WO2003014167A1 - Procede de polymerisation utilisant un organosilane specifique en tant que donneur externe - Google Patents

Procede de polymerisation utilisant un organosilane specifique en tant que donneur externe Download PDF

Info

Publication number
WO2003014167A1
WO2003014167A1 PCT/NL2002/000531 NL0200531W WO03014167A1 WO 2003014167 A1 WO2003014167 A1 WO 2003014167A1 NL 0200531 W NL0200531 W NL 0200531W WO 03014167 A1 WO03014167 A1 WO 03014167A1
Authority
WO
WIPO (PCT)
Prior art keywords
process according
group
atom
anyone
hetero
Prior art date
Application number
PCT/NL2002/000531
Other languages
English (en)
Inventor
Geerling Willem Wijsman
Lieven K. Van Looveren
Henricus Johannes Arts
Original Assignee
Dsm N.V.
Bp Corporation North America Inc.
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 Dsm N.V., Bp Corporation North America Inc. filed Critical Dsm N.V.
Publication of WO2003014167A1 publication Critical patent/WO2003014167A1/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

Definitions

  • the present invention relates to a process for the polymerization of one or more ⁇ -olefins in the presence of a catalyst system comprising a transition metal compound, an organo-metal compound as co-catalyst, and, as an external electron donor, at least one organosilane compound in which the silicon atom has at least one hetero atom containing substituent.
  • a catalyst system comprising a transition metal compound, an organo-metal compound as co-catalyst, and, as an external electron donor, at least one organosilane compound in which the silicon atom has at least one hetero atom containing substituent.
  • the present invention offers an improved process for the polymerization of one ore more ⁇ -olefins in which the above disadvantage is reduced.
  • R ⁇ R 2 and R 3 are hydrocarbon-based substituents
  • the elements of the catalyst system will be described in more detail below.
  • Transition metal compound The transition metal in this compound has been chosen from groups 4-6 of the Periodic Table of the Elements (Newest IUPAC notation); more preferably, the transition metal has been chosen from group 4; the greatest preference is given to titanium (Ti) as transition metal.
  • Titanium containing compounds useful in the present invention as catalyst generally are supported on hydrocarbon-insoluble, magnesium or silicon containing supports, generally in combination with an internal electron donor compound.
  • Such supported titanium- containing ⁇ -olefin polymerization catalyst compound is formed typically by reacting a titanium (IV) compound, an organic internal electron donor compound and a magnesium or silicon containing support.
  • such supported titanium-containing reaction product may be further treated or modified with an additional electron donor or Lewis acid species.
  • Suitable magnesium-containing supports include magnesium halides; a reaction product of a magnesium halide such as magnesium chloride or magnesium bromide with an organic compound, such as an alcohol or an organic acid ester, or with an organometallic compound of metals of groups 1-3; magnesium alcoholates; or magnesium alkyls.
  • One possible magnesium-containing support is based on at least one magnesium carboxylate prepared in a reaction between a hydrocarbyl magnesium (halide) compound with carbon dioxide.
  • transition metal compound is described in US patent 4,581,342.
  • the compound described therein is prepared by complexing a magnesium alkyl composition with a specific class of hindered aromatic esters such as ethyl 2,6-dimethylbenzoate followed by reaction with a compatible precipitation agent such as silicon tetrachloride and a suitable titanium(IV) compound in combination with an organic internal electron donor compound in a suitable diluent.
  • a compatible precipitation agent such as silicon tetrachloride
  • titanium(IV) compound in combination with an organic internal electron donor compound in a suitable diluent.
  • the possible solid catalyst components listed above only are illustrative of many possible solid, magnesium-containing, titanium halide-based, hydrocarbon-insoluble catalyst compounds useful in the process of the present invention and known to the art. This invention is not limited to a specific supported catalyst compound.
  • Titanium (IV) compounds useful in preparing the solid, titanium- containing catalyst compound of invention preferably are titanium halides and haloalcoholates having 1 to about 20 carbon atoms per alcoholate group. Mixtures of titanium compounds can be employed if desired. Preferred titanium compounds are the halides and haloalcoholates having 1 to about 8 carbon atoms per alcoholate group.
