WO1997043321A1 - Systeme catalyseur stereospecifique pour la polymerisation des olefines et processus de polymerisation en plusieurs etapes au moyen de ce systeme catalyseur - Google Patents

Systeme catalyseur stereospecifique pour la polymerisation des olefines et processus de polymerisation en plusieurs etapes au moyen de ce systeme catalyseur Download PDF

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WO1997043321A1
WO1997043321A1 PCT/FI1997/000280 FI9700280W WO9743321A1 WO 1997043321 A1 WO1997043321 A1 WO 1997043321A1 FI 9700280 W FI9700280 W FI 9700280W WO 9743321 A1 WO9743321 A1 WO 9743321A1
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catalyst system
polymerization
donor
compound
group
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PCT/FI1997/000280
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Mika Härkönen
Reijo Perälä
Knut Fosse
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Borealis A/S
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Publication of WO1997043321A1 publication Critical patent/WO1997043321A1/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
    • C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond

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  • the present invention relates to a catalyst system suited for the polymerization of olefins, said system comprising at least a procatalyst based on a titanium compound, an organoalu- minium cocatalyst and at least two silane compounds of which at least one has high stereospecificity, but low hydrogen sensitivity, and at least one has high hydrogen sensitivity, but optionally lower stereospecificity.
  • the invention relates also to multistaged polymerization processes using this catalyst system.
  • Olefins are conventionally polymerized using a Ziegler-Natta catalyst system comprising a procatalyst and a cocatalyst as its essential components.
  • the procatalyst is formed by a transition metal compound of subgroups 4-8 of the periodic system of elements (Hubbard, IUPAC 1970).
  • the cocatalyst is formed by an organic compound of a metal of major groups 1-3 of the periodic system of elements.
  • the transition metal conventionally is a titanium, zirconium, or vanadium compound, advantageously a titanium compound, and in fact, titanium has been found a particularly advantageous transition metal.
  • Said compounds typically are halides or oxyhalides, or alternatively, organic compounds, conventionally alkoxides, alcoholates or haloalkoxides. Other kinds of organic compounds are less frequently used, while not necessarily unknown in the art.
  • the transition metal compound can be expressed in the form of the following generalized formula:
  • M is a transition metal of subgroups 4-8, advantageously Ti, Zr or V, while R' and R" represent the similar or dissimilar organic groups chiefly having a backbone of 1-20 carbons, M is a transition metal and X is a halogen, advantageously chlorine.
  • n and m are an integer in the range 0 - p.
  • the most advantageous compounds are selected from the group consisting of titanium alkoxides, halides and haloalkoxides, in particular when the halogen is chlorine.
  • suitable compounds include titanium tetramethoxide, tetraethoxide, tetrapro- poxides, tetrabutoxides and similar oxides, corresponding titanium alkoxyhalides in which 1-3 alkoxide groups are replaced by a halogen, chlorine in particular, and titanium halides, TiBr 4 and TiCl 4 in particular.
  • the most commonly used of these compounds is TiCl 4 .
  • two or a greater number of transition metal compounds can be used in the form of different mixtures.
  • the cocatalyst most commonly consists of an organic compound of a metal of major groups 1-3. While usually an aluminium compound is employed, also boron, zinc and alkali metal compounds have been used.
  • the aluminium compound can be written using the formula (2):
  • R is an organic hydrocarbon group, advantageously an C r C 2o alkyl
  • X is a halogen
  • n is an integer in the range 1 - 3.
  • cocatalyst can be used simul ⁇ taneously in the form of various mixtures.
  • a catalyst system contains components having catalyst improving and modifying characteristics.
  • the procatalyst can be prepared on a more or less inert support, whereby the procatalyst component may be in solid state even if the transition metal compound as such is not in solid form.
  • the procatalyst can be complexed with a so-called internal donor compound capable of electron donation so as to improve the stereospecificity and/or activity of the catalyst system.
  • the preparation of the procatalyst can be implemented using an auxiliary component which may be a dissolving or slurrying medium and from which a portion is possibly complexed with the procatalyst composition. Such a compound may also act as an electron donor.
  • the cocatalyst feed which typically takes place separately from the procatalyst composition not earlier than to the polymerization process, can be complemented with electron donor compound with a particular goal of improving the stereospecificity of the end product.
  • the electron donor is called an external donor.
  • a separate support com- pound is required provided that the transition metal compound of the procatalyst is not one itself.
