EP1141044A1 - Composant catalyseur solide pour la polymerisation d'olefines, catalyseur pour la polymerisation d'olefines et procede de production de polymere olefinique - Google Patents

Composant catalyseur solide pour la polymerisation d'olefines, catalyseur pour la polymerisation d'olefines et procede de production de polymere olefinique

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Publication number
EP1141044A1
EP1141044A1 EP00971440A EP00971440A EP1141044A1 EP 1141044 A1 EP1141044 A1 EP 1141044A1 EP 00971440 A EP00971440 A EP 00971440A EP 00971440 A EP00971440 A EP 00971440A EP 1141044 A1 EP1141044 A1 EP 1141044A1
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EP
European Patent Office
Prior art keywords
catalyst component
compound
component according
polymerization
solid catalyst
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP00971440A
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German (de)
English (en)
Inventor
Masaki Montell SDK Sunrise Ltd. FUSHIMI
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Basell Poliolefine Italia SRL
Original Assignee
Basell Poliolefine Italia SRL
Basell Technology Co BV
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Publication date
Priority claimed from JP32422599A external-priority patent/JP2001139622A/ja
Priority claimed from JP32421199A external-priority patent/JP2001139618A/ja
Priority claimed from JP32420999A external-priority patent/JP2001139621A/ja
Application filed by Basell Poliolefine Italia SRL, Basell Technology Co BV filed Critical Basell Poliolefine Italia SRL
Publication of EP1141044A1 publication Critical patent/EP1141044A1/fr
Withdrawn legal-status Critical Current

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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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F110/04—Monomers containing three or four carbon atoms
    • C08F110/06—Propene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2410/00—Features related to the catalyst preparation, the catalyst use or to the deactivation of the catalyst
    • C08F2410/03—Multinuclear procatalyst, i.e. containing two or more metals, being different or not
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2410/00—Features related to the catalyst preparation, the catalyst use or to the deactivation of the catalyst
    • C08F2410/04—Dual catalyst, i.e. use of two different catalysts, where none of the catalysts is a metallocene

Definitions

  • the present invention relates to a solid catalyst component for olefin polymerization, a catalyst therefrom obtained and to a process for producing an olefin polymer having broad molecular weight distribution using said catalyst.
  • Japanese Patent Publication No. 12105/1964 discloses the use of an iron halogen crystal coated with molecular layer of a titanium compound.
  • Japanese Patent Publication No. 50806/1985 discloses the use of a reaction product of a vapor of a metal such as iron or the like and titanium as a solid catalyst component.
  • the production of a solid catalyst by co-pulverizing an adduct of iron chloride and an electron-donor compound with a ball mill and then reacting the resulting product with a titanium compound is described in USP 4,439,538.
  • these catalysts are characterized by a low polymerization activity and in particular by a very low stereospecif ⁇ city because the amounts of isotactic polypropylene produced is extremely low, and it is far from satisfying the present industrial requirement.
  • a solid component obtained by contacting a halide of a metal such as iron or the like which is pretreated with an electron donor, a silicon halide and a transition metal as a catalyst is disclosed in Japanese Patent Publication Nos. 46799/1978, 3479/1979, 45486/1981 and 5201/1983.
  • the combined use of a magnesium chloride-supported catalyst or a TiCl 3 catalyst and a halide of a transition metal such as iron or the like as a solid catalyst component is described in Japanese Patent Laid-Open No. 43626/1993 while the addition of a transition metal halogen compound such as iron chloride in a magnesium chloride-based catalyst is disclosed in Japanese Patent Laid-Open Nos. 22302/1981, 151785/1976, 878/1977, 50207/1991, 178406/1992, 112007/1984, 147410/1983, 113007/1984 and 208615/1997.
  • the above-described methods induce a differentiation of the catalyst and, consequently, the resulting polymer may show a molecular weight distribution which is slightly broadened in comparison with an non-added catalyst system.