  • Examples of such compounds include TiCI 4 , TiBr 4 , Ti(OCH 3 )CI 3 , Ti(OC 2 H 5 )CI 3 , Ti(OC 4 H 9 )CI 3 , Ti(OC 6 H 5 )CI 3 , Ti(OC ⁇ H 13 )Br 3 , Ti(OC 8 H 17 )CI 3 , Ti(OCH 3 ) 2 Br 2 , Ti(OC 2 H 5 ) 2 CI 2 , Ti(OC 6 H 13 ) 2 CI 2 , Ti(OC 8 H 17 ) 2 Br 2 , Ti(OCH 3 ) 3 Br, Ti(OC 2 H 5 ) 3 CI, Ti(OC 4 H 9 ) 3 CI, Ti(OC 6 H 13 ) 3 Br and Ti(OC 8 H 17 ) 3 CI.
  • Titanium tetrahalides particularly titanium tetrachloride (TiCI 4 ) are most preferred.
  • Internal electron donors useful in the preparation of a stereospecific supported titanium-containing catalyst compound can be organic compounds containing one or more atoms of oxygen, nitrogen, sulphur and phosphorus. Such compounds include organic acids, organic acid esters, alcohols, ethers, aldehydes, ketones, amines, amine oxides, amides, thiols and various phosphorous acid esters and amides, and the like. Mixtures of internal electron donors can be used if desired. Specific examples of useful oxygen- containing internal electron donor compounds include organic acids and esters. Useful organic acids contain from 1 to about 20 carbon atoms and 1 to about 4 carboxyl groups.
  • Preferred internal electron donor compounds include esters of aromatic acids.
  • Preferred internal electron donors are alkyl esters or aromatic mono- and dicarboxylic acids, and halogen, hydroxyl-, oxo-, alkyl-, alkoxy-, aryl-, and aryloxy-substituted aromatic mono- and dicarboxylic acids.
  • alkyl esters of benzoic and halobenzoic acids wherein the alkyl group contains 1 to about 6 carbon atoms such as methyl benzoate, methyl bromobenzoate, ethyl benzoate, ethyl chlorobenzoate, ethyl bromobenzoate, butyl benzoate, isobutyl benzoate, hexyl benzoate, and cyclohexyl benzoate, are preferred.
  • Other preferable esters include ethyl p-anisate and methyl-p-toluate.
  • An especially preferred aromatic ester is a dialkylphthalate ester in which the alkyl group contains from about two to about ten carbon atoms. Examples of preferred phthalate esters are diisobutylphthalate, ethylbutylphthalate, diethylphthalate, and di-n-butylphthalate.
  • the internal electron donor component is used in an amount ranging from about 0.001 to about 1.0 mol per gram atom of the transition metal and preferably from about 0.005 to about 0.8 mol per gram atom. Best results are achieved when this ratio ranges from about 0.01 to about 0.6 mol per gram atom of the transition metal.
  • the solid reaction product prepared as described herein may be contacted with at least one Lewis acid prior to polymerization.
  • Lewis acids are generally liquids at treatment temperatures and have a Lewis acidity high enough to remove impurities such as un-reacted starting materials and poorly affixed compounds from the surface of the above- described solid reaction product.
  • Preferred Lewis acids include halides of group 4, 5, 13-15 metals which are in the liquid state at temperatures up to about 170°C. Specific examples of such materials include BCI 3 , AIBr 3 , TiCI 4 , TiBr , SiCI , GeCI 4 , SnCI 4 , PCI 3 and SbCI 5 .
  • Preferable Lewis acids are TiCI and SiCI 4 . Mixtures of Lewis acids can be employed if desired.
  • Such Lewis acid may be used in a compatible diluent.
  • the above-described solid reaction product may be washed with an inert liquid hydrocarbon or halogenated hydrocarbon before the contact with the Lewis acid. If such a wash is conducted it is preferred to substantially remove the inert liquid prior to contacting the washed solid with the Lewis acid.
  • the catalyst preferably is prepared in the substantial absence of such materials. Catalyst poisons can be excluded by carrying out the preparation under an atmosphere of an inert gas such as nitrogen or argon, or an atmosphere of an ⁇ -olefin, or any other method known in the art.
  • purification of any diluent to be employed also aids in removing poisons from the preparative system.
  • the catalyst preferably contains from about 1 to about 6 wt.% transition metal, from about 10 to about 25 wt.% magnesium, and from about 45 to about 65 wt.% halogen.
  • Preferred catalysts for use in this invention contain from about 1.0 to about 5 wt.% transition metal, from about 15 to about 21 wt.% magnesium, and from about 55 to about 65 wt.% chlorine. Most preferred is titanium as transition metal.
  • the transition metal compound used in this invention may be prepolymehzed with an ⁇ -olefin before use as a polymerization catalyst.
  • the transition metal compound and an organometal compound as a cocatalyst such as triethylaluminum
  • an ⁇ -olefin such as propylene
  • an external electron donor such as a silane and preferably an organosilane as used in the process of the present invention
