WO2010040235A1 - Polymérisation vivante et quasi-vivante d'oléfines catalysée par un métallocène - Google Patents

Polymérisation vivante et quasi-vivante d'oléfines catalysée par un métallocène Download PDF

Info

Publication number
WO2010040235A1
WO2010040235A1 PCT/CH2008/000426 CH2008000426W WO2010040235A1 WO 2010040235 A1 WO2010040235 A1 WO 2010040235A1 CH 2008000426 W CH2008000426 W CH 2008000426W WO 2010040235 A1 WO2010040235 A1 WO 2010040235A1
Authority
WO
WIPO (PCT)
Prior art keywords
ethene
catalyst
composition
polymerization
activator
Prior art date
Application number
PCT/CH2008/000426
Other languages
English (en)
Inventor
Peter Chen
Déborah MATHIS
Fereshteh Rouholahnejad Kasgari
Fabio Di Lena
Original Assignee
Eth Zurich
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 Eth Zurich filed Critical Eth Zurich
Priority to PCT/CH2008/000426 priority Critical patent/WO2010040235A1/fr
Publication of WO2010040235A1 publication Critical patent/WO2010040235A1/fr

Links

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
    • C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F10/02—Ethene
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F210/16—Copolymers of ethene with alpha-alkenes, e.g. EP rubbers
    • 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
    • C08F2410/00—Features related to the catalyst preparation, the catalyst use or to the deactivation of the catalyst
    • C08F2410/01—Additive used together with the catalyst, excluding compounds containing Al or B
    • 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

