WO1993011164A1 - Procede de preparation d'un catalyseur de polymerisation d'olefine comprenant des particules de grosseur egale - Google Patents

Procede de preparation d'un catalyseur de polymerisation d'olefine comprenant des particules de grosseur egale Download PDF

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Publication number
WO1993011164A1
WO1993011164A1 PCT/FI1992/000322 FI9200322W WO9311164A1 WO 1993011164 A1 WO1993011164 A1 WO 1993011164A1 FI 9200322 W FI9200322 W FI 9200322W WO 9311164 A1 WO9311164 A1 WO 9311164A1
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Prior art keywords
reaction
ticl
hydrogen chloride
release
carrier particles
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Application number
PCT/FI1992/000322
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English (en)
Inventor
Thomas Garoff
Jukka Koskinen
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Neste Oy
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 Neste Oy filed Critical Neste Oy
Priority to JP5509851A priority Critical patent/JPH07501568A/ja
Priority to EP92924733A priority patent/EP0614466A1/fr
Publication of WO1993011164A1 publication Critical patent/WO1993011164A1/fr
Priority to NO941970A priority patent/NO941970L/no

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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

Definitions

  • the invention relates to a method for the preparation of a particulate procatalyst composition intended for the poly ⁇ merization of olefins by reacting the carrier particles consisting of a MgCl 2 -C 2 H 5 OH-complex with TiCl 4 .
  • the Ziegler- Natta-catalyst system which consists of a so-called pro ⁇ catalyst and a co-catalyst
  • the procatalyst is based on a compound of a transition metal belonging to any of the groups IVA-VIII (Hubbard) of the periodical table of the elements
  • the co-catalyst is based on an or- ganometallic compound of a metal belonging to any of the groups IA-III(A) (Hubbard) of the periodical table of the elements.
  • the catalyst system can also comprise a carrier, on which the transition metal compound is layered, and electron donor compounds improving and modifying the cata ⁇ lytic properties.
  • polyolefins In laboratory conditions polyolefins have been obtained using the procatalysts prepared in this manner. The acti- vity of the catalyst has been good. The particle size, particle size distribution and other properties of the polyolef ns have been satisfactory.
  • the product contains, namely, com ⁇ pared with a product prepared with a laboratory procata- lyst very great amounts of finely-divided substance or material, the diameter of which is less than 1mm.
  • the product contains, namely, com ⁇ pared with a product prepared with a laboratory procata- lyst very great amounts of finely-divided substance or material, the diameter of which is less than 1mm.
  • the aim of the invention is to provide a method for the preparation of a particulate procatalyst composition inte- ded for the olefin polymerization.
  • the procatalyst compo ⁇ sition should be created using a method giving a usable particle size distribution, from which the finely-divided material is essentially missing.
  • the particles must be suitable for use as to their shape, chemical com ⁇ position, activity and stereospecifity.
  • An aim is simul ⁇ taneously a polyolefin, the particle shape, isotacticity and crystallinity, melt viscosity and bulk density of which are suitable for use.
  • the carrier and thus also the procatalyst composition contains a great deal of finely-divided ma ⁇ terial.
  • the particle size distribution of the procatalyst composition then repeats in the polymerization in the particle size distribution, whereby even the polymer comp ⁇ rises a great deal of finely-divided material.
  • Figure 4 also shows that the release of the hydrogen chloride should be restricted so that not more than about 5% could be discharged in a minute, preferably about 2% at the most of the total amount of hydrogen chloride release stoichiometrically in the reaction. This is another way to express the prevention of a quantitatively heavy discharge of hydrogen chloride.
  • the release of the hydrogen chloride created in the reaction between the carrier particles and the titanium tetrachloride is disricited to a molar velocity that does not exceed the threefold, preferably double, value of the molar mean velocity of the release.