  • an inert hydrocarbon such as hexane
  • the polymer/catalyst weight ratio of the resulting prepolymerized component is about 0.1 :1 to about 20:1.
  • Prepolymerization forms a coat of polymer around the catalyst particles which in many instances improves the particle morphology, activity, stereospecificity, and attrition resistance.
  • a particularly useful prepolymerization procedure is described in U.S. Patent 4,579,836.
  • an organo-metal hydride and/or a metal alkyl compound is used as a co- catalyst.
  • the metal in this compound is chosen from groups 1-3 and 12-13 of the Periodic Table of Elements. Preferred is a metal alkyl and, more preferably, an alkyl aluminum compound.
  • Preferred metal alkyls are compounds of the formula MR m wherein M is chosen from groups 2, 12 or 13, each R is independently an alkyl radical of 1 to about 20 carbon atoms, and m corresponds to the valence of M.
  • useful metals, M include magnesium, calcium, zinc, cadmium, aluminum, and gallium.
  • suitable alkyl radicals, R include methyl, ethyl, butyl, hexyl, decyl, tetradecyl, and eicosyl. From the standpoint of polymerization performance, preferred metal alkyls are those of magnesium, zinc, and aluminum wherein the alkyl radicals contain 1 to about 12 carbon atoms.
  • Such compounds include Mg(CH 3 ) 2 , Mg(C 2 H 5 ) 2 , Mg(C 2 H 5 )(C 4 H 9 ), Mg(C 4 H 9 ) 2 , Mg(C 6 H 13 ) 2 , Mg(C 12 H 25 ) 2 , Zn(CH 3 ) 2 , Zn(C 2 H 5 ) 2> Zn(C 4 H 9 ) 2 , Zn(C 4 H ⁇ )(C 8 H 17 ), Zn(C 6 H 13 ) 2 , Zn(C 12 H 25 ) 2 , AI(CH 3 ) 3 , AI(C 2 H 5 ) 3 , AI(C 3 H 7 ) 3> AI(C 4 H 9 ) 3 , AI(C 6 H 13 ) 3 , and AI(C ⁇ 2 H 25 ) 3 .
  • a magnesium, zinc, or aluminum alkyl containing 1 to about 6 carbon atoms per alkyl radical is used.
  • Alkyl aluminum compounds are most preferred. Best results are achieved through the use of trialkylaluminums containing 1 to about 6 carbon atoms per alkyl radical, and particularly thethylaluminum and triisobutylaluminum or a combination thereof.
  • metal alkyls having one or more halogen or hydride groups can be employed, such as ethylaluminum dichloride, diethylaluminum chloride, ethylaluminum sesquichlohde or diisobutylaluminum hydride.
  • useful organo-metal compound to transition metal atomic ratios in such catalyst system are about 10 to about 500 and preferably about 30 to about 300.
  • the organosilane compound is present in the catalyst system as an external electron donor, meaning that this compound is added to the reaction system, and not used in the preparation of the transition metal compound (vide a) supra).
  • the organosilane compound used in the process of the present invention has the formula:
  • R ⁇ R 2 and R 3 are hydrocarbon-based substituents
  • the respective groups in this organosilane compound will be dealt with below:
  • Q ⁇ is a hetero-atom, selected from the group of nitrogen, phosphorus, oxygen and sulphur, having an electro-negative character. Because of its good electron-donating capacity, there is a preference for Q being oxygen.
  • R is a possibly present substituent to Q 1t depending on the valency state of
  • R 2 and R 3 are hydrocarbon-based substituents, meaning that R 2 and R 3 can be a substituent containing only carbon and hydrogen atoms, but also that R 2 and R 3 can be a substituent that, next to carbon and hydrogen atoms also contains one or more hetero-atoms, also selected from the group of nitrogen, phosphorus, oxygen and sulphur, either in the backbone or in pendant groups.
  • R 2 and /or R 3 are an alkoxy group; in more preference a methoxy or ethoxy group.
  • M. Harkonen et.al. disclose in Macromol. Chem. 192, 2857-63 (1991) that 1,1-dimethoxy-3,4-benzo-1 ,2 siloxacyclohexane has been tested on its performance as external electron donor and found not suitable. Therefore, this specific organosilane compound has been disclaimed from use in the present invention. According to the present invention it has been found that when R 2 and R 3 are not. simultaneously a methoxy group, such organosilane compound can successfully be used as an external donor.
  • R 2 is a cycloalkyl (preferably a cyclohexyl) group and R 3 is an alkoxy group (preferably a methoxy or ethoxy group; most preferred an ethoxygroup).
  • R 2 and R 3 form a second ring structure, preferably a ring structure in which a second hetero-atom Q 2 , also selected from the group of nitrogen, phosphorus, oxygen and sulphur, is present.
  • R 2 and R 3 form an analogous structure as the group, and as a result, everything noted herein above with respect to the R 1 t Qi and R» groups holds mutatis mutandis also for the second ring structure.
  • Ri is also a hydrocarbon-based substituent (the term being as defined above). It forms, together with the Q ⁇ (R 4 ) s group a ring attached to the silicon atom.