Definitions

  • the present invention concerns the field of quasi-living and living polymerization of ethene (ethylene) and higher olefins at room temperature or above us- ing specific metallocene-based catalyst system, as well as the polymers and copolymers produced using such catalyst system.
  • Cp*2ZrCl2/MAO system has been termed a "lazy catalyst" for decades. Consequently, little work has been done on systems as sterically hindered as Cp* 2 ZrCl 2 , with steric hindrance quantified by the coordi- nation gap aperture (cga) , defined by Brintzinger (P.
  • BArF activators the term BArF as used herein encompasses fluoroaryl boranes and fluoroaryl borates
  • the metallocene catalyst system or composition of the present in- vention that is suitable for quasi-living or living polymerization of ethene is manifested by the features that it is prepared from (i) a sterically-hindered metallocene of composition (L m Cp) 2MR2 wherein M is a transition metal selected from Ti, Zr, and Hf, L is independent from each other an organic ligand, tn is 2 to 5, preferably 5, R is independent of each other a halogen or a C1-C7 alkyl, cyclohexylmethyl or benzyl and (ii) an activator with the proviso that in case that L is CH3 , m is 5 and R is Cl, the activator is alkylalumoxane, and the metallocene and the activator are aged together prior to contact with the olefin, preferably the ethene or
  • a preferred catalyst is a symmetrically bis alkylated catalyst with R being selected from linear or branched C ] __7-alkyl groups, preferably linear Ci_7-alkyl groups, cycloalkyl methyl groups and benzyl group, and/or L may be the same or different but preferably are the same, preferably L is CH3.
  • the metallocene is Cp* 2 ZrCl 2 and the alkylalumoxane activator is methylalu- moxane (MAO) .
  • R may be clorine or R is a hydrocarbyl residue, preferably with at least two carbons and possessing at least one /3-hydrogen .
  • a hitherto preferred catalyst is Cp* 2 Zr (CH 2 CH 2 CH 2 CH 3 ) 2 .
  • the composition may also comprise a scavenger, in particular a scavenger selected from tetraisobu- tyldialuminoxane (MMAO) and triisobutylaluminum (Al 1 Bu 3 ) , and/or a purifying agent, in particular ⁇ Bu 2 PhOH.
  • a scavenger in particular a scavenger selected from tetraisobu- tyldialuminoxane (MMAO) and triisobutylaluminum (Al 1 Bu 3 )
  • a purifying agent in particular ⁇ Bu 2 PhOH.
  • Some compositions, such as those with catalysts with R being chlorine or methyl or butyl are necessarily or preferably aged, especially under intended reaction conditions for at least about 20 minutes prior to contact with olefin.
  • the catalyst composition of the present invention can be used to prepare polyethylene at temperatures above 25°C, in particular polyethylene with a polydispersity index M w /M n
  • the catalyst composition of the present invention can also be used to prepare copolymers of ethene and a higher ⁇ -olefin.
  • a method for producing polyolefins, in particular ethene comprising polyolefins, especially polyethylene, in a reaction mixture comprises adding to the reaction mixture a catalyst composition of the present invention.
  • the catalyst composition and/or the reaction mixture are subjected to a pre-treatment preferably a pre-treatment with scavenger such as MMAO and/or 11 Bu 2 PhOH.
  • the method is suitable for manufacturing polyethylene at temperatures above 25°C, in particular polyethylene with a polydispersity index M w /M n ⁇ 1.7, and/or for manufacturing highly linear polyethylene, and/or for manufacturing copolymers of ethene and a higher ⁇ -olefin.
  • electrospray ionization mass spectrometry can be used to analyze oligomer distributions produced by either coordi- native quenching of the polymerization reaction ((a) C. Hinderling, P. Chen, Angew. Chem. Int. Ed. Engl., 1999, 38, 2253; (b) C. Hinderling, P. Chen, Int. J. Mass Spec.
  • the distributions could be fitted to a kinetic scheme from which rates for initiation, propagation, chain- transfer to monomer (or zirconium) , and chain-transfer to aluminum could be extracted.
  • Examples in the published work were shown for the Cp2ZrCl2/MAO catalyst system, which is recognized in practice as a rather ordinary single-site Ziegler-Natta catalyst.
  • the re- suits for the sterically much more hindered Cp* 2 ZrCl 2 /MAO catalyst system looked very different. The more hindered catalyst had been long known as a poor catalyst .
  • the hitherto accepted explanation was that propagation rates at the highly hindered active site are low.
  • the inventors found that, under the particular conditions of activation, there is essentially no conversion of the precatalyst Cp*2ZrCl2 into the active species, even with molar excesses of MAO that worked for other systems. Accordingly, the inventors surmised that the poor activity of the system derived from inefficient initiation; no statement concerning the propagation rate can be deduced from the experiments in the prior art .
  • MAO with indefinite oligomeric structure in solution, has been the first highly effective activator of metallocene catalysts. It still remains an economically viable co-catalyst in industry. Normally it is been used in large excess relative to the transition metal species for optimum activation.
  • Commercial MAO solution always contains free tri-methylaluminum (TMA) .