  • the invention is based on the idea that the reaction bet ⁇ ween the carrier particles and the TiCl 4 is maintained in such a way that a sudden discharge of the hydrogen chlori ⁇ de is prevented during the activation.
  • the attenuation of the sudden discharge i.e. the distribution of the hydrogen chloride release can be carried out by any suitable chemi ⁇ cal and/or physical means.
  • the prevention of sudden chemi ⁇ cal discharges is in the technical chemistry a general measure and the present invention is not related to cer- tain embodiments of this general measure only, but ex ⁇ pressly to the use of this measure to prevent the forma ⁇ tion of finely-divided material in a procatalyst.
  • the release of the hydrogen chloride can be distributed by selecting a correct adding order and adding velocity of the reagents.
  • the adding order preferably is such that the TiCl 4 is added -to the carrier particles and not vice ver ⁇ sa.
  • the carrier particles have preferably been suspended into an inert reaction medium.
  • TiCl 4 is controllably added to a liquid suspension of carrier particles consisting of MgCl 2 -C 2 H 5 OH-complex during 0.5 to 3 hours, preferably about 1.0 hour.
  • the medium of liquid suspension in regard to reagents inert hydrocarbons are usually used, the amount of which can be regulated so as to decrease the discharge tendency of the hydrogen chloride.
  • the controlled, slow adding of TiCl 4 reduces the discharge risk of the hydrogen chloride by producing hydrogen chlo ⁇ ride more slowly (see the reaction formula (1) ). Hydrogen chloride has then time to diffund out from the carrier particles before oversaturation of hydrogen chloride in the solution, leading to gas formation in the pores takes place. Moreover, at least some stages in the reactions between a MgCl 2 -C 2 H 5 0H-complex and TiCl 4 apparently are exothermic, whereby the slow adding of TiCl 4 enables a slow removal of heat from the carrier particles and thus prevents the carrier particles from heating locally above the discharge temperature of the hydrogen chloride.
  • TiCl 4 shall preferably be added in so low a temperature that no fast reaction nor a discharge of hydrogen chloride will take place. According to one embodiment TiCl 4 is added at the temperature -30 to -10°C and preferably at the temperature -25 to -15°C.
  • thermodynamic and/or physical balancing systems in the pores of the carrier particles and the TiCl 4 -solu- tion hydrogen chloride is released during a long time after the adding of the TiCl 4 .
  • the release of the hydrogen chloride created in the reac- tion can also be distributed by using a strong agitation during the reaction between the carrier particles and the TiCl 4 .
  • the strength of the agitation is dependent of many factors such as other means for distributing the release of the hydrogen chlorid, it can be said that the amount of agitation exceeds in this invention the conven ⁇ tional agitation values and causes an essential distribu ⁇ tion of the release of the hydrogen chloride.
  • the agitation has often been accused for the breaking of the carrier parti ⁇ cles, it is very surprising that the adding of agitation will help keeping the carrier particles undamaged.
  • the realization to add agitation to reach the aims of this invention must be seen against this background. Be it mentioned that in the reactor used in connection with this invention the starting speed of rotation of the mixer was raised when going over to the method according to this invention from the value 15rpm to the value 30rpm.
  • Another way to increase the material and heat transfer distributing the release of the hydrogen chloride is to alter the viscosity of the liquid reaction mixture. This can take place, as mentioned above, by selecting a suitab ⁇ le dispersion medium such as C 5 -C 8 -hydrocarbon, but it can also take place by adding to the reaction mixture extra liquid reducing the viscosity.
  • a further way to distribute the release of the hydrogen chloride created in the reaction is to use an overpressure during the reaction.
  • the overpressure has both a thermo ⁇ dynamic and a physical influence on the release of the hydrogen chloride.
  • the thermodynamic influence is based on the prevention of the evaporation of the hydrogen chlori ⁇ de, which reflects back to the distribution reaction op- tionally creating hydrogen chloride and slowing it down.