  • R ⁇ has the following structure:
  • Re. R7, Re. Rg, Rio. Rn. R12 and R 13 are hydrogen or a hydrocarbon-based substituent.
  • R 2 is a cycloalkyl (preferably cyclohexyl) group
  • R 3 is an alkoxy (preferably ethoxy) group
  • R 2 is an alkyl
  • R 3 is an alkoxy
  • R is a (CReR ) p -group
  • an organosilane compound selected from the group comprising: * 1 -cyclohexyl-1 -ethoxy-5,6-benzo-1 ,2-siloxacyclohexane * 1-methoxy-1-methyl-3,4-benzo-1 ,2-siloxacycloheptane
  • the external organosilane electron donor is usually added to the other catalyst system components or added separately to the polymerization reactor, preferably in a molar ratio relative to the transition metal of from 0.1 :1 to 250:1.
  • the above-described catalyst system is useful in the polymerization of ⁇ -olefins such as ethylene and propylene, and are most useful in stereospecific polymerization of one of more ⁇ -olefins containing 3 or more carbon atoms such as propylene, 1-butene, 1-pentene-1, 4-methyl-1-pentene and 1-hexene, as well as mixtures thereof and mixtures thereof with ethylene.
  • the catalyst system is particularly effective in the stereospecific polymerization of propylene or mixtures thereof with up to about 15 mol % ethylene or a higher ⁇ -olefin. Such polymerization is known to a person skilled in the art.
  • highly crystalline poly- ⁇ -olefins are prepared by contacting at least one ⁇ -olefin with the above- described catalyst system under polymerizing conditions.
  • Such conditions include polymerization temperature and time, monomer pressure, avoidance of contamination of catalyst, choice of polymerization medium in slurry processes, the use of ingredients (like hydrogen) to control polymer molecular weights, and other conditions well known to persons of skill in the art. Slurry-, bulk-, and gas- phase polymerization processes are contemplated herein.
  • catalysts are used in amounts ranging from about 0.2 to 0.02 milligrams of catalyst to gram of polymer produced.
  • polymerization should be carried out at temperatures sufficiently high to ensure reasonable polymerization rates and avoid unduly long reactor residence times, but not so high as to result in the production of unreasonably high levels of stereorandom products. Generally, temperatures range from about 40°C to about 150°C with about 40°C to about 95°C being preferred from the standpoint of attaining good catalyst performance and high production rates. More preferably, the polymerization process according to this invention is carried out at temperatures ranging from about 50°C to about 80°C.
  • ⁇ -Olefin polymerization according to this invention is carried out at monomer pressures of about atmospheric or above. Generally, monomer pressures range from about 0,1 to 5 MPa although in gas phase polymerizations, monomer pressures should not be below the vapor pressure at the polymerization temperature of the ⁇ -olefin(s) to be polymerized.
  • the polymerization time will generally range from about V_ to several hours in batch processes with corresponding average residence times in continuous processes. Polymerization times ranging from about 1 to about 4 hours are typical in autoclave-type reactions. In slurry processes, the polymerization time can be regulated as desired. Polymerization times ranging from about V_ to several hours are generally sufficient in continuous slurry processes.
  • Diluents suitable for use in slurry polymerization processes include alkanes and cycloalkanes (such as pentane, hexane, heptane, n-octane, isooctane, cyclohexane, and methylcyclohexane); alkylaromatics (such as toluene, xylene, ethylbenzene; isopropylbenzene, ethyl toluene, n-propyl- benzene, diethylbenzenes, and mono- and dialkylnaphthalenes); halogenated and hydrogenated aromatics (such as chlorobenzene, chloronaphthalene, orthodichlorobenzene, tetrahydronaphthalene, decahydronaphthalene); high molecular weight liquid paraffins or mixtures thereof, and other well-known diluents.
  • gas-phase polymerization processes which are the preferred mode, include both stirred bed reactors and fluidized bed reactor systems; they are described in U.S. Patents 3,957,448; 3,965,083; 3,971 ,768; 3,970,611; 4,129,701; 4,101 ,289; 3,652,527; and 4,003,712, all incorporated by reference herein.
  • Typical gas phase ⁇ -olefin polymerization reactor systems comprise a reactor vessel to which ⁇ -olefin monomer(s) and a catalyst system can be added and which contain an agitated bed of forming polymer particles.
  • the components of the catalyst system are added together or separately through one or more valve-controlled ports in the reactor vessel.