  • the latter case is true for the transition metal compounds listed above.
  • Widely varied types of solid inorganic or organic compounds can be used as the support. Typical of these are oxides of silicon, aluminium, titanium, magnesium, chromium, thorium or zirconium or mixtures of these oxides, salts of different inorganic acids such as salts of the said metals or earth alkali or earth metals including magnesium silicate and calcium silicate, calcium chloride, calcium sulfate, etc. (cf., e.g. , FI Patent 85 710).
  • Important compounds as supports have been found from magnesium compounds including, e.g. , alkoxides, hydroxides, hydroxyhalogenides and halogenides, of which the latter ones, particularly magnesium dichloride is an extremely important support for procatalyst compositions.
  • Supports are typically subjected to different treatments before their use, whereby they can be heat-treated by, e.g. , calcining; they can be chemically treated to remove so-called surface hydroxyl groups; they can be mechanically treated by, e.g., grinding in a ball mill or spray mill (cf., e.g. , FI Patent 83 330).
  • An important support group is formed by magnesium halides, particularly MgCl 2 , which can be advantageously complexed with alcohols, whereby the complexed support can be brought to a morpholo ⁇ gically advantageous form by crystallization and/or solidification from an emulsion by a spray-drying technique or from a melt by a spray-crystallization technique (cf. , e.g., FI Patent 80 055).
  • organic supports comprise different polymers either in native form or modified. Of such supports worth mentioning are different poly olefins (polymers made from ethene, propene and other olefins), as well as different polymers of aromatic olefinic compounds (PS, ABS, etc.).
  • the oiefin monomers being polymerized can assume different spatial configurations when bonding to polymer molecule being formed, this formation generally requires a particular controlling compound capable of complexing the procatalyst so that the new monomer unit being joined to the polymer chain can principally adopt a certain position only.
  • a particular controlling compound capable of complexing the procatalyst so that the new monomer unit being joined to the polymer chain can principally adopt a certain position only.
  • electron donors or simply donors.
  • the donor may also render other properties besides the above-mentioned stereospecificity; for instance, the donor may improve the catalyst activity by increasing the bonding rate of the monomer units to the polymer molecule.
  • Such a donor which is incorporated by complexing in the procatalyst already during its preparation is called an internal donor.
  • donors include a plurality of alcohols, ketones, aldehydes, carboxylic acids, derivatives of carboxylic acids such as esters, anhydrides, halides, as well as different ethers, silanes, siloxanes, etc. Simultaneous use of several donors is also possible. Advantageous compounds in this respect have been found to be, e.g. , mono- and diesters of aromatic carboxylic acids and aliphatic alcohols, whose simultaneous use facilitates exchange esterification in conjunction with the use of a donor compound (cf. FI Patent 86 866).
  • a stereospecificity-controlling compound which is fed into the polymerization reactor only in conjunction with the cocatalyst is called an external donor.
  • Such donors are often the same compounds as those employed as internal donors, while in many cases the external donor in a single polymerization reaction advantageously should not be the same com ⁇ pound as the internal donor, because then the unlike properties of the different compounds can be exploited particularly if the combination of different donors amplifies the effect of their properties and if they have synergistic coeffects. Hence, finding a suitable optimum of such coeffects is the primary goal in the selection of different donors.
  • Advantageous external donors are different silane compounds, particularly alkoxysilanes (e.g. EP Patent 231 878 and EP Patent 261 961).
  • EP Patent 385 765 and EP Patent Application 601 496 to broaden molecular weight distribution with high productivity there may be used two alkoxysilane compounds: [I] R 1 2 Si(OR 2 ) 2 where R 1 is an alkyl, cycioalkyl or aryl group whose carbon atom adjacent to Si is secondary or tertiary carbon atom, and R 2 is a hydrocarbon group, and [II] R ln 2 Si(OR 2 ) 4 .
  • tetraethoxy silane and dicyclopentyldimet- hoxy silane as external donors are used together and then relatively high melt flow rate and moderately broad molecular weight distribution can be achieved.
  • the number of monomer units joining to a polymer molecule may vary from a few units to millions of units.
  • the molecular weight of a commercial-grade solid polyolefin is in the range of 10,000 - 1,000,000 g/mol. If the degree of polymerization remains lower, the product is a soft and plastic wax or paste-like plastisol, even a viscose liquid which may find use in special applications. A degree of polymerization exceeding one million is difficult to attain, and moreover, such a polymer often is too hard for most applications or too difficult to process.