  • the physical influence is based on the fact that a higher pressure raises the gasifying temperature of the hydrogen chloride and prevents the gasification at a certain tempe ⁇ rature.
  • overpressure is used during the reaction which is in the order of 1 to 100 bars, preferably about 1 to 50 bars and most preferably 1 to 5 bars.
  • the release of the hydrogen chloride created in the reac ⁇ tion can also be distributed by leading to the reaction mixture or above it nitrogen gas.
  • the use of an inert gas flow influences principally physically so that the hydro ⁇ gen chloride content reduced by the environment accelera ⁇ tes the removal of the hydrogen chloride created in the reaction from the pores, whereby the saturation point of the hydrogen chloride corresponding to the gasification point will never be reached. It is, however, worth while using the nitrogen or other inert gas carefully for ther- modynamically its influence is the opposite i.e. by remo ⁇ ving rapidly hydrogen chloride from the pores of the car ⁇ rier particles the possible distribution reaction creating hydrogen chloride will be accelerated and will produce abundantly of heat causing discharging of hydrogen chlori ⁇ de.
  • the releasing temperature of the hydrogen chloride can be raised and its release dist ⁇ ricited according to the aim of the invention.
  • the pro- ducts of the reaction between the complex and TiCl 4 such as ethoxytitanium chloride and hydrogen chloride, can also be removed by changing during the reaction the excess amount of TiCl 4 .
  • the composition of the MgCl 2 -C 2 H 5 0H-complex has a decisive effect on how rapidly the hydrogen chloride created in the reaction between the complex and TiCl 4 is released.
  • the preliminary results and the reaction formula (1) show that the discharge velocity increases when the C 2 H 5 OH-content increases.
  • the molar ratio between the MgCl 2 and C 2 H 5 0H of the MgCl 2 -C 2 H 5 OH-complex used as the material of the car ⁇ rier particles is between 2.5 to 3.5 and preferably bet- ween about 2.7 to 3.3.
  • the C 2 H 5 OH-content must be below about 60% of the weight of the procatalyst carrier material.
  • carrier particles the size of which is below about 150 ⁇ m.
  • the success of the invention is also influenced by the water content, mechanical strength, particle morphology and particle size distribution of the carrier particles. Therefore it has been noticed that such carrier particles consisting of MgCl 2 -C 2 H 5 0H-complex are particularly suit ⁇ able for the method according to the invention that have been prepared by a spray-crystallization method.
  • Par ⁇ ticles prepared by this kind of a method are mechanically much stronger than e.g. the particles prepared by spray- evaporation and are thus particularly suitable for the method according to the invention, in which the discharge tendency of the hydrogen chloride sets high mechanical requirements for the particles. Simultaneously, particles are created giving a pore volume in the procatalyst, which is suitable for the method according to the invention.
  • the release of the hydrogen chloride can also be accelera ⁇ ted by the presence of an internal donor in the reaction mixture of carrier particles and TiCl 4 . This is due to the fact that the reactions of the donor taking place in con ⁇ nection with the adding usually are exothermic. If the donor is added at a stage or in a temperature range where a discharge of the hydrogen chloride is possible, it may, in fact, lead to an uncontrolled release of the hydrogen chloride. This can happen e.g. when the reaction mixture after the adding of the TiCl 4 is heated to a temperature of about +20°C and and the donor is added to the reaction mixture.
  • the above-mentioned measures for the distribution of the release of the hydrogen chloride created in the reaction can, according to the invention, be used alone or then combined in any possible way. According to one embodiment of the invention the measures are used in the manner shown in figure 5.
  • A is a slow increase of temperature after the first adding of TiCl 4 .
  • B is the delay of the reaction after the adding of the donor
  • C is a more rapid increase of temperature for the comple ⁇ tion of the first reaction between the carrier and the TiCl 4 ,
  • D is the completion of the first reaction between the carrier and the TiCl 4
  • E is the second treatment of the carrier with TiCl 4
  • F is the washing
  • G is the drying.