  • the catalyst obtained by these methods is not industrially desirable because the control of the catalyst production is complicated. It was impossible to obtain efficiently (with a high catalytic activity) a polymer showing a molecular weight distribution (measured by the polydispersity index (PI) > 5.0) which is broad enough to improve the molding efficiency.
  • the present inventors have found that when olefin polymerization is carried out using a catalyst component specified below, a polyolefin having a broad molecular weight distribution and excellent in moldability is obtained at good efficiency and good isotactic index.
  • a solid catalyst component (A) for olefin polymerization comprising a titanium compound, an electron donor compound (Dl) and a compound of a transition metal compound selected from Mn, Fe, Co, Ni and Zn; said electron-donor compound (Dl) being selected from those of formula (I):
  • Z represents a carbon atom, a silicon atom, a methylene chain or a substituted methylene chain
  • R 1 ? R 2 and R 3 may be the same or different and each represents a linear or branched alkyl group having 1 to 18 carbon atoms, an alicyclic group, an aryl group, an alkylaryl group or an arylalkyl group
  • Ri or R 2 may be hydrogen.
  • the compound of transition metal is selected from the halides of manganese, iron, cobalt, nickel and zinc.
  • the chlorides of said metals are preferred. It is also preferable the use of those chlorides having the crystal structure of cadmium chloride.
  • preferred compounds can include manganese chloride, iron chloride(II), cobalt chloride, nickel chloride and zinc chloride. Among them manganese chloride and iron chloride(II) are preferred and iron chloride is especially preferable. Further, a mixture of two or more of these compounds is also suitable.
  • the titanium compound is selected from those of formula Ti(OR 4 ) n-p Xp, where n is the valence of titanium, X is halogen, p is a number between 0 and n and R 4 has the same meaning of R.
  • the preferred titanium compounds used in the catalyst component of the present invention are those in which p is from 1 to n and particularly TiCl 4 and TiCl 3 ; furthermore, also Ti- haloalcoholates can be advantageously used.
  • titanium compounds examples include titanium halides such as titanium tetrachloride, titanium trichloride, titanium tetrabromide and the like; titanium alkoxides such as titanium butoxide, titanium ethoxide and the like; alkoxytitanium halides such as phenoxytitanium chloride and the like. Further, a mixture of two or more of these compounds is also usable.
  • the electron-donor compound (Dl) represented by the general formula (I) Z may be a methylene chain or a substituted methylene chain having 1 to 10 carbon atoms, preferably 1 to 6 carbon atoms.
  • the substituent of the substituted methylene chain may be a linear, branched or cyclic hydrocarbon group having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, or an aromatic hydrocarbon group having 6 or more carbon atoms.
  • Z is preferably a carbon atom.
  • R 3 is preferably an alkyl group having 1 to 10 carbon atoms.
  • Ri is methyl, ethyl, propyl or isopropyl
  • R 2 may be ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, 2-ethylhexyl, cyclohexylmethyl, phenyl or benzyl.
  • R 2 may be ethyl, butyl, sec-butyl, tert-butyl, 2-ethylhexyl, cyclohexylethyl, diphenylme hyl, p-chlorophenyl, 1-naphthyl or 1-decahydronaphthyl. Still further, R 1 and R 2 may be the same, and may be ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, neopentyl, isopentyl, phenyl, benzyl or cyclohexyl.
  • a diether compound a diester compound, an alkoxy ester compound and a keto ester compound are preferable.