  • the molecular weight control of the polymer has an important role, which can be accomplished by means of so-called chain-length controlling agents.
  • the chain-controlling agent added to the polymerization reaction is hydrogen whose benefit is not to introduce any undesirable group in the molecule. If the hydrogen addition is capable of controlling the molecular weight of the produced polymer, the polymerizati ⁇ on catalyst is said to be hydrogen sensitive. Different catalyst systems also have different hydrogen sensitivities, whereby different amounts of hydrogen will be required to polymers having the same melt flow rate. On the other hand, hydrogen addition elevates the polymerization activity of the catalyst.
  • Polymerization can be carried out in gas phase, whereby either gaseous monomer or an inert gas or a mixture thereof is fed to the reactor so that the entering gas keeps the growing polymer in the form of particles on which the growth of the polymer molecules takes place.
  • the reaction temperature is so high that even one or more monomers can be vaporized that are liquid under normal conditions.
  • the polymer particles are removed continuously from the reactor, and the monomer or monomer mixture feed is continuous.
  • the reaction products removal and precursor feed may also be intermittent.
  • the polymer particle layer which advantageously is kept in a fluidized state can be stirred by mechanical agitation. A great number of different agitator means and agitation systems are available.
  • Gas-phase polymerization is often carried out in a circulating fluidized-bed reactor in which the solid particles form a bed maintained in fluidized state by the upward directed flow of the gaseous feed medium.
  • the fluidized bed may also be formed by inert solids comprised of most varied inorganic and organic compounds.
  • a medium is required that is liquid at the poly- merization temperature, whereby said medium may comprise a single monomer or a greater number of monomers (usually referred to as bulk polymerization), or a separate solvent or diluting agent capable of dissolving or slurrying the monomer or/and the poly ⁇ mer.
  • the medium may then be a hydro- carbon solvent particularly including alkanes and cycloalkanes such as propane, butane, isobutane, pentane, hexane, heptane, cyclohexane, etc.
  • the polymerization reactor may be a conventional mixing vessel reactor complemented with widely varying additional arrangements, or alternatively, a loop- or ring-type tubular reactor in which the polymer slurry is circulated by means of different feed, end product removal and agitating arrangements.
  • catalyst systems of low hydrogen sensitivity may involve problems in the addition of required amount of hydrogen, because only a certain maximum concentration of oxygen can be dissolved in the medium.
  • Polymerization can be carried out in a multi-stage process, consisting two or more consecutive polymerization reactors connected in series.
  • the reactors can be either gas- phase or liquid-phase reactors or a combination thereof.
  • Preferably a combination of a loop reactor and a gas-phase reactor can be used.
  • An advantage gained from multi-stage processes can be a more narrow overall residence time distribution giving a more even particle size and polymer composition distribution.
  • Another target for the multi-stage processes is to run the reactors in different polymeriza- tion conditions giving new possibilities for product property tailoring. For example, having different hydrogen concentration in the each stage will broaden the molecular weight distribution (MWD) of the final product.
  • the polymerization can be carried out in at least two rectors and the donor having a very high hydrogen sensitivity is then fed first and the donor having a worse, even poor hydrogen sensitivity is fed into the second or several of more subsequent reactors.
  • MWD can be broa ⁇ dened by adding a highly hydrogen sensitive external donor to the first reactor and an external donor having a markedly lower hydrogen sensitivity to the second reactor, resulting that in the second reactor a donor mixture is actually used.
  • the external donors having a high hydrogen sensitivity give also a poor isotacticity to propene homopolymers.
  • MWD Molecular weight distribution
  • Polydispersity (Mw/Mn) of polypropylene produced by a continuous polymerization reactor with the above mentioned catalyst system is typically about 4 - 5.
  • stiffness of polypropylene can be increased.
  • simul ⁇ taneously impact strength usually decreases.
  • broadness of MWD influences the processability of the polymer.
  • MWD The broadness of MWD is measured most usually by gel permeation chromatography (GPC), which gives the polydispersity (Mw/Mn). Another relatively common method is based on the effects of MWD on rheological properties. Measuring the shear thinning or elasticity of molten polymer samples, e.g. Shear Thinning Index (SHU) or Elasticity Index, gives good information on the broadness of MWD. Broadened MWD increases usually both elasticity and shear thinning of polymer melts.