  • the invention it is advantageous to carry out one or several of the above-mentioned measures for the distribution of the release of the hydrogen chloride crea ⁇ ted in the reaction in the points I, II, and III marked in the figure.
  • the measures can be optimized, taking into consideration the whole pro ⁇ cess, for each reactor and the desired product.
  • the TiCl 4 used in the synthesis was liquid and non-aque ⁇ ous.
  • the MgCl 2 -C 2 H 5 OH-complex carrier was prepared from complex melt, to the composition of which MgCl 2 *3.5C 2 H 5 OH was ad ⁇ justed. Melt was sprayed at the temperature of about 120 to 130°C through a nozzle structure distributing it, the temperature of the reception zone of which was about 30 to 50°C. From the reception zone the melt drops were conduct ⁇ ed through a slightly colder zone for the final hardening of the particles. Moreover, the the particles were sieved so as to have the particle size below about 150 ⁇ m. The composition of the final particles was about MgCl 2 • 3C 2 H 5 OH.
  • the morphology of the carrier particles was spectacular.
  • the particle size distribution was between 1.50 to 3.4 (span) and the particles did not contain finely-divided material.
  • the microscope pictures of the carrier particles have been presented in connection with the microscope pictures of the procatalysts and the polymers in the handling of the results.
  • the amount of the carrier was 44kg and the ratio TiCl 4 (mole)/carrier C 2 H 5 0H (mole) was 10.
  • the ratio LIAV (kg)/carrier (kg) was 4.5 and the ratio TiCl 4 (mo ⁇ le)/Mg (mole) was 30.
  • the agitation velocity was 15rpm.
  • the second treatment with TiCl 4 was carried out by adding the reagent into a purified solid intermediary product.
  • the temperature still was 110°C, the agitation velocity 15rpm and the reaction time 2 hours.
  • the ratio TiCl 4 (mo- le)/Mg (mole) being also now 30.
  • the product was washed four times with a hydrogen carbon solvent (LIAV) so that the ratio LIAV (kg)/carrier (kg) was 9. During the washing the agitation velocity was about the same as above. After this the product was dried with a N 2 -gas flow at the temperature 70°C without agita ⁇ tion.
  • LIAV hydrogen carbon solvent
  • the other treatment with TiCl 4 was carried out by adding the reagent into a purified solid intermediary product.
  • the temperature still was 110°C, the agitation velocity 15rpm and the reaction time about two hours.
  • the ratio TiCl 4 (mole)/Mg (mole) also now 30.
  • the product was washed four times with a hydrogen carbon solvent (LIAV) so that the ratio LIAV (kg)/carrier (kg) was 9. During the washing the agitation velocity was about the same as above. After this the product was dried with a N 2 -gas flow at the temperature 70°C without agita ⁇ tion.
  • LIAV hydrogen carbon solvent
  • the ratio LIAV (kg)/carrier (kg) was 9.0 and the ratio TiCl 4 (mo- le)/Mg (mole) was 30.
  • the temperature was slow ⁇ ly raised with the velocity of 0.22°C/min. to the tempera- ture +20°C.
  • the agitation had been reduced from the original value of 30rpm to the usual value of 15rpm in order to decrease the mechanical strain caused by the agitation.
  • the temperature was raised with the mean velocity of about l°C/min. to the value 110°C, whereby the overpressu ⁇ re and the N 2 -flow were removed.
  • the agitation velocity still was 15rpm.
  • the temperature and the agitation were maintained in about 1 hour, after which the activation residues with the TiCl 4 excess amounts were removed by rinsing through the sieve bottom of the reactor.
  • the other treatment with TiCl 4 was carried out by adding the reagent into a purified solid intermediary product.
  • the ratio TiCl 4 (mole)/Mg (mole) was also now 30.
  • LIAV hydro ⁇ gen carbon solvent
  • procatalysts of the comparative examples and the embodiments prepared in laboratory or pilot-scale were tested under standard polymerization conditions.
  • a 2-liter bench reactor was used. 20 to 30mg of procatalyst was used in each test polymerization run. To this amount 620 ⁇ ml of triethyl aluminium co-catalyst and 200 ⁇ ml of 25% heptane solution of an internal cyklohexylmethyl methoxysilane donor were added.
  • intermediary medium 900ml of hep ⁇ tane was used. The polymerizations were carried out at the temperature of +70°C and in the propene monomer pressure of 10 bars.
  • the partial pressure of hydrogen during the polymerization was 0.2 bars, llmmol H 2 was added to adjust the molecular weight.
