogen atoms of the 1,3,5 - triazacyclohexane may independently be substituted or not.
  • the substituents may be hydrocarbon radicals.
  • the substituents are benzyl. In the present invention, the 1 ,3,5 -tribenzyl 1,3,5-triazacyclohe
  • the catalyst After treatment with the tridentate ligand compound, the catalyst is optionally activated. Depending on the tridentate ligand compound used, the man in the art has to test if the catalyst has to be activated, or not, with a cocatalyst.
  • the activation compound is preferably a fluorinated boron compound and /or an aluminium compound.
  • the catalyst is activated with a cocatalyst.
  • the catalyst is first activated with a fluorinated boron compound and then with an aluminium compound.
  • the aluminium compound is preferably triisobutylaluminium and the fluorinated boron compound is preferably N,N -dimethylanilinium tetrakis(pentafluorophenyl)borate.
  • the heterogeneous chromium catalyst obtainable according to the method of the invention is novel over that disclosed by the Chemical abstract of JP 10 130319.
  • JP 10 130319 does not disclose an activation step of a chromium based silica support at a temperature from 400°C to 900°C. Moreover it does not disclose a chromium multi -dentate coordination complex as the invention does. Indeed, the Chemical abstract of JP 10 130319 discloses a chromium multi -dentate coordination complex, which is treated with a silylamide salt. This is not the case in the invention.
  • Example 1 preparation of the heterogeneous catalyst according to the invention.
  • silica support 10 g silica support was introduced in a 50 ml flask.
  • a solution of chromium trioxide prepared by dissolving 0.2 g of chromium trioxide in 20 ml water was added to the support at room temperatur e in order to get a chromium content of 1 weight percent of chromium based on the total weight of the chromium and the support.
  • the chromium silica -containing support is dried in air at around 150 °C. then sieved in order to achieve fra ctions from 0.2 to 0.4 mm and loaded in a sealed vessel where the activation treatment took place under dry air for 6 hours at 720°C.
  • the chromium silica-containing support was further reduced under carbon monoxide for thirty minutes at 400°C.
  • 1.2 g of the reduced precursor catalyst was placed in a 5 ml flask to which were added 2 ml solution of 0.04 M 1,3,5 -tribenzyl 1,3,5-triazacyclohexane ligand prepared by dissolving 1.43 g of 1 ,3,5 -tribenzyl 1,3,5-triazacyclohexane ligand in 100 mi of extra dry dichloromethane.
  • the reduced precursor catalyst and the ligand reacted for 10 minutes at room temperature.
  • the catalyst was washed at room temperature with 10 to 15 ml of dichloromethane.
  • the dichloromethane was further removed by evaporation at 40°C.
  • a light purple catalyst powder was produced.
  • the catalyst was further activated with 1.3 to 2 equivalents of N.N -dimethylanilinium tetrakis(pentafluoraphenyl) borate prepared by adding 5 mg of said fluorinated boron compound to 2.5 ml of dichloromethane.
  • the solvent was removed from the catalyst by evaporation at 40°C. Afterwards, the catalyst was still activated with 25 to 50 equivalents of triisobutylaluminium .
  • the UV-Vis spectrum of the catalyst according to the invention showed three major maxima located respectively at 13500 cm “1 , 20700 cm “1 and 30500 cm “1 . These positions are characteristic for the chromium trivalent d -d transitions that occur in the complex. These positions are not present in the spectrum of the reduced precursor catalyst that has not been treated with the ligand.
  • the maxima are shifted comparing with the homogeneous (Bz) 3 TAC-CrCl3 complex because the silica lattice replaced the chlorine ligands from the homogeneous complex.
  • Th e UV-Vis spectrum of the homogeneous (Bz) 3 TAC-CrCI 3 complex presented also the characteristic 3 d -d transitions of Cr 3+ in Cr complexes with nitrogen ligands.
  • HCI hydrochloric acid
  • the new maxima positions of the catalyst of the invention treated with HC I were closer to the positions of the homogeneous complex (Bz) 3 TAC-CrCl 3 . Indeed, after the treatment, the Cr-O bond of the catalyst of the invention was broken and the supported complex was converted into the homogeneous complex. The colour of the treated catalyst intensified from light purple to dark purple, which is the colour of the homogeneous complex.
  • the spectrum of the catalyst of the invention treated with water differed also widely from those of the untreated catalyst indicating the presence of ne w species.
  • EXAFS Extended X-ray Absorption Fine Structure Spectroscopy
  • the EXAFS pattern of the heterogeneous chromium catalyst shown in figure 1 indicated a very good fit of the theoretical curve (dashed line) with this related to the catalyst of the invention (unbroken line).
  • Table III p resents the molecular structure of the catalyst of the invention obtained by EXAFS and the molecular structure reported for the homogeneous catalyst (Bz) 3 TAC-CrCl3- Table III
  • a first analysis of the structure of the catalyst of the invention according to EXAFS data makes us suppose that the closest atom to the Cr centre is one oxygen atom, at a very short distance, which implies a very strong bond. Consequently, the anchored complex is linked via one oxygen atom with the silica surface. Three nitrogen atoms are fou nd also around Cr centre at the same distance reported for the reference catalyst as well as for the carbon atoms. Further, a silicon atom is present, in fact the linkage of oxygen with the surface. According to these data, we can conclude that an anchored complex was formed on the silica surface and makes us suppose that the molecular structure of the heterogeneous chromium catalyst of the invention is the structure illustrated in figure 3.