  • GPC gel permeation chromatography
  • MWD of polypropylene can be broadened by using a special type of alkoxy silane as an external donor.
  • the MWD of polypropylene is broadened by using a catalyst system having a 1: 1 mixture of two different alkoxysilanes as an external donor.
  • the polymerization reaction can be complemented, besides the mono ⁇ mers, procatalyst and cocatalyst, with at least two silane compounds capable of improving the stereospecificity of the resulting polymer product.
  • the mixture of said compounds contains A) at least one silane compound having a low hydrogen sensitivity but a very high stereospecificity and it has a formula (3):
  • R' is a aliphatic cyclic or branched hydrocarbon group having at least four carbon atoms and Me is a methyl group
  • R" is a branched or cyclic alkyl group containing at least 3 carbon atoms, a linear alkyl group containing at least 6 carbon atoms or aryl group containing 6 to 12 carbon atoms and Et is an ethyl group
  • the melt flow rate ratio of polyolefins produced by the catalyst composition is:
  • MFR(A) and MFR(B) defined according to ISO standard 1133 is melt flow rate of the polyolefin produced by a catalyst system including the external donor A and respectively B and the isotacticity ratio of polyolefins produced by the catalyst composi ⁇ tion is:
  • XS(B) and XS(A) are the isotacticities of the polyolefin (defined as the solubility in xylene at 25 °C) produced by a catalyst system including the external donor A and respectively B.
  • the molar ratio of the donor B and A can be in range of 0,5 and 0,95.
  • the solubility in xylene is defined as follows: a propylene homo or copolymer sample (about 2 g) is refluxed for an hour in 250 ml of xylene at 135 °C under nitrogen flow and agitation in a two-neck bottle. Then the mixture is allowed to cool to 25 °C. The undissol- ved polymer, a precipitate, is filtered out. The filtrate is then evaporated under nitrogen flow and dried in a vacuum oven at 90 °C and the cooled residue is weighted.
  • XS is calculated as:
  • A is the weight of the sample (g)
  • B is the amount of xylene (ml)
  • C is the amount of filtrate (ml)
  • D is the evaporation residue (g).
  • this composition makes the polymerization reaction extremely hydrogen sensitive, that is, the molecular weight of the produced polymer can be controlled in an improved manner over prior-art techniques by adjusting the amount of hydrogen added to the reaction and particularly makes it possible to produce a polymer with a low molecular weight which gives a high melt flow rate MFR.
  • the extraordinary result of this invention is an unexpectedly high isotacticity of the of the high MFR propene homopolymer produced with the donor combination used in this reaction. It has been suggested that the structure of the branched or cyclic or long linear hydrocarbon group R" of the donor B gives this extraordinary result.
  • the catalyst according to this invention can be used in multi-stage polymerization processes. The donor mixture can be fed to the first reaction stage or the more hydrogen sensitive donor B can be fed to the first reactor and the less hydrogen sensitive donor A to the second reactor which actually means the donor mixture is used in the second stage.
  • oiefin refers to a hydrocarbon containing at least one carbon-carbon double bond.
  • Such compounds particularly comprise different alkenes such as linear monoalkenes including ethene, propene, butenes, pentenes, etc.
  • the olefins may also be compounds branched with a hydrocarbon group, of which a simple example is 4-methyl- 1-pentene.
  • one or a greater number of the above-mentioned compounds can be used in the reaction.
  • particularly important compounds are the homo- and copolymers of propene.
  • asymmetric unsaturated hydrocarbons of conventional monoolefins only ethene is symmetric
  • the stereo ⁇ specificity is determined by the tacticity of the polymer so that if the subsequent units being added to the growing polymer chain always assume a similar position with regard to the double bond, an isotactic polymer is formed, and if the subsequent units always assume a position opposite to that of the preceding unit, a syndiotactic polymer is formed, and if the subsequent units assume a random position, an atactic polymer is formed.
  • any form may find optimum use in a certain application as the polymer properties may also be controlled by its type of tacticity.
  • the isotactic form is the most desirable. Its degree of crystallization is highest, it has high mechanical strength, is also otherwise most durable and is not sticky.
  • the propene can be copolymerized with ethene, whereby such copolymer is suited for applications requiring transparency, high impact resistance or good seaming capability.