  • the polymerization was continued for three hours. Thereafter the activity of the procatalyst was measured on the basis of the polymerization yield.
  • the solvent portion of the polymer was measured by dissolving a certain polymer amount into the solvent and measuring the evaporation residue of the pure solution.
  • the bulk density and the particle size distribution of all the polymer samples were determined. In connection with the particle size distribution measurements the total amount of the finely-divided material was estimated.
  • the diameter of which was smal ⁇ ler than 1mm was defined as finely-divided material.
  • the isotacticity was measured by means of heptane elution and the isotacticity index was measured by using the results of the evaporation residue measurements.
  • the melt index was measured at the temperature of 230°C by using a 2.16kg weight.
  • the titanium content, the donor content, the particle size distribution, the catalyst yield, the catalyst activity, the polymer-isotacticity, the polymer melt index and the polymer-bulk density of the procatalysts of the embodi ⁇ ments prepared in laboratory and in pilot-scale were nor ⁇ mal for catalysts of corresponding type.
  • the titanium content varied between 2.4 and 3.6% by weight in laboratory catalysts and between 2.4 and 4.5% by weight in pilot-procatalysts.
  • the donor content varied between 15.9 and 19.2% by weight in laboratory-procatalysts and between 9.7 and 15.4% by weight in pilot-procatalysts (in embodiment 1 the pilot-scale donor feed was unsuccessful).
  • the procatalyst yield was satisfactory varying between 74 and 99% in pilot-run and between 82 and 92% in laboratory. This shows that finely-divided material has not e.g. been rinsed off to any in any greater extent in the pilot-run compared to the laboratory-run.
  • the activity of the pilot-procatalysts was at its best 15.8kgPP/g cat, which is a good value and of the same order as in the procatalysts prepared in laboratories.
  • the polymer melt indices varied in laboratory procatalysts between 4.3 and 9.6 and in pilot-procatalysts between 5.0 and 7.4 (the MI of the fourth run was exceptionally 19.4) corresponding the melt index of a normal polypropene.
  • pilot-scale When going over to pilot-scale a remarkable improvement can be achieved with the measures according to the inven ⁇ tion compared with the procatalysts according to the com ⁇ parative examples.
  • the portion of the fine ⁇ ly-divided material of the polymer can be reduced to at least about the fourth and at the utmost to even less than a tenth of the results of the comparative tests.
  • the pilot comparative example 1 where the adding order of the reagents was different (see the directions above) as much as 70% by weight was obtained as the portion of the fine ⁇ ly-divided substance, which value is much higher than those of the pilot embodiments.
  • Fig. 1 Formation of the finely-divided substance in PP- polymer when comparing pilot-catalyst to laboratory cata ⁇ lyst,
  • Fig. 2 Correlation between the amount of the finely-di ⁇ vided fraction of the polymer and the maximum releasing velocity (ml/min) of the HCl created in the catalyst syn ⁇ thesis,
  • Fig. 3 Release of HCl when heating a system containing a MgCl 2 -C 2 H 5 0H-complex, HCl and TiCl 4 ,
  • Fig. 4 The rate of HCl gas release as a function of the temperature, when the system contains a MgCl 2 -C 2 H 5 0H-comp- lex, TiCl 4 , and HCl,
  • Fig. 5 A preferred use of the measures according to the invention in a procatalyst process; (A) slow increase of temperature after a TiCl 4 -addition, (B) delay of the reac- tion during the adding of the donor and after it, (C) increase of temperature for the completion of the reacti ⁇ on, (D) first titanization, (E) second titanization, (F) washing, (G) drying,
  • Fig. 6 Releasing velocity of the hydrogen chloride (lower curve) as a function of the temperature (upper curve) and time
  • Fig. 7 Total amount of finely-divided substance (d ⁇ l mm) in polymers prepared with laboratory- and pilot-catalysts of the comparative examples (old) and the embodiments _, Fig. 8: carrier of embodiment 1, length unit lOO ⁇ m,
  • Fig. 9 laboratory procatalyst of embodiment 1 (25 ⁇ m),
  • Fig. 10 pilot procatalyst of embodiment 1 (25 ⁇ m),
  • Fig. 11 polymer obtained with laboratory procatalyst of embodiment 1,
  • Fig. 12 polymer obtained with pilot procatalyst of embo ⁇ diment 1.