  • the diether compound include 2-(2-ethylhexyl)-l,3-dimethoxypropane, 2-isopropyl- 1 ,3-dimethoxypropane, 2-butyl- 1 ,3-dimethoxypropane, 2-sec-butyl- 1 ,3- dimethoxypropane, 2-cyclohexyl-l,3-dimethoxypropane, 2-phenyl-l,3-diethoxypropane, 2- cumyl- 1 ,3-diethoxypropane, 2-(2-phenylethyl)- 1 ,3-dimethoxypropane, 2-(2-cyclohexylethyl)- 1 ,3-dimethoxypropane, 2-(diphenylmethyl)-l ,3-dimethoxypropane, 2-(2-fluor
  • diester compound can include diethyl 2,2-diisopropylmalonate, diethyl 2,2-diisobutymalonate, diethyl 2,2-diisopentylmalonate, diethyl 2,2- diisohexylmalonate, diethyl 2,2-diisoheptylmalonate, diethyl 2,2-di(2- cyclopentylethyl)malonate, diethyl 2,2-di(2-cyclohexylethyl)malonate, diethyl 2-isopropyl-2- isobutylmalonate, diethyl 2-isopropyl-2-isopentylmalonate, diethyl 2-isopropyl-2- isohexylmalonate, diethyl 2-isopropyl-2-isoheptylmalonate, diethyl 2-isopropyl-2-(2- cyclopentylethyl)malonate
  • alkoxy ester compound can include ethyl 3-ethoxy-2- phenylpropionate, ethyl 3-ethoxypropionate, ethyl 3-ethoxy-2-mesitylpropionate, ethyl 3- butoxy-2-(methoxyphenyl)propionate, methyl 3-i-propoxy-3-phenylpropionate, ethyl 3- ethoxy-3-phenylpropionate, ethyl 3-ethoxy-3-tert-butylpropionate, ethyl 3-ethoxy-3- adamantylpropionate, ethyl 3-ethoxy-2-tert-butylpropionate, ethyl 3-ethoxy-2-tert- amylpropionate, ethyl 3-ethoxy-2-adamantylpropionate, ethyl 3-ethoxy-2- bicyclo[2,2,l]heptylpropionate, ethyl
  • keto ester compound can include methyl 3-acetylpropionate, ethyl 3- acetylpropionate, butyl 3-acetylpropionate, ethyl 3-propionylpropionate, butyl 3- propionylpropionate, n-octyl 3-propionylpropionate, dodecyl 3-propionylpropionate, pentamethylphenyl 3-propionylpropionate, ethyl 3-(isopropionyl)propionate, butyl 3-
  • the solid catalyst component ofthe invention can be prepared with different methods some of whose are disclosed below.
  • the catalyst component is obtained by contacting a titanium halide with the solid obtained by co-milling the transition metal halide and an electron-donor compound (Dl).
  • the transition metal halide in an anhydrous state and the electron donor compound Dl are milled together up to reaching the desired particle or crystallite size.
  • the so obtained product can be treated one or more times with an excess of TiCl 4 at a temperature between 80 and 135°C. This treatment is followed by washings with hydrocarbon solvents until chloride ions disappeared.
  • the co-milling of may be carried out by using milling equipment such as a ball mill, a vibrating ball mill, an impact type mill or a colloid mill.
  • Such operation can normally be carried out at a temperature near room temperature while cooling can be performed for the convenience of the operation in case when the strong exothermic reaction is observed.
  • the period of time necessary for such co-milling varies according to several factors well known to the skilled in the art like type and efficiency ofthe mill, extent of loading, presence of diluents etc.
  • Another preferred method comprises (a) contacting the transition metal compound with one or more organic or inorganic compound, and then (b) contacting the resulting product with a titanium halide; the electron-donor compound (Dl) being present in at least one of the steps
  • step (a) the use of an organic compound in step (a) is preferred.
  • organic compounds can be used hydrocarbon compounds halogenated hydrocarbons and silicon organic compound.
  • silicon organic compounds is most preferred.
  • the method comprising (a) contacting a transition metal salt and a silicon organic compound, and optionally other components, in order to form an adduct of said transition metal salt with the organic silicon compound, and (b) contacting the said adduct with a titanium compound in the presence of Dl.
  • the adduct is preferably represented by a general formula (II) described below:
  • M represents a manganese, an iron, a cobalt, a nickel or a zinc atom, and preferably a manganese, an iron or a cobalt atom, most preferably an iron atom.
  • X represents a halogen atom and preferably a chlorine, a bromine or an iodine atom.
  • R4 and R 5 may be same or different, each represents a hydrocarbon group having 18 or less carbon atoms, and preferably a straight chain or branched hydrocarbon group having 1 to 10 carbon atoms, or a cyclic hydrocarbon group having 3 to 6 carbon atoms, r is zero or an integer in the range of 1 to 3 and q is a number from more than 0 to equal or less than 4, preferably from 0.1 to 2.
  • the contact between the transition metal compound and the organic silicon compound in order to prepare the adduct can occur under different conditions.
  • such adduct may be obtained by mixing under heating the transition metal salt and the organic silicon compound in a hydrocarbon solvent such as hexane and the like, or by co-milling the transition metal salt with the organic silicon compound followed by washing the solid substance with an hydrocarbon such as hexane.
  • the co-milling of a transition metal salt and an organic silicon compound may be carried out by the same techniques and apparatuses disclosed above.
  • a vibrating ball mill having the inner volume of 1 liter and the diameter of 10 cm which contains 50% apparent volume of stainless steel balls with a diameter of 1 cm, filled with 20 g of the material to be milled and vibrated with the amplitude of 6 mm and frequency of 30 Hz, the completion of the milling takes more than 30 minutes, preferably more than 1 hour and particularly good results are obtaining carrying out the milling for a period between 3 and 24 hours.
  • the amount of the organic silicon compound is preferably equal or lower than 10 mols, and more preferably equal or lower than 2 mols with respect to 1 mol ofthe transition metal salt.
  • the preparation of the catalyst component of the invention may also be carried out in such a way that it finally results said catalyst being supported on, or impregnated in, a substance generally used as a catalyst support, for example, silica or alumina.
  • a quantitative relation of each component in the solid catalyst component is optional so long as the effects of the invention are identified.
  • the content of the transition metal is in the range of 0.1 to 1,000, preferably in the range of 2 to 200 in terms of a molar ratio to titanium.
  • the content ofthe electron-donor compound (Dl) is in the range of 10 or less, preferably in the range of 0.01 to 5 in terms of a molar ratio to titanium.
  • the solid catalyst component ofthe invention is used in combination with an organoaluminum compound in the preparation of a catalyst system for the polymerization of olefins.
  • organoaluminum compound used in the catalyst for olefin polymerization of the invention particularly preferred are those represented by the formula A1R 6 S X 3 - S where R is a hydrocarbon group having from 1 to 20 carbon atoms, X is halogen and s is from 1 to 3.
  • R is a hydrocarbon group having from 1 to 20 carbon atoms
  • X is halogen and s is from 1 to 3.
  • organoaluminum compounds are the trialkyl aluminum compounds such as for example triethylaluminum, triisobutylaluminum, tri-n-butylaluminum, tri-n-hexylaluminum, tri-n-octylaluminum. It is also possible to use mixtures of trialkylaluminum's with alkylaluminum halides, alkylaluminum hydrides or alkylaluminum sesquichlorides such as AlEt 2 Cl and Al 2 Et 3 Cl 3 . Also alkylalumoxanes can be used.
  • the amount ofthe organoaluminum compound used in the polymerization is such that molar ratio relative to the titanium atom in the solid catalyst component for olefin polymerization is generally from 0.5 to 10,000 and preferably in case organoaluminum compound of formula (III) are used from 1 to 1000.
  • the solid catalyst component of the present invention is used in combination with another solid catalyst component (B) comprising Ti, Mg, and halogen as essential elements.
  • said solid catalyst component B also contains an electron donor compound (D2).
  • the solid catalyst component (B) comprises a titanium compound having at least one Ti-halogen bond and an electron donor compound supported on a Mg halide.
  • the catalyst components (B) in which the Ti compound is TiCl 4 or TiCl the Mg halide is MgCl and the electron donor compound (D2) is selected from ethers, ketones, amines and esters of organic mono or bicarboxylic acids, such as phthalates, benzoates, glutarates and succinates.
  • the catalyst component (B) can be prepared according to several methods. According to one of these methods, the magnesium dichloride in an anhydrous state and the electron donor compound are milled together. The so obtained product can be treated one or more times with an excess of TiCl 4 at a temperature between 80 and 135°C. This treatment is followed by washings with hydrocarbon solvents until chloride ions disappeared.
  • the product obtained by co-milling the magnesium chloride in an anhydrous state, the titanium compound and the electron donor compound is treated with halogenated hydrocarbons such as 1,2- dichloroethane, chlorobenzene, dichloromefhane, etc.
  • halogenated hydrocarbons such as 1,2- dichloroethane, chlorobenzene, dichloromefhane, etc.
  • the treatment is carried out for a time between 1 and 4 hours and at temperature of from 40°C to the boiling point of the halogenated hydrocarbon.
  • the product obtained is then generally washed with inert hydrocarbon solvents such as hexane.
  • a further method comprises the reaction between magnesium alcoholates or chloroalcoholates (in particular chloroalcoholates prepared according to U.S. 4,220,554) and an excess of TiCl 4 comprising the electron donor compound in solution at a temperature of about 80 to 120°C.
  • the solid catalyst component can be prepared by reacting a titanium compound of formula Ti(OR 4 ) n-p X p , where n is the valence of titanium, X is halogen, p is a number between 0 and n and R 4 has the same meaning of R, preferably TiCl 4 , with a magnesium chloride deriving from an adduct of formula MgCl «pROH, where p is a number between 0.1 and 6, preferably from 2 to 3.5, and R is a hydrocarbon radical having 1-18 carbon atoms.
  • the adduct can be suitably prepared in spherical form by mixing alcohol and magnesium chloride in the presence of an inert hydrocarbon immiscible with the adduct, operating under stirring conditions at the melting temperature of the adduct (100-130 °C). Then, the emulsion is quickly quenched, thereby causing the solidification of the adduct in form of spherical particles. Examples of spherical adducts prepared according to this procedure are described in USP 4,399,054 and USP 4,469,648.
  • the so obtained adduct can be directly reacted with the Ti compound or it can be previously subjected to thermally controlled dealcoholation (80-130 °C) so as to obtain an adduct in which the number of moles of alcohol is generally lower than 3 preferably between 0.1 and 2.5.
  • the reaction with the Ti compound can be carried out by suspending the adduct (dealcoholated or as such) in cold TiCl 4 (generally 0 °C); the mixture is heated up to 80-130 °C and kept at this temperature for 0.5-2 hours.
  • the treatment with TiCl 4 can be carried out one or more times.
  • the succinate of formula (I) can be added during the treatment with TiCl 4 .
  • the treatment with the electron donor compound can be repeated one or more times.
  • the weight ratio of the solid catalyst component (A) and the solid catalyst component (B) in the mixed solid catalyst component of the invention is not particularly limited. Generally, the amounts of A and B are such that is 0.01 ⁇ ([A]/[A] + [B])) ⁇ 0.99, preferably 0.1 ⁇ ([A]/([A]+[B])) ⁇ 0.9.
  • the solid catalyst component (A) and the solid catalyst component (B) may preliminarily be mixed before being charged into a polymerization reactor or may be charged separately into a polymerization reactor and mixed in the polymerization reactor.
  • An organoaluminum compound according to the formulae and conditions above described is used also when a mixture of (A) and (B) is used as solid catalyst component. Both in case the component ofthe invention (A) is used alone and in combination with (B) the catalyst system obtained by the contact with the organoaluminum compound is conveniently added with another electron donor compound (D3) (external donor).
  • D3 electron donor compound
  • the electron-donor compound (D3) used as the third component in the invention can be equal to or different from the electron donor compound present on component (B).
  • it is suitably selected from an organosilicon compound having an alkoxy group, a nitrogen- containing compound, a phosphorus-containing compound and an oxygen-containing compound.
  • an organosilicon compound having an alkoxy group is preferably used.
  • the amount of the third component used is preferably in the range of 0.001 to 5, especially preferably in the range of 0.01 to 1 in terms of a molar ratio to the organoaluminum compound.
  • a preferred class of silicon compounds containing an alkoxy group is that of formula R a 8 R b 9 Si(OR 10 ) c , where a and b are integer from 0 to 2, c is an integer from 1 to 3 and the sum (a+b+c) is 4; R 8 , R 9 , and R 10 are C1-C18 hydrocarbon groups optionally containing heteroatoms.
  • organosilicon compound having the alkoxy group examples include tetramethoxysilane, tetraethoxysilane, tetrabutoxysilane, tetraisobutoxysilane, trimethylmethoxysilane, trimethylethoxysilane, triethylmethoxysilane, triethylethoxysilane, ethylisopropyldimethoxysilane, propylisopropyldimethoxysilane, diisopropyldimethoxysilane, diisobutyldimethoxysilane, isopropylisobutyldimethoxysilane, di-tert-butyldimethoxysilane, tert-butylmethyldimethoxysilane, tert-butylethyldimethoxysilane, tert-butyl-n- propyldimethoxysilane, tert
  • nitrogen-containing compound examples include 2,6-substituted piperidines such as 2.6-diisopropylpiperidine, 2,6-diisopropyl-4-methylpiperidine, N-methyl-2,2,6,6- tetramethylpiperidine and the like; 2,5-substituted azolidines such as 2,5-diisopropylazolidine, N-methyl-2,2,5,5-tetramethylazolidine and the like; substituted methyl enediamines such as N,N,N',N'-tetramethylmethylenediamine, N,N,N',N'-tetraethylmethylenediamine and the like; substituted imidazolines such as 1 ,3-dibenzylimidazolidine, and l,3-dibenzyl-2- phenylimidazolidine and the like; and so forth.
  • piperidines such as 2.6-diisopropylpiperidine, 2,6-di
  • the olefin used in the invention is generally an olefin having at most 12 carbon atoms. Typical examples thereof include ethylene, propylene, butene-l,4-methylpentene-l, hexene-1, octene-1 and the like. In practicing the polymerization, two or more olefins may be copolymerized (for example, copolymerization of ethylene and propylene).
  • the solid catalyst component (A) or (A)+(B) and the organoaluminum compound or these and the third component in the invention may separately be introduced into the polymerization vessel, or two or all of these may be mixed preliminarily.
  • the polymerization can be conducted in an inert solvent, in a liquid monomer (olefin) or in a gaseous phase. Further, in order to obtain a polymer having a practical melt flow, a molecular weight modifier (generally, hydrogen) may co-exist.
  • a molecular weight modifier generally, hydrogen
  • a value of a polydispersity index (PI) of the polymer produced with the above catalyst system is generally higher than 5.0.
  • PI polydispersity index
  • Preferable is a value in the range of 5.0 ⁇ PI ⁇ 30. More preferable is a value in the range of 5.0 ⁇ PI ⁇ 20.
  • the polymerization is generally carried out at temperature of from 20 to 120 °C, preferably of from 40 to 80 °C.
  • the operating pressure is generally between 0.5 and 10 MPa, preferably between 1 and 5 MPa.
  • the operating pressure is generally between 1 and 6 MPa preferably between 1.5 and 4 MPa.
  • Hydrogen or other compounds capable to act as chain transfer agents can be used to control the molecular weight of polymer.
  • the production of the solid catalyst component and the polymerization were conducted substantially in the absence of water and under an atmosphere of nitrogen.
  • the stereoregularity of the polymer is expressed as the amount of the xylylene-insoluble fraction (XI%) of a polymer at 25°C which is determined with the following method: 2.5 g of a polymer was dissolved in 250 ml of xylylene at 135°C, and the solution was then cooled to
  • the amount of the polymer precipitated was weighed after drying and defined as the amount ofthe xylylene-insoluble fraction (XI%).
  • the value of the polydispersity index (PI), an index by which to evaluate the breadth of the molecular weight distribution of a polymer was measured by the following method.
  • a polymer was compression-molded at 230°C for 5 minutes to form a disk-like measuring sample having a thickness of 1.5 mm and a diameter of 25 mm.
  • the measurement was conducted using Rheometer RMS80 manufactured by Rheometrics, and the calculation was conducted by the method described in Zeichner, G. R., Patel, P. D.: 2nd World Congr. of
  • Example 1 The procedure disclosed in Example 1 was repeated with the only difference that anhydrous magnesium chloride was used instead of MnCl 2 .
  • Example 1 The procedure disclosed in Example 1 was repeated with the only difference that 30 g of anhydrous magnesium chloride, 4.0 g of anhydrous iron (II) chloride and 6.9 g of 2-isopropyl-
  • Example 1 The procedure disclosed in Example 1 was repeated with the only difference that 30 g of anhydrous iron(II) chloride (by Aldrich) and 5.1 g of 2,2-isobutyl-l,3-diethoxypropane were charged into the vibrating mill.
  • Example 2 A polymerization test was carried out according to the procedure disclosed in Example 1 using 11 mg of the solid catalyst component obtained in Example 1 and 91 mg of triethylaluminum. Consequently, 24 g of a polypropylene powder was obtained having a XI of
  • Example 2 A polymerization test was carried out according to the procedure disclosed in Example 1 using 13 mg of the solid catalyst component obtained in Example 1, 158 mg of triethylaluminum and 48 mg of texyltrimethoxysilane. Consequently, 33 g of a polypropylene powder was obtained having a XI of 98.1 % and a PI value of 9.4.
  • This washing was conducted until the chlorine ion was not detected in the washed solution.
  • Example 2 The polymerization was carried out according to the procedure disclosed in Example 1 using 7 mg of the above-obtained solid catalyst component, 91 mg of triethylaluminum and 16 mg of texyltrimethoxysilane. Consequently, 62 g of a polypropylene powder was obtained having a
  • Example 5 The procedure disclosed in Example 5 was repeated with the only difference that 1.06 g of
  • Example 2 The polymerization was carried out according to the procedure disclosed in Example 1 using 8 mg of the above-obtained solid catalyst component, 91 mg of triethylaluminum and 16 mg of texyltrimethoxysilane. Consequently, 53 g of a polypropylene powder was obtained having a
  • Example 5 The procedure disclosed in Example 5 was repeated with the only difference that 0.84 g of 3- methoxy-3-tert-butylpropionate were used instead of 2-isopropyl-2-isopentyl-l,3- dimethoxypropane .
  • Example 5 The procedure disclosed in Example 5 was repeated with the only difference that 0.62 g of 3-
  • Example 1 The procedure disclosed in Example 1 was repeated with the only difference that 30 g of anhydrous cobalt(II) chloride(by Aldrich) and 4.9 g of 2-isopropyl-2-isopentyl-l,3- dimethoxypropane were charged into the vibrating mill.
  • polymerization was carried out according to the procedure disclosed in Example 1 using 9 mg of the above-obtained solid catalyst component, 91 mg of triethylaluminum and 16 mg of texyltrimethoxysilane. Consequently, 27 g of a polypropylene powder was obtained. The XI of this polypropylene powder was 95.9%. The PI value was 8.8.
  • anhydrous ferrous chloride (II) purchased from Aldrich and 6.5 g of tetraethoxysilane were introduced into a cylindrical vessel for vibrating ball mill made of stainless steel with an inner volume of 1 liter, about half volume being packed with stainless steel balls having a diameter of 10 mm.
  • This vessel was set in a vibrating ball mill and the contents were pulverized during 12 hours with the amplitude of 6 mm and the frequency of 30
  • a solid substance was thus obtained containing 19.6 weight % of tetraethoxysilane and 35.8 weight % of iron atom therefore corresponding to the formula FeCl 2 » 0.15(Si(OC 2 H5) 4 ).
  • Example 10 The procedure of Example