  • Propylene was polymerized using a high yield catalyst in liquid propylene for 1 hour at 70 °C.
  • TEA was introduced to approximately 35 ml of dried heptane and the external donor was added into the mixture. The solution was allowed to react 5 minutes with occasional mixing. A half of the solution was fed into a 5 dm 3 polymerization autoclave (at a temperature of about 18 °C) and another half was contacted with the catalyst. After 10 minutes contact time the catalyst suspension was also added into the polymerization autoclave. 220 mmol hydrogen from feeding cylinder and 1400 g of liquid propylene were added.
  • Example 3 The polymer was produced as in Example 1, except that the molar ratio of IBTEO and DCPDMS was 90/10.
  • the polymerization results are summarized in Table 1.
  • the polymer was produced as in Example 1 , except that the molar ratio of IBTEO and DCPDMS was 80/20.
  • the polymerization results are summarized in Table 1.
  • the polymer was produced as in Example 1 , except that the molar ratio of IBTEO and DCPDMS was 50/50.
  • the polymerization results are summarized in Table 1.
  • the polymer was produced as in Example 1, except that the combination of triethoxy octyl silane (OCTEO) and dicyclopentyl dimethoxy silane (DCPDMS) with the molar ratio of 50/50 was as external donor was used.
  • OTEO triethoxy octyl silane
  • DCPDMS dicyclopentyl dimethoxy silane
  • the polymer was produced as in Example 5, except that the molar ratio of OCTEO and DCPDMS was 90/10.
  • the polymerization results are summarized in Table 1.
  • Example 2 Polymerization was done as in Example 1 , except that triethoxy isobutyl silane (IBTEO) was used as external donor in the first stage and after a half of the material was polymeri ⁇ zed dicyclopentyl dimethoxy silane (DCPDMS) diluted with pentane was added into the polymerization autoclave. A hydrogen amount of 500 mmol instead of 220 mmol was used. The results are seen below.
  • IBTEO triethoxy isobutyl silane
  • DCPDMS dicyclopentyl dimethoxy silane
  • the propene copolymers were produced in a pilot plant having a loop reactor and a fluidized bed gas-phase reactor connected in series.
  • the catalyst, cocatalyst and a donor were fed into the loop reactor.
  • the reaction medium of the loop was flashed away before the solid polymer containing the active catalyst entered the gas-phase reactor.
  • a prepolymerized MgCl 2 supported Ti-catalyst (prepared according to patent FI 86 866) was used in the polymerization.
  • Cocatalyst was triethyl aluminum (TEA) and as external donor was used a mixture of IBTEO and DCPDMS in a molar ratio of 70/30.
  • Al/Ti mol ratio was 150 and Al/donor mol ratio 5.
  • the polymerization temperature used in both stages was 70 °C.
  • the production rate ratio between the first and second stage was 45/55. Hydrogen feed was used into both the reactors to control the MFR.
  • the XS of the final product was 2,3 w-% .
  • the polymer was produced as in Example 1 , except isobutyl trimethoxy silane (IBTMO) was used as external donor instead of the IBTEO/DCPDMS mixture.
  • the amount of hydrogen was 70 mmol instead of 220 mmol.
  • the polymerization results are summarized in Table 2.
  • the polymer was produced as in Comparative example 1 , except triethoxy isobutyl silane (IBTEO) was used as external donor instead of IBTMO.
  • IBTEO triethoxy isobutyl silane
  • the polymer was produced as in Comparative example 1 , except triethoxy octyl silane (OCTEO) was used as external donor instead of IBTMO.
  • OTEO triethoxy octyl silane
  • the polymer was produced as in Comparative example 1 , except dicyclopentyl dimethoxy silane (DCPDMS) was used as external donor instead of IBTMO.
  • DCPDMS dicyclopentyl dimethoxy silane
  • the polymer was produced as in Example 8, except that as external donor only dicyclo ⁇ pentyl dimethoxy silane (DCPDMS) and the hydrogen feed into the both reactors were similar as in example 8.
  • MFR of the final product 3,6 g/10 min.
  • XS of the final product was 2,3 w-% .