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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)
  • Polymerization Catalysts (AREA)

Abstract

Selon cette invention, on prépare une composition de procatalyseur particulaire destinée à la polymérisation d'oléfines en faisant réagir les particules porteuses composées d'un complexe MgCl2-C2H5OH avec du TiCl4. Lorsque ce procédé est appliqué à une échelle pilote, il a été remarqué que la composition de procatalyseur obtenue produisait un polymère oléfinique, dont la partie composée d'un matériau finement divisé était trop importante et pouvait en provoquer la détérioration. Ceci était dû au fait que les particules de la composition de procatalyseur s'étaient décomposées en un matériau finement divisé au cours de la synthèse, la structure de ce matériau étant alors reproduite, au cours de la polymérisation, dans la structure du polymère par le phénomène dit de répétition. Selon l'invention, il a été remarqué, de façon imprévue, que le fractionnement des particules porteuses n'était pas le résultat d'une contrainte mécanique, par exemple, mais était dû au fait que, lorsque les particules porteuses réagissent avec le TiCl4, une libération importante de chlorure d'hydrogène est initialement provoquée par la réaction qui fractionne les particules porteuses. Celles-ci peuvent, selon l'invention, demeurer intactes au cours de la réaction dans la mesure où l'on répartit la libération du chlorure d'hydrogène, dans la réaction ou à partir de la réaction, à une vitesse molaire ne dépassant pas cinq fois la valeur de la vitesse molaire moyenne de la libération. L'on effectue ceci, entre autres, en ajoutant les réactifs avec une lenteur inhabituelle, à des températures et des vitesses de chauffage plus basses, en intensifiant l'agitation, en utilisant une surpression et/ou en amenant un gaz inerte diluant dans le mélange de réaction.
PCT/FI1992/000322 1991-11-29 1992-11-27 Procede de preparation d'un catalyseur de polymerisation d'olefine comprenant des particules de grosseur egale WO1993011164A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
JP5509851A JPH07501568A (ja) 1991-11-29 1992-11-27 均一サイズの粒子からなるオレフィン重合用触媒の製造方法
EP92924733A EP0614466A1 (fr) 1991-11-29 1992-11-27 Procede de preparation d'un catalyseur de polymerisation d'olefine comprenant des particules de grosseur egale
NO941970A NO941970L (no) 1991-11-29 1994-05-26 Fremgangsmåte for fremstilling av en olefinpolymerisasjonskatalysator som består av partikler med lik störrelse

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FI915630A FI92327C (fi) 1991-11-29 1991-11-29 Menetelmä tasakokoisia hiukkasia omaavan olefiinipolymerointikatalyytin valmistamiseksi
FI915630 1991-11-29

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WO1993011164A1 true WO1993011164A1 (fr) 1993-06-10

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EP (1) EP0614466A1 (fr)
JP (1) JPH07501568A (fr)
FI (1) FI92327C (fr)
NO (1) NO941970L (fr)
WO (1) WO1993011164A1 (fr)