  • ⁇ -Olefin monomer typically, is provided to the reactor through a recycle gas system in which un-reacted monomer removed as off-gas and fresh feed monomer are mixed and injected into the reactor vessel.
  • a quench liquid which can be liquid monomer, can be added to the polymerizing ⁇ -olefin through the recycle gas system in order to control temperature.
  • the reactor is a stirred, essential horizontal sub-fluidized bed reaction.
  • ⁇ -olefin polymers can be exothermically produced as powders in fluidized bed reactors wherein the fluidization is provided by a circulating mixture of gases that includes the monomer(s).
  • the fluidizing gases leaving the reactor can be re-circulated with cooling before reintroduction to the reactor in order to remove the heat of reaction and keep the fluidized bed temperature at the desired temperature.
  • Preferably (a portion of) the re-circulating stream (the off gas) is cooled to condense a portion of said gas to liquid, after which the condensed and cooled products are (at least partially) recycled to the reactor. It is advantageous to remove the latent heat of vaporization, in addition to the sensible heat accumulated in the gas, since the latent heat of vaporization is much larger per degree of cooling than the sensible heat of the uncondensed stream.
  • a variety of methods can be used for reintroduction of the cooled recycle gas and liquids to the reactor. Often, most of the cooled recycle gas is injected into the reactor through a distributor plate below the fluid bed. The condensed recycle liquids may be entrained in the recycle gas or injected directly into the bed through some sort of nozzle assembly. Examples of the above technologies are shown in U.S. Pat. Nos. 3,595,840; 4,543,399; 4,588,790 and 5,352,749, all incorporated by reference herein.
  • polymerization is carried out under conditions that exclude oxygen, water, and other materials that act as catalyst poisons.
  • the polymer upon completion of polymerization, or when it is desired to terminate polymerization or deactivate the catalyst system in the process of the present invention, can be contacted with water, alcohols, acetone, or other suitable catalyst deactivators in a manner known to persons skilled in the art.
  • the products produced in accordance with the process of this invention are normally solid, predominantly isotactic poly- ⁇ -olefins.
  • Polymer yields are sufficiently high relative to the amount of catalyst employed so that useful products can be obtained without removal of catalyst residues. Further, levels of stereorandom by-products are sufficiently low so that useful products can be obtained without removal thereof.
  • the polymeric products produced in the presence of the mentioned catalyst system can be fabricated into useful articles by extrusion, injection molding, and other common techniques. The invention described herein is illustrated, but not limited, by the following Examples and comparative experiments.
  • Example B Synthesis of spiro-[4,4]-3,4,8,9-dibenzo-2,2,7,7-tetramethyl-1,6- dioxa-5-sila-nonane
  • Example E Synthesis of a mixture of silane compounds, composed mainly of 1 -methoxy-1 -methyl-3,4-benzo-1 ,2-siloxacycloheptane
  • the lower (urea hydrochloride) phase was separated and the organic phase was purified by distillation under reduced pressure (200 Pa) to give 85 g of a product isomer mixture (boiling point 85 °C at 200 Pa) consisting of at least 70 %
  • Example F Synthesis of a mixture of silane compounds, composed mainly of spiro-[6,6]-dibenzo-[2,3:9,10]-5-sila-1 ,8-dioxa-undodecane a. Reaction between o-allylphenol and dichlorosilane
  • the product was purified (96 %) by distillation and characterised by H- and 13 C-NMR; main impurities were cyclohexytriethoxysilane (1.3 %) and cyclohexylbutoxydiethoxysilane (2.7 %) as analysed by GC-MS.
  • a mixture of the TEAI cocatalyst and the organosilane compound was dosed in a typical concentration range of 0.20 - 0.25 mol/l.
  • the mixture was prepared in a nitrogen atmosphere dry-box kept free from oxygen and water.
  • the TEAI/organosilane compound solution was adjusted to the reactor under nitrogen atmosphere with a glass pipette.
  • the weighted amount of catalyst was dosed to the reactor with nitrogen and small amounts of purified heptane, afterwards filling up the reactor with purified heptane to a final amount of 5500 ml.
  • the reactor was purged with a mixture of propylene (dosed by a dip tube) and hydrogen (dosed in the gas-phase) with a constant flow of 1000 Nl/hour and 10 Nl/hour respectively during 2 min.