  • TMA is known to easily form Me-bridged di-nuclear species which are catalytically inactive and to promote chain transfer.
  • Busico and co-workers used 2,6-di-tert- buthylphenol ( ⁇ Bu 2 Ph-OH) as an efficient method to trap free TMA (Busico, V., Cipullo, R, Cutillo, F., Friederichs, N., Tonca, S., Wang, B., J. Am. Chem. Soc . 2003, 125, 12402) .
  • the distribution of DCC-trapped oligomer distributions can be fit using a kinetic model in which the chain transfer to aluminum is effectively irreversible.
  • a genetic algorithm an optimization method based on natural selection, was used to find the best set of rate constants.
  • the mass distribution and fits resulting from the best rate constants for propagation and chain transfer to Al in two different temperatures are shown in Fig. 5 for data taken at two different polymerization tempera- tures .
  • Cp*2 ZrCl 2 /MAO the inventors reasoned that the formation of the dimeric reservoir species could be also suppressed in a more sterically hindered complex, e.g. a preferably symmetrically bis alkylated catalyst with the alkyl groups selected from lin- 25 ear or branched C ⁇ _7-alkyl groups, preferably linear C ⁇ _ 7 -alkyl groups, cycloalkyl methyl and benzyl.
  • Cp*2ZrCl2 was alkylated with n-butyllithium.
  • the resulting Cp* 2 Zr (CH 2 CH 2 CH 2 CH 3 ) 2 could be activated by BArF.
  • the catalyst system polymerized ethene with no in-
  • inventive process is based on steri- cally-hindered metallocene catalysts, for example, Cp*2ZrR2, where R is optionally a halogen or a hydrocar- byl residue including hydrocarbyl residues with ⁇ - hydrogens as already outlined above.
  • Activators include MAO, arylboranes and aryl- borates, optionally together with tetraisobutyldialumi- noxane (MMAO) and/or triisobutylaluminum.
  • MMAO tetraisobutyldialumi- noxane
  • triisobutylaluminum triisobutylaluminum.
  • DCC N, N' -dicyclohexylcarbodiimide
  • DCC N, N' -dicyclohexylcarbodiimide
  • DCC N, N' -dicyclohexylcarbodiimide
  • Fig. 8 Number-average molecular mass (M n ) vs. polymerization time t for ethene homopolymers prepared at 60 °C in the presence of Fig. 9: Inverse of number-average degree of polymerization (P n ) vs. inverse of polymerization t for ethene homopolymers prepared at 60 °C in the presence of (Me 5 Cp) 2 ZrCl 2 /MAO.
  • Fig. 10 Polymerization activity (a), polydispersity index (b) , number average and weight average molecular weight of the polymers (c) , and percentage of the number of polymer chains to the number of Zr vs . time for Cp* 2 ZrCl 2 /MAO/ t Bu2Ph-OH catalytic system.
  • Fig. 11 Inverse of the number-average degree of polymerization [Pn) against time of ethene polymerization for Cp*2ZrCl2/MAO/ t Bu2Ph-OH catalytic system at 45°C.
  • Fig. 12 Polymerization activity (a), polydispersity index (b) , number average and weight aver- age molecular weight of the polymers (c) , and percentage of the number of polymer chains to the number of Zr vs . temperature for Cp* 2 ZrCl2/MAO catalytic system at 2 bar total pressure.
  • Fig. 13 Polymerization activity (a), polydispersity index (b) , number average and weight aver- age molecular weight of the polymers (c) , and percentage of the number of polymer chains to the number of Zr vs . temperature for Cp*2ZrCl2/MAO/ t Bu2Ph-OH catalytic system.
  • Fig. 14 Polymerization activity (a), polydispersity index (b) , number average and weight aver- age molecular weight of the polymers (c) , and percentage of the number of polymer chains to the number of Zr vs . pressure for Cp*2 z rCl2/MA0 catalytic system.
  • Fig. 15 Ethene flow during polymerization vs. time with Cp*2ZrCl2/MAO at 40 0 C at different pres- sures .
  • Fig. 16 Polymerization activity (a), polydispersity index (b) , number averaged and weight averaged molecular weight of the polymers (c) , and percentage of the number of polymer chains to the number of Zr vs. pressure for Cp*2ZrCl2/MAO/ t Bu 2 Ph-OH catalytic system.
  • Fig. 17 Polymerization activity (a) and polydispersity index (b) , number averaged and weight averaged molecular weight of the polymers product (c) , and percentage of the number of polymer chains vs Al : Zr ratio for (Me 5 Cp) 2 ZrCl 2 ZMAO catalytic system.
  • Fig. 18 Polymerization activity (a), polydispersity index (b) , number average and weight average molecular weight of the polymers (c) , and percentage of the number of polymer chains vs Al : Zr ratio for Cp*2ZrCl2/MAO/ t Bu 2 Ph-OH catalytic system.
  • Fig. 19 Polymerization activity (a), polydispersity index (b) , number average and weight average molecular weight of the polymers (c) , and percentage of the number of polymer chains to the number of Zr vs. %MMA0/MA0 in Cp* 2 ZrCl 2 /MAO/MMAO catalytic system.
  • the non-filled black symbols on the right side of the plots are result for Cp 2 ZrCl2 /MMAO system.
  • Fig. 20 13 C NMR spectrum of polyethylene prepared with Cp*2 Zr (CH3) 2/BArP showing no visible branching in the polymer.
  • Fig. 21 13 C NMR spectra of ethylene- 1-hexene copolymer produced by Cp*2ZrBu2 activated by B(CgF5)3 at 40 0 C in neat 1-hexene with an ethylene pressure of 1.5 bar .
  • Fig. 22 Ethylene flow against time for the
  • Fig. 23 Ethylene flow versus time for the Cp*2 ZrBu 2 catalyzed polymerization showing a constant ethylene uptake already at the very beginning of the reaction.