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1998044009A1 (fr) * 1997-03-29 1998-10-08 Montell Technology Company B.V. Produits d'addition dichlorure de magnesium/alcool, leur procede de preparation et constituants pour catalyseurs obtenus a partir de ceux-ci
US6323152B1 (en) 1998-03-30 2001-11-27 Basell Technology Company Bv Magnesium dichloride-alcohol adducts process for their preparation and catalyst components obtained therefrom
US6407028B1 (en) 1997-03-29 2002-06-18 Basell Technology Company Bv Magnesium dichloride-alcohol adducts, process for their preparation and catalyst components obtained therefrom
US6962889B2 (en) 2004-01-28 2005-11-08 Engelhard Corporation Spherical catalyst for olefin polymerization
US7135531B2 (en) 2004-01-28 2006-11-14 Basf Catalysts Llc Spherical catalyst for olefin polymerization
US7638585B2 (en) 2008-05-13 2009-12-29 Basf Catalysts, Llc Catalyst flow
US8003559B2 (en) 2008-05-13 2011-08-23 Basf Corporation Internal donor for olefin polymerization catalysts
US8003558B2 (en) 2008-07-29 2011-08-23 Basf Corporation Internal donor for olefin polymerization catalysts

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1987007620A1 (fr) * 1986-06-09 1987-12-17 Neste Oy Procede de fabrication de constituants catalytiques pour la polymerisation d'olefines
EP0424049A2 (fr) * 1989-10-20 1991-04-24 Borealis A/S Procédé et équipement pour la préparation d'un support de catalyseur de polymérisation

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1987007620A1 (fr) * 1986-06-09 1987-12-17 Neste Oy Procede de fabrication de constituants catalytiques pour la polymerisation d'olefines
EP0424049A2 (fr) * 1989-10-20 1991-04-24 Borealis A/S Procédé et équipement pour la préparation d'un support de catalyseur de polymérisation

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1998044009A1 (fr) * 1997-03-29 1998-10-08 Montell Technology Company B.V. Produits d'addition dichlorure de magnesium/alcool, leur procede de preparation et constituants pour catalyseurs obtenus a partir de ceux-ci
US6127304A (en) * 1997-03-29 2000-10-03 Montell Technology Company Bv Magnesium dischloride-alcohol adducts and catalyst components obtained therefrom
US6407028B1 (en) 1997-03-29 2002-06-18 Basell Technology Company Bv Magnesium dichloride-alcohol adducts, process for their preparation and catalyst components obtained therefrom
US6437061B1 (en) 1997-03-29 2002-08-20 Basell Technology Company Bv Magnesium dichloride-alcohol adducts, process for their preparation and catalyst components obtained therefrom
US6686307B2 (en) 1997-03-29 2004-02-03 Basell Technology Company B.V. Magnesium dichloride-alcohol adducts
US6323152B1 (en) 1998-03-30 2001-11-27 Basell Technology Company Bv Magnesium dichloride-alcohol adducts process for their preparation and catalyst components obtained therefrom
US6962889B2 (en) 2004-01-28 2005-11-08 Engelhard Corporation Spherical catalyst for olefin polymerization
US7135531B2 (en) 2004-01-28 2006-11-14 Basf Catalysts Llc Spherical catalyst for olefin polymerization
US7638585B2 (en) 2008-05-13 2009-12-29 Basf Catalysts, Llc Catalyst flow
US8003559B2 (en) 2008-05-13 2011-08-23 Basf Corporation Internal donor for olefin polymerization catalysts
US8003558B2 (en) 2008-07-29 2011-08-23 Basf Corporation Internal donor for olefin polymerization catalysts

Also Published As

Publication number Publication date
FI915630A0 (fi) 1991-11-29
NO941970D0 (no) 1994-05-26
EP0614466A1 (fr) 1994-09-14
JPH07501568A (ja) 1995-02-16
FI92327B (fi) 1994-07-15
NO941970L (no) 1994-05-26
FI915630A (fi) 1993-05-30
FI92327C (fi) 1994-10-25

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