  • the reactor vent valve was closed and the temperature increased to 45 °C, starting a prepolymerization of the catalyst system. Meanwhile, the pressure increased to around 0.14 MPa depending on the activity of the catalyst system. After an additional 2 minutes at 45 °C, the pressure was increased to 0.7 MPa, meanwhile increasing the temperature to 70 °C dosing 1000 Nl/hour propylene and a constant concentration of hydrogen of 1.5 % measured by gaschromatography and a H 2 -sensor.
  • the temperature and pressure increase took about 20 to 25 minutes.
  • the reactor was vented off in around 20 minutes to 0.11 MPa, while cooling to room temperature.
  • the reactor settings were controlled by an operating system and the data are recorded automatically.
  • the collected polymer slurry was centrifuged and the resulting homopolymer powder was dried in a vacuum oven at 60 °C.
  • the amount of atactic polymer (aPP) was determined by drying a specified amount of the heptane solution after reaction.
  • Gas-phase polymerizations were performed in a set of two horizontal, cylindrical reactors in series, wherein a homopolymer was formed in the first reactor and optionally a typical ethylene - propylene copolymer rubber in the second one to prepare an impact copolymer.
  • the first reactor was operated in a continuous way, the second one in a batch manner. In the synthesis of the homopolymer, the polymer was charged into the secondary reactor blanketed with nitrogen.
  • the first reactor was equipped with an off-gas port for recycling reactor gas through a condenser and back through a recycle line to the nozzles in the reactor. Both reactors had a volume of one gallon (3.8-liter) measuring 10 cm in diameter and 30 cm in length.
  • liquid propylene was used as the quench liquid; for the synthesis of copolymers the temperature in the second reactor was kept constant by a cooling jacket.
  • the catalyst was introduced into the first reactor as a 5 - 7 wt.% slurry in hexane through a liquid propylene-flushed catalyst addition nozzle.
  • a mixture of the organosilane compound and TEAI in hexane at an Al/Ti ratio of 180 and Si/Ti ratio of 8 were fed separately to the first reactor through a different liquid propylene flushed addition nozzle.
  • For the synthesis of impact copolymers an Al/Mg ratio of 10 and an Al/Si ratio of 6 was used.
  • polypropylene powder produced in the first reactor passed over a weir and was discharged through a powder discharge system into the second reactor.
  • the polymer bed in each reactor was agitated by paddles attached to a longitudinal shaft within the reactor that was rotated at about 50 rpm in the first and at about 75 rpm in the second reactor.
  • the reactor temperature and pressure were maintained at 71 °C and 2.2 MPa in the first and for the copolymer synthesis at 66 °C and 2.2 MPa in the second reactor.
  • By varying the amount of hydrogen in the first reactor homopolymers with different melt flow rates were obtained.
  • M M n ratio between weight average molecular weight and number average molecular weight
  • the polypropylene products made by a catalyst system according to this invention, were compounded on a PM-20 extruder under standard conditions.
  • the polymers were stabilized by adding typically 0.3 wt.% Irganox ® B225 and 0.05 wt.% calcium stearate.
  • Injection moulding parts were produced typically on a Arburg Injection Moulder.
  • the stiffness of the material was measured by a standard procedure described in ASTM D790. A notched Izod measurement at room temperature was performed according to ISO 180/4A. The tensile test was performed based on ISO R37/2.
  • the crystallization properties of the polymers were determined on a PERKIN ELMER DSC-7 calorimeter which was connected by an interface TAC/7DX instrument controller using the standard procedure described in ASTM D3417/3418 E793/794. A sample weight in between 4 and 6 mg was used. At 40 °C an isotherm waiting time of 5 minutes was applied, after which the temperature was increasing with a scan speed of 10°C/min to 200°C. This is the so-called first heating curve. After again an isotherm waiting time of 5 minutes the temperature was decreased with a scan speed of 10°C/min to 40°C. This is the so-called cooling curve.
  • Typical homopolymers were prepared using the in Table 3 indicated organosilane compounds.
  • a H 2 /MFR relationship was determined for selected organosilane compounds E and G and compared with reference compound DIBDMS.
  • a higher hydrogen response was found for organosilane compound G compared to the reference as illustrated by a higher resulting MFR at comparable ⁇ -concentrations in the feed as illustrated in Figure 2. Broadening of the MWD was observed for organosilane E with respect to the DIBDMS reference.