  • Fig. 25 Number average molecular weight (M n ) and polydispersity indexes (PDI) as a function of time for the polymers catalyzed by both Cp*2ZrMe 2 and Cp*2 z rBu2- The polymers were prepared in 50 mL bulk po- lymerization and aliquots from 1 to 3.5 minutes were removed
  • Fig. 26 Polydispersities for polymerizations catalyzed by the dibutyl and dimethyl catalysts in the same conditions. A noticeable difference can be observed. Conditions: 40 0 C, 2 bar ethylene, 1 bar argon, 3.5E-4 catalyst concentration, 1 cocatalyst equivalent, 4 scavenger equivalents.
  • Fig. 27 The trends of the average molecular weights, the polydispersity, the number of polymer chains and the activity against the temperature are depicted. Conditions: 3 min. polymerizations, 40 0 C, 2 bar ethylene, 1 bar argon, 3.5E-4 catalyst concentration, 0.5 cocatalyst equivalent, 4 scavenger equivalents.
  • Fig. 28 Linear trend between the growth of molecular weight and the time at 40 0 C and 60 0 C.
  • Fig. 29 The trends of the average molecular • ⁇ weights, the polydispersity, the number of polymer chains and the activity against the ethylene pressure are depicted. Conditions: 3 min. polymerization, 40 0 C, 1 bar argon, 3.5E-4 catalyst concentration, 0.5 cocatalyst equivalent, 4 scavenger equivalents.
  • Fig. 30 The trends of the average molecular weights, the polydispersity, the number of polymer chains and the activity against the cocatalyst equivalent are depicted.
  • Fig. 32 The trend of the average molecular weights, the polydispersity, the number of polymer chains and the activity against the scavenger equivalent (MMAO and Al 1 B ⁇ ) are depicted.
  • Example 1.1 Time dependency of polymerization Example 1.1.
  • Fig. 6- (a) indicates poor activation of the catalyst, however it must be emphasised that these ac- tivities are only at Al : Zr ratio of 12. Usually higher ratio of MAO is used to optimize the activity. Nevertheless the activity increases smoothly and stays constant after a few minutes. From the ethene uptake recorded during the polymerization of sample A early increase in the activation during the first 200 s of polymerization (Fig. 7) was assigned to the induction period. The later constant flow up to 10 min confirmed the persistence of the number of active sites over the time of the polymerization. The number average and weight average molecular weight are increasing with time although in this system the growth of the former is slow during the induction period. For a living polymerization a linear increase in the number average molecular weight with zero intercept would be expected.
  • Fig. 6- (d) reveals that the number of chains exceeds somewhat the number of theoretically available catalytic sites (number of Zr) as a result of chain transfer to Al.
  • the extrapolation of a lin- ear trend to time zero shows that the number of active sites at the beginning of polymerization before chain transfer to Al is 6% which is in the accepted range.
  • the ethene flow over time of this experiment is shown in Fig. 7.
  • the polydispersity of the product polymer at first minutes of polymerization has a Poisson distribution with a PDI close to that of living polymeri- zation.
  • Keii and coworkers defined a
  • TMA trimethylaluminum
  • the activity showed the same induction period as in Cp* 2 ZrCl 2 /MAO system.
  • the activity, polydispersity, and the number of chains remained constant after the in- duction period, consistent with the monotonic increase in the number average and weight average molecular weights.
  • the higher polydispersity in Fig. 6 and 10 is an artefact, due to insufficient stirring in a new reactor used in this experiment.
  • the Keii equation (eq.l) gives a higher propagation rate and a chain transfer frequency of 5 times less than the already small value found for the Cp* 2 ZrCl2/MAO system (no ⁇ u 2 Ph-OH) under otherwise identical conditions.
  • Limiting number average degree of po- lymerization was predicted to be 81 kDa at 45°C.
  • Fig. 12- (a) summarizes the temperature dependency of the activity in two different pressures (1.0 and 1.5 bar ethene) . The early increase in the activity was attributed to the increase in activation and abundance of active sites at higher temperature.
  • the polydispersity index depends on the molecular weight in non-living polymerization. Further discussion will appear below.
  • Example 1.3 Cp*2ZrCl2/MAO pretreated with vacuum; higher activity
  • MAO was imposed to vacuum for 10s.
  • the solution was saturated with 1.5 bar ethylene prior to introduce the precatalyst .
  • Example 1.4. Dependency on Ethene Pressure.
  • Example 1.4. a) Cp*2ZrCl2/MAO The activity of the catalyst with respect to ethene pressure was investigated at limited range of pressure at 40 0 C for 4 min polymerization (results presented in Fig. 14) . The range of the pressures was selected so that visible precipitation of polymer was not observed before 4 min.
  • Example 1.4 b) Cp* 2 ZrCl 2 /MAO/ 1 ⁇ Bu 2 Ph-OH
  • the trend for the pressure in this system was found to be different (Fig. 16) .
  • the activity did not increase and stayed more or less in the same range as the pressure decreased.
  • the same was true for the number of chains and the polydispersity but obviously the average molecular weights increased with pressure.
  • the linear increase in M n is further proof of lack of /3-hydride transfer to monomer.