  • a more precise analysis of the structure of the catalyst of the invention took into account the data recorded by the X -ray absorption near edge spectroscopy (XANES) and by the fluorescence Extended X -ray Absorption Fine Structure Spectroscopy (EXAFS).
  • Table IV presents the molecular structure of the catalyst of the invention taking into account the XANES and EXAFS datas and the molecular structure reported for the homogeneous catalyst (Bz) 3 TAC-CrCl3-
  • the molecular structure of the heterogeneous chromium catalyst of the invention is illustrated in figure 4.
  • a polymerisation was conducted by using two reactors.
  • the catalyst prepared as described hereabove was introduced in a first reactor.
  • Toluene was used as diluent in the reactor and ethylene was continuously added in the reactor at a rate of 30 ml/min.
  • the polymerisation was performed under slurry conditions at normal pressure and at room temper ature for 30 minutes. After 30 minutes, the solid phase was separated from the liquid phase. The separation was fulfilled with a double pointed needle and the liquid phase was transferred from the first reactor to a second one.
  • Example 2 Catalysis of the heterogeneous catalys t according to the invention at normal pressure.
  • the catalyst of the invention prepared according to example 1 was carried out under slurry conditions at normal pressure and at a temperature of 90°C during 60 min.
  • the polymerisation was perfo rmed in a slurry reactor connected to a bubbler.
  • the catalyst of the invention was introduced into the reactor.
  • Toluene was used as diluent in the reactor and in the bubbler.
  • Ethylene was continuously added in the reactor at a rate of 30 ml/min.
  • Hexene was determined in the liquid phase of the reactor and of the bubbler as well as in the gas phase coming out from the bubbler by gas chromatography and gas chromatograph-mass spectrometry.
  • the distribution of the hexene (g) in the reactor, bubbler and gas phas e are shown in Table IV.
  • Example 3 comparative example
  • the polymerisation of ethylene to hexene was conducted in the same conditions as in example 2.2 excepted that the polymerisation occurred in the presence of the homogeneous complex (Bz) 3 TAC-CrCI 3 used for comparison.
  • the distribution of the hexene (g) in the reactor, bubbler and gas phase are shown in Table IV.
  • the activity of the catalyst of the invention was determined through the turnover number (TON), define d as the number of moles of hexene divided by the number of moles of chromium.
  • TON represents the number of molecules of hexene formed on a chromium site.
  • the amount of hexene formed, and the TON for the different Cr complexes are given in Table IV.
  • Table IV showed that the heterogeneous catalyst of the invention has a higher polymerisation activity per catalyst site than those of the homogeneous catalyst according to K ⁇ ln et al. used herein as comparative. This result was unexpected.
  • Example 4 Catalysis of the heterogeneous catalyst according to the invention under pressure.
  • the polymerisation of ethylene was carried out under slurry conditions at room temperature and at 3 MPa ethylene pressure with a maximal incoming flow of 100 ml/min.
  • the stirring rate was 700 rpm.
  • a solid polymer was formed with a polymerisation activity of 192 g polyethylene/mole Cr/h.
  • the distribution of hexene (g) in the reactor is given in table IV.
  • the reaction at 3 MPa resulted in a significant increase in the formation of polyethylene, while the amount of unbounded 1 -hexene decreases in the reaction mixture. It is clear that most of the 1 -hexene formed has been incorporated into the growing po lyethylene chain, resulting in a decrease of the TON.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Catalysts (AREA)
EP05749989A 2004-02-11 2005-02-09 Heterogene chromkatalysatoren Withdrawn EP1713747A1 (de)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP05749989A EP1713747A1 (de) 2004-02-11 2005-02-09 Heterogene chromkatalysatoren

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
EP04100506A EP1564198A1 (de) 2004-02-11 2004-02-11 Heterogene Chromkatalysatoren
EP04018325 2004-08-03
EP05749989A EP1713747A1 (de) 2004-02-11 2005-02-09 Heterogene chromkatalysatoren
PCT/EP2005/050565 WO2005082815A1 (en) 2004-02-11 2005-02-09 Heterogeneous chromium catalysts

Publications (1)

Publication Number Publication Date
EP1713747A1 true EP1713747A1 (de) 2006-10-25

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EP (1) EP1713747A1 (de)
WO (1) WO2005082815A1 (de)

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH10130319A (ja) * 1996-10-29 1998-05-19 Nippon Poriorefuin Kk エチレン系重合体用触媒製造及び重合体の製造法
EP0967234A1 (de) * 1998-06-24 1999-12-29 Fina Research S.A. Herstellung von Polyethylen
GB9826755D0 (en) * 1998-12-04 1999-01-27 Bp Chem Int Ltd Oligomerisation process
US6828268B1 (en) * 1999-11-05 2004-12-07 Phillips Petroleum Company Polymerization catalyst systems and processes using alkyl lithium compounds as a cocatalyst

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO2005082815A1 *

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