Landscapes

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

Abstract

L'invention concerne un procédé de polymérisation d'une ou de plusieurs α-oléfines en présence d'un système catalytique spécifique. Ce procédé consiste, de façon caractéristique, à utiliser un composé spécifique d'organosilane en tant que donneur d'électrons externes, le silicium étant incorporé dans un noyau ne comportant qu'un seul hétéroatome.
PCT/NL2002/000531 2001-08-10 2002-08-06 Procede de polymerisation utilisant un organosilane specifique en tant que donneur externe WO2003014167A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP01203035.9 2001-08-10
EP01203035 2001-08-10

Publications (1)

Publication Number Publication Date
WO2003014167A1 true WO2003014167A1 (fr) 2003-02-20

Family

ID=8180777

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/NL2002/000531 WO2003014167A1 (fr) 2001-08-10 2002-08-06 Procede de polymerisation utilisant un organosilane specifique en tant que donneur externe

Country Status (1)

Country Link
WO (1) WO2003014167A1 (fr)

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7619049B1 (en) 2009-04-13 2009-11-17 Formosa Plastics Corporation, U.S.A. Cyclic organosilicon compounds as electron donors for polyolefin catalysts
US7790819B1 (en) 2009-04-13 2010-09-07 Formosa Plastics Corporation, U.S.A. Bicyclic organosilicon compounds as electron donors for polyolefin catalysts
KR101040388B1 (ko) * 2007-01-30 2011-06-09 주식회사 엘지화학 트리옥사실로칸을 포함하는 올레핀 중합용 촉매 및 이를이용한 올레핀 중합 방법
WO2014009204A1 (fr) * 2012-07-11 2014-01-16 Wacker Chemie Ag Oxasilacycles et leur procédé de production
US9309358B2 (en) 2012-07-11 2016-04-12 Wacker Chemie Ag Crosslinkable siloxanes by acid-catalyzed polymerization of oxasilacycles
CN115703851A (zh) * 2021-08-16 2023-02-17 上海立得催化剂有限公司 一种高性能烯烃聚合催化剂的制备方法及其应用

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2983744A (en) * 1955-11-17 1961-05-09 Du Pont Heterocycles
US6057407A (en) * 1997-01-08 2000-05-02 Bp Amoco Corporation High melt flow propylene polymer produced by gas-phase polymerization

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2983744A (en) * 1955-11-17 1961-05-09 Du Pont Heterocycles
US6057407A (en) * 1997-01-08 2000-05-02 Bp Amoco Corporation High melt flow propylene polymer produced by gas-phase polymerization

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
HAERKOENEN M ET AL: "EXTERNAL SILANE DONORS IN ZIEGLER-NATTA CATALYSIS. AN APPROACH TO THE OPTIMUM STRUCTURE OF THE DOOR", MAKROMOLEKULARE CHEMIE, MACROMOLECULAR CHEMISTRY AND PHYSICS, HUTHIG UND WEPF VERLAG, BASEL, CH, vol. 192, 1991, pages 2857 - 2863, XP000942627, ISSN: 0025-116X *
XIN, SHIXUAN ET AL: "Reactions of silanes with allylic alcohols catalyzed by titanocene derivatives: an approach to catalytic cross dehydrocoupling/co- intramolecular hydrosilation", J. ORGANOMET. CHEM. (1995), 499(1-2), 181-91, XP004023802 *

Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR101040388B1 (ko) * 2007-01-30 2011-06-09 주식회사 엘지화학 트리옥사실로칸을 포함하는 올레핀 중합용 촉매 및 이를이용한 올레핀 중합 방법
US7619049B1 (en) 2009-04-13 2009-11-17 Formosa Plastics Corporation, U.S.A. Cyclic organosilicon compounds as electron donors for polyolefin catalysts
US7790819B1 (en) 2009-04-13 2010-09-07 Formosa Plastics Corporation, U.S.A. Bicyclic organosilicon compounds as electron donors for polyolefin catalysts
WO2010120794A1 (fr) * 2009-04-13 2010-10-21 Formosa Plastics Corporation, U.S.A. Composés organiques du silicium bicycliques en tant que donneurs d'électrons pour des catalyseurs de polyoléfines
CN102481569A (zh) * 2009-04-13 2012-05-30 美国台塑公司 作为给电子体用于聚烯烃催化剂的双环有机硅化合物
JP2012523491A (ja) * 2009-04-13 2012-10-04 フオルモサ・プラステイクス・コーポレイシヨン・ユー・エス・エイ ポリオレフィン触媒のための電子供与体としての二環式有機ケイ素化合物
WO2014009204A1 (fr) * 2012-07-11 2014-01-16 Wacker Chemie Ag Oxasilacycles et leur procédé de production
CN104470935A (zh) * 2012-07-11 2015-03-25 瓦克化学股份公司 氧杂环硅烷及其制备方法
JP2015527312A (ja) * 2012-07-11 2015-09-17 ワッカー ケミー アクチエンゲゼルシャフトＷａｃｋｅｒ Ｃｈｅｍｉｅ ＡＧ オキサシラサイクルおよびこれらの製造方法
US9284340B2 (en) 2012-07-11 2016-03-15 Wacker Chemie Ag Oxasilacycles and method for the production thereof
US9309358B2 (en) 2012-07-11 2016-04-12 Wacker Chemie Ag Crosslinkable siloxanes by acid-catalyzed polymerization of oxasilacycles
CN115703851A (zh) * 2021-08-16 2023-02-17 上海立得催化剂有限公司 一种高性能烯烃聚合催化剂的制备方法及其应用
CN115703851B (zh) * 2021-08-16 2024-03-19 上海立得催化剂有限公司 一种高性能烯烃聚合催化剂的制备方法及其应用