  • Example 1.5 Al/Zr Ratio: Example 1.5. a) Cp* 2 ZrCl 2 /MA.O system Increase in Al/Zr ratio improved the degree of activation and increased the number of chains but as it was accompanied with detectable chain transfer, the product chains had lower average molecular weight (Fig. 17) . Activation with Al/Zr ratio of 6 or lower was not possible for experimental reasons.
  • Al/Zr 100 for hitherto unknown reasons. In any case, the decrease cannot be explained by a chain transfer to metal as such transfer is supposed not to change the activity. In addition, chain transfer to metal should increase the number of chains and reduce the molecular weight .
  • Example 1.6 MMAO as Co-activator in the catalytic system Cp*2ZrCl2/MAO/MMAO.
  • Example 2.1 Polymerization of ethene with Cp*2Zr (CH 3 ) 2/BArF/MMAO. Productivity
  • the reaction was artificially retarded by adding an overpressure of argon to which ethene was then added.
  • the lower ethene concentration then reduced the productivity to allow a fair assessment of the polydispersity .
  • Example 2.3 Polymerization of ethene with Cp*2Zr (CH 3 )2/BArF/MMAO. Linearity
  • Example 2.4 Cp*2Zr (CH 2 CH 2 CH 2 CH 3 ) 2/BArF. Co- polymerization of ethene and 1-hexene.
  • Table 1 shows and compares the results for GPC analysis of Cp 2 ZrCl 2 , Cp* 2 ZrBu 2 and Cp* 2 ZrCl 2 .
  • the activity of Cp 2 ZrCl 2 and Cp* 2 ZrCl 2 were compared in a TMA free system. The activity of the latter shows that this catalyst is more active than the former in a TMA free system.
  • the number of chains in run.2, Cp* 2 ZrCl 2 was 3.2% of number of Zr and in run.l, for Cp 2 ZrCl 2 , this was 14.0%.
  • Cp* 2 ZrCl 2 catalyst the activated catalyst has the form Cp* 2 ZrMe + and first insertion of monomer to the Zr-Me bond was slower than propagation.
  • Cp* 2 ZrBu + has already butyl groups ready for migratory insertion of an ethene it was supposed that the polymer produced by Cp* 2 ZrBu 2 as the precatalyst must have lower polydisper- sity. In contrast, however, it resulted to a higher polydispersity .
  • both Bu groups are abstracted and the active form for both catalysts is Cp* 2 ZrMe + . Larger polydispersity of Cp* 2 ZrBu 2 must be related to slower activation by MAO during the abstraction of bulkier i -butyl group. Table 1. The results for GPC analysis of different catalysts in ethene polymerization.
  • the polymer samples were analyzed by high temperature GPC using 1 , 2 , 4-trichlorobenzene as solvent.
  • Mn was found to grow linearly with time and the polydispersity was found to stay constant over the polymerization time (Fig. 25) .
  • the molecular weight distributions were broader than expected because the reaction was so fast that mass transport problems could not be avoided with the type of reactor and reaction conditions available. Nevertheless these conditions were optimal for analyzing the behavior of the molecular weight as a function of time.
  • the molecular weights obtained with two different catalysts were in the same range if taking into account the experimental error.
  • the number of polymer chains increased until 60 0 C but then, deactivation mechanisms took place which reduced the number of chains or maybe the number of active site during the preactivation pe- riod.
  • the maximum activity was found at 25 0 C, reflecting a competition between the rate of propagation and the solvation of ethylene.
  • the molecular weights were found to grow linearly with the time at 40 0 C and 60 0 C (Fig. 28) . At higher temperature, the molecular weight of the polymer chains growed slower because the solvation of ethylene was reduced. The molecular weight, the polydispersity, the number of polymer chains and the activity against the conditions variation where analyzed. The trends found for the average molecular weights, the polydispersity, the number of polymer chains and the activity against the temperature are depicted in Fig. 27.
  • the conditions used were 3 min. polymerization, 40 0 C, 1 bar argon, 3.5E-4 catalyst concentration, 0.5 cocatalyst equivalent, 4 scavenger equivalents.
  • Fig. 30 The trends of the average molecular weights, the polydispersity, the number of polymer chains and the activity against the cocatalyst equivalent are depicted in Fig. 30.
  • the conditions used were 3 min. polymerization, 40 0 C, 2 bars ethylene, 1 bar argon, 3.5E-4 catalyst concentration, 4 scavenger equivalent.
  • V Variation of the scavenger equivalent
  • the more scavenger equivalents the more chain transfer is possible and the more active sites should be generated (theoretically for 100% active sites (ternary system) one equivalent of scavenger should be sufficient; but with high equivalents of scavenger, the system was found to be cleaner and the catalyst to be more alive) .
  • the molecular weight has been found to slightly diminish and the polydispersity to increase.
  • Fig. 38, 39 and 40 The trends of the average molecular weights, the polydispersity, the number of polymer chains and the activity against the scavenger equivalent for different scavenger equivalents (MMAO and Al 1 B ⁇ ) are depicted in Fig. 38, 39 and 40. All polymerizations were performed for 3 min. at 40 0 C, 2 bars ethylene, 1 bar argon, with 2E-3 catalyst concentration, 1 cocatalyst equivalent (Fig. 31), 1E-3 catalyst concentration, 1 cocatalyst equivalent (Fig. 32) .