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  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
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  • Polymers & Plastics (AREA)
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Abstract

On peut polymériser des oléfines ou des mélanges d'oléfines, en particulier du propylène ou des mélanges de propylène avec, de préférence, de l'éthylène, à l'aide d'un système catalyseur Ziegler-Natta contenant un ou plusieurs composés permettant de réguler la stéréospécificité du polymère obtenu, c'est-à-dire d'en augmenter le caractère isostatique et la rigidité. Ce composé dénommé donneur externe peut également avoir d'autres effets. On peut utiliser à cette fin un mélange de deux ou plusieurs composés comprenant au moins deux silanes dont au moins un présente une sensibilité très élevée à l'hydrogène et un autre, une faible sensibilité à l'hydrogène mais une stéréospécificité élevée. Le premier composé est de préférence choisi dans le groupe des diméthoxysilanes à groupes d'hydrocarbures cycliques aliphatiques ou ramifiés, par exemple le diméthoxy-dicyclopentylsilane, tandis que le deuxième composé est choisi dans le groupe des triéthoxysilanes à groupe ramifié volumineux ou alkyle linéaire, de préférence un groupe i-butyle, n-octyle et phényle.
PCT/FI1997/000280 1996-05-15 1997-05-12 Systeme catalyseur stereospecifique pour la polymerisation des olefines et processus de polymerisation en plusieurs etapes au moyen de ce systeme catalyseur WO1997043321A1 (fr)

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AU27024/97A AU2702497A (en) 1996-05-15 1997-05-12 Stereospecific catalyst system for olefin polymerization and multistaged polymerization processes using this catalyst system

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FI962087A FI104080B (fi) 1996-05-15 1996-05-15 Olefiinien polymerointiin tarkoitettu stereospesifinen katalyyttisysteemi ja monivaiheiset polymerointiprosessit, joissa tätä systeemiä käytetään
FI962087 1996-05-15

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WO1998045338A1 (fr) * 1997-04-07 1998-10-15 Engelhard Corporation Modification de la repartition du poids moleculaire d'un polymere a l'aide de systemes de silanes melanges dans des catalyseurs de polymerisation a haute activite
WO1999029749A1 (fr) * 1997-12-10 1999-06-17 Exxon Chemical Patents Inc. Polymeres de propylene elastomeres
WO1999058585A1 (fr) * 1998-05-14 1999-11-18 Exxon Chemical Patents Inc. Matieres polymeres obtenues a partir de melanges d'electrodonneurs
US6087459A (en) * 1998-05-14 2000-07-11 Exxon Chemical Patents Inc. Polymeric materials formed using blends of electron donors
WO2000068315A1 (fr) * 1999-05-07 2000-11-16 Borealis Technology Oy Polymeres de propylene de haute rigidite et leur obtention
US6197910B1 (en) 1997-12-10 2001-03-06 Exxon Chemical Patents, Inc. Propylene polymers incorporating macromers
US6303715B1 (en) * 1998-12-04 2001-10-16 Samsung General Chemicals Co., Ltd. Method for polymerization and copolymerization of alpha-olefin
US6566294B2 (en) 2000-12-21 2003-05-20 Exxonmobil Chemical Patents Inc. Multi-donor catalyst system for the polymerization of olefins
WO2008063409A1 (fr) * 2006-11-10 2008-05-29 Phillips Sumika Polypropylene Company Compositions à base de copolymère éthylène-propylène et procédés de fabrication et d'utilisation de celles-ci
WO2009152268A1 (fr) * 2008-06-11 2009-12-17 Lummus Novolen Technology Gmbh Catalyseurs ziegler-natta hautement actifs, leur procédé de production et leur utilisation
US8685879B2 (en) 2011-04-29 2014-04-01 Basf Corporation Emulsion process for improved large spherical polypropylene catalysts
WO2014102813A1 (fr) 2012-12-31 2014-07-03 Reliance Industries Limited Système de catalyseur hétérogène de ziegler-natta et procédé de polymérisation d'oléfines l'utilisant
CN105542038A (zh) * 2015-11-14 2016-05-04 新疆独山子天利高新技术股份有限公司 硅氧烷混合物及调控小本体聚丙烯工艺聚合速度的方法