Similar Documents

Publication Publication Date Title
US4829038A (en) Alpha-olefin polymerization catalyst system including an advantageous modifier component
EP0250229B2 (fr) Procédé de polymérisation d'alpha-oléfine
US4581342A (en) Supported olefin polymerization catalyst
EP1866347A2 (fr) Composant donneur pour catalyseur de polymerisation de propylene
WO2002096558A1 (fr) Compositions catalyseurs de polymerisation olefinique ameliorees et procede d'elaboration
WO2006010414A1 (fr) Compositions copolymeres de propylene de transparence elevee
MX2011005542A (es) Composicion de procatalizador incluyendo donador interno de silil ester y metodo.
WO2006096621A2 (fr) Constituant donneur de catalyseur polymere propylenique
JP2001505249A (ja) オレフィンの重合用成分および触媒
EP1613670B1 (fr) Catalyseur de polymerisation d'olefine contenant du cycloalcane dicarboxylate comme donneur d'electrons
EP0951488B1 (fr) Polymere de propylene a indice de fluage eleve produit par polymerisation de phase gazeuse
WO2002096957A1 (fr) Compositions de catalyseur de polymerisation d'olefine et methode de preparation
US4990478A (en) Silane-modified supported polyolefin catalyst to produce a broadened molecular weight distribution product
EP0773241B1 (fr) Composant catalytique solide pour la polymérisation d'oléfines et catalyseur de polymérisation d'oléfines
WO2003014167A1 (fr) Procede de polymerisation utilisant un organosilane specifique en tant que donneur externe
US20100240846A1 (en) Catalyst component for the polymerization of olefins based on 1,3-diethers
EP3357938B1 (fr) Procédé de préparation d'un catalyseur métallocène pour la préparation d'une polyoléfine
EP0880549A2 (fr) Systeme catalyseur et composants
EP0576413B1 (fr) Donneurs d'électrons pour la polymérisation améliorée d'oléfines
EP0368344B1 (fr) Procédé de préparation de polymères d'alpha-oléfines
JP2001151816A (ja) プロピレン系重合体およびその製造方法
JPH09194651A (ja) ポリプロピレン樹脂組成物
JP2008534722A (ja) オレフィン類の重合用触媒成分
JP3913916B2 (ja) 有機ケイ素化合物及びα−オレフィンの重合方法
CA1320737C (fr) Systeme de catalyseur pour la polymerisation d'alpha-olefines, comportant un modificateur de la composition a proprietes avantageuses

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: A1

Designated state(s): AE AG AL AM AT AU AZ BA BB BG BY BZ CA CH CN CO CR CU CZ DE DM DZ EC EE ES FI GB GD GE GH HR HU ID IL IN IS JP KE KG KP KR LC LK LR LS LT LU LV MA MD MG MN MW MX MZ NO NZ OM PH PL PT RU SD SE SG SI SK SL TJ TM TN TR TZ UA UG US UZ VC VN YU ZA ZM

Kind code of ref document: A1

Designated state(s): AE AG AL AM AT AU AZ BA BB BG BR BY BZ CA CH CN CO CR CU CZ DE DK DM DZ EC EE ES FI GB GD GE GH GM HR HU ID IL IN IS JP KE KG KP KR KZ LC LK LR LS LT LU LV MA MD MG MK MN MW MX MZ NO NZ OM PH PL PT RO RU SD SE SG SI SK SL TJ TM TN TR TT TZ UA UG US UZ VC VN YU ZA ZM ZW

AL Designated countries for regional patents

Kind code of ref document: A1

Designated state(s): GH GM KE LS MW MZ SD SL SZ UG ZM ZW AM AZ BY KG KZ RU TJ TM AT BE BG CH CY CZ DK EE ES FI FR GB GR IE IT LU MC PT SE SK TR BF BJ CF CG CI GA GN GQ GW ML MR NE SN TD TG

Kind code of ref document: A1

Designated state(s): GH GM KE LS MW MZ SD SL SZ TZ UG ZM ZW AM AZ BY KG KZ MD RU TJ TM AT BE BG CH CY CZ DE DK EE ES FI FR GB GR IE IT LU MC NL PT SE SK TR BF BJ CF CG CI CM GA GN GQ GW ML MR NE SN TD TG

121 Ep: the epo has been informed by wipo that ep was designated in this application
DFPE Request for preliminary examination filed prior to expiration of 19th month from priority date (pct application filed before 20040101)
REG Reference to national code

Ref country code: DE

Ref legal event code: 8642

122 Ep: pct application non-entry in european phase
NENP Non-entry into the national phase

Ref country code: JP

WWW Wipo information: withdrawn in national office

Country of ref document: JP