Abstract

L'invention porte sur une composition de catalyseur appropriée pour la polymérisation quasi-vivante ou vivante de l'éthène et la copolymérisation de l'éthène et d'autres oléfines. Cette composition est préparée à partir de (i) un métallocène stériquement encombré ayant la composition (LmCp)2MR2 dans laquelle M représente un métal de transition choisi parmi Ti, Zr et Hf, chaque L représente indépendamment des autres un ligand organique, m représente 2 à 5, de préférence 5, chaque R représente indépendamment des autres un halogène ou un alkyle en C1-C7, cyclohexylméthyle ou benzyle et (ii) un activateur et facultativement un fixateur. De plus, pour certains systèmes il s'est avéré avantageux de faire vieillir la composition de catalyseur avant utilisation. Cette composition de catalyseur permet de produire du polyéthylène à des températures au-dessus de 25°C avec une faible polydispersité et une linéarité élevée.
PCT/CH2008/000426 2008-10-09 2008-10-09 Polymérisation vivante et quasi-vivante d'oléfines catalysée par un métallocène WO2010040235A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
PCT/CH2008/000426 WO2010040235A1 (fr) 2008-10-09 2008-10-09 Polymérisation vivante et quasi-vivante d'oléfines catalysée par un métallocène

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/CH2008/000426 WO2010040235A1 (fr) 2008-10-09 2008-10-09 Polymérisation vivante et quasi-vivante d'oléfines catalysée par un métallocène

Publications (1)

Publication Number Publication Date
WO2010040235A1 true WO2010040235A1 (fr) 2010-04-15

Family

ID=39929843

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CH2008/000426 WO2010040235A1 (fr) 2008-10-09 2008-10-09 Polymérisation vivante et quasi-vivante d'oléfines catalysée par un métallocène

Country Status (1)

Country Link
WO (1) WO2010040235A1 (fr)

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0283739A2 (fr) * 1987-03-10 1988-09-28 Chisso Corporation Dihalogénures de bis(cyclopentadiényl di-, tri- ou tétrasubstitué)-zirconium
DE4332009A1 (de) * 1993-09-21 1995-03-30 Hoechst Ag Verfahren zur Herstellung von Organometallfluoriden
WO2008010865A2 (fr) * 2006-07-19 2008-01-24 Exxonmobil Chemical Patents Inc. Procédé de production de fluides de viscosité élevée

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0283739A2 (fr) * 1987-03-10 1988-09-28 Chisso Corporation Dihalogénures de bis(cyclopentadiényl di-, tri- ou tétrasubstitué)-zirconium
DE4332009A1 (de) * 1993-09-21 1995-03-30 Hoechst Ag Verfahren zur Herstellung von Organometallfluoriden
WO2008010865A2 (fr) * 2006-07-19 2008-01-24 Exxonmobil Chemical Patents Inc. Procédé de production de fluides de viscosité élevée

Non-Patent Citations (4)

* Cited by examiner, † Cited by third party
Title
"Toward a Living Polymerization of Ethylene at High Temperature", INTERNATIONAL SYMPOSIUM ON HOMOGENOUS CATALYSIS, 10 July 2008 (2008-07-10), Florence, Italy, XP002505354 *
CHRISTOPH JANIAK, KATHARINA C. H. LANGE, UWE VERSTEEG, DIETER LENTZ, PETER H. M. BUDZELAAR: "Ethene Polymerization Activity and Coordination Gap Aperture in non-ansa Alkyl-substituted Cyclopentadienyl- and Phospholyl-zirconium/MAO Catalysts", CHEMISCHE BERICHTE, vol. 129, 31 December 1996 (1996-12-31), pages 1517 - 1529, XP002504659 *
FABIO DI LENA: "Microkinetic study of metallocene catalyzed ethene polymerization by electrospray ionization mass spectrometry", 15 April 2008, ETH ZÜRICH, XP002505355 *
SAITO J ET AL: "LIVING POLYMERIZATION OF ETHYLENE WITH A TITANIUM COMPLEX CONTAINING TWO PHENOXY-IMINE CHELATE LIGANDS", 3 August 2001, ANGEWANDTE CHEMIE. INTERNATIONAL EDITION, WILEY VCH VERLAG, WEINHEIM, PAGE(S) 2918 - 2920, ISSN: 1433-7851, XP001075307 *

Similar Documents

Publication Publication Date Title
Chien et al. Isospecific polymerization of propylene catalyzed by rac-ethylenebis (indenyl) methylzirconium cation
JP6770960B2 (ja) 分岐ポリオレフィンの調製方法
EP1373332B1 (fr) Constituant catalytique de polymerisation d'olefines, systeme catalytique et procede de polymerisation mettant en application ce systeme catalytique
EP2220128B2 (fr) Procédé de fabrication de polyoléfines par polymérisation vivante par transfert de chaîne et coordination
Wilen et al. Polar Activation in Copolymerization of Propylene and 6-tert-Butyl-[2-(1, 1-dimethylhept-6-enyl)]-4-methylphenol over a Racemic [1, 1'-(Dimethylsilylene) bis (. eta. 5-4, 5, 6, 7-tetrahydro-1-indenyl)] zirconium Dichloride/Methylalumoxane Catalyst System
Proto et al. Isotactic-specific polymerization of propene with supported catalysts in the presence of different modifiers
WO1997014727A1 (fr) Systeme de polymerisation homogene d'olefine, a base d'un compose metallocene et a activite accrue
JP2018500430A (ja) 一又は複数の末端官能化された分岐を有するポリオレフィンの調製方法
EP2496612A1 (fr) Composant de catalyseur pour la polymérisation d'oléfines ayant un ligand guanidinate
EP1749841A1 (fr) Supports actives et fluores contenant des complexes organo-ferreux
Chien et al. Olefin copolymerization with metallocene catalysts. II. Kinetics, cocatalyst, and additives
Deng et al. Polymerization of methyl methacrylate with achiral 4B group metallocene compounds
CN113527352A (zh) 一种吡啶胺基铪化合物及其制备方法与应用
KR102375854B1 (ko) 폴리프로필렌 및 그 제조방법
CN111116801B (zh) 一种烯烃-不饱和羧酸共聚物的制备方法
Ioku et al. Effects of Cocatalysts on Propene Polymerization with [t‐BuNSiMe2 (C5Me4)] TiMe2
Götz et al. Influence of Aluminium Alkyl Compounds on the High‐Pressure Polymerization of Ethylene with Ternary Metallocene‐Based Catalysts. Investigation of Chain Transfer to the Aluminium
US9434795B2 (en) Production of vinyl terminated polyethylene using supported catalyst system
WO2010040235A1 (fr) Polymérisation vivante et quasi-vivante d'oléfines catalysée par un métallocène
JP7205983B2 (ja) 無水炭化水素溶媒を用いた助触媒化合物の製造方法
Doi et al. Synthesis of “living” polyolefins with soluble Ziegler-Natta catalysts and application to block copolymerization
KR101238784B1 (ko) 아민기로 가교된 메탈로센 촉매, 이의 제조방법 및 상기 메탈로센 촉매를 이용한 에틸렌-알파 올레핀 공중합체의 제조방법
Ranieri et al. Site count: is a high-pressure quenched-flow reactor suitable for kinetic studies of molecular catalysts in ethylene polymerization?
Götz et al. Investigations on ternary metallocene‐based catalyst systems
Chen et al. (1, 3-Propanediyl) silylene-bis (1-indenyl) dichlorozirconium. Synthesis and polymerization catalysis

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 08800472

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 08800472

Country of ref document: EP

Kind code of ref document: A1