WO2020035962A1 (fr) * 2018-08-13 2020-02-20 東邦チタニウム株式会社 Catalyseur pour la polymérisation d'oléfines, procédé pour la production d'un catalyseur pour la polymérisation d'oléfines, procédé pour la production d'un polymère d'oléfines et polymère d'oléfines

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WO1995021203A1 (fr) * 1994-02-04 1995-08-10 Exxon Chemical Patents Inc. Systeme catalyseur a deux donneurs d'electrons pour la polymerisation d'olefines
EP0676419A1 (fr) * 1994-04-06 1995-10-11 Fina Technology, Inc. Systèmes catalytiques pour la polymérisation des oléfines ayant une stéréoséléctivité améliorée et une large distribution du poids moléculaire

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EP0385765A2 (fr) * 1989-03-02 1990-09-05 Mitsui Petrochemical Industries, Ltd. Procédé de polymérisation d'oléfines et catalyseur pour polymérisation d'oléfines
EP0601496A1 (fr) * 1992-12-04 1994-06-15 Mitsui Petrochemical Industries, Ltd. Procédé de préparation de polymère d'oléfine
WO1995021203A1 (fr) * 1994-02-04 1995-08-10 Exxon Chemical Patents Inc. Systeme catalyseur a deux donneurs d'electrons pour la polymerisation d'olefines
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WO1998045338A1 (fr) * 1997-04-07 1998-10-15 Engelhard Corporation Modification de la repartition du poids moleculaire d'un polymere a l'aide de systemes de silanes melanges dans des catalyseurs de polymerisation a haute activite
WO1999029749A1 (fr) * 1997-12-10 1999-06-17 Exxon Chemical Patents Inc. Polymeres de propylene elastomeres
US6197910B1 (en) 1997-12-10 2001-03-06 Exxon Chemical Patents, Inc. Propylene polymers incorporating macromers
WO1999058585A1 (fr) * 1998-05-14 1999-11-18 Exxon Chemical Patents Inc. Matieres polymeres obtenues a partir de melanges d'electrodonneurs
US6087459A (en) * 1998-05-14 2000-07-11 Exxon Chemical Patents Inc. Polymeric materials formed using blends of electron donors
US6303715B1 (en) * 1998-12-04 2001-10-16 Samsung General Chemicals Co., Ltd. Method for polymerization and copolymerization of alpha-olefin
US6747103B1 (en) 1999-05-07 2004-06-08 Borealis Technology Oy High-stiffness propylene polymers and a process for the preparation thereof
WO2000068315A1 (fr) * 1999-05-07 2000-11-16 Borealis Technology Oy Polymeres de propylene de haute rigidite et leur obtention
US6566294B2 (en) 2000-12-21 2003-05-20 Exxonmobil Chemical Patents Inc. Multi-donor catalyst system for the polymerization of olefins
WO2008063409A1 (fr) * 2006-11-10 2008-05-29 Phillips Sumika Polypropylene Company Compositions à base de copolymère éthylène-propylène et procédés de fabrication et d'utilisation de celles-ci
WO2009152268A1 (fr) * 2008-06-11 2009-12-17 Lummus Novolen Technology Gmbh Catalyseurs ziegler-natta hautement actifs, leur procédé de production et leur utilisation
EA019316B1 (ru) * 2008-06-11 2014-02-28 Люммус Новолен Текнолоджи Гмбх Высокоактивные катализаторы циглера-натта, способ получения катализаторов и их использование
US10358513B2 (en) 2008-06-11 2019-07-23 Lummus Novolen Technology Gmbh High activity Ziegler-Natta catalysts, process for producing catalysts and use thereof
US8685879B2 (en) 2011-04-29 2014-04-01 Basf Corporation Emulsion process for improved large spherical polypropylene catalysts
WO2014102813A1 (fr) 2012-12-31 2014-07-03 Reliance Industries Limited Système de catalyseur hétérogène de ziegler-natta et procédé de polymérisation d'oléfines l'utilisant
US9884927B2 (en) 2012-12-31 2018-02-06 Reliance Industries Limited Heterogeneous ziegler-natta catalyst system and a process for olefin polymerization using the same
CN105542038A (zh) * 2015-11-14 2016-05-04 新疆独山子天利高新技术股份有限公司 硅氧烷混合物及调控小本体聚丙烯工艺聚合速度的方法
WO2020035962A1 (fr) * 2018-08-13 2020-02-20 東邦チタニウム株式会社 Catalyseur pour la polymérisation d'oléfines, procédé pour la production d'un catalyseur pour la polymérisation d'oléfines, procédé pour la production d'un polymère d'oléfines et polymère d'oléfines

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AU2702497A (en) 1997-12-05
FI962087A0 (fi) 1996-05-15
FI104080B1 (fi) 1999-11-15
FI104080B (fi) 1999-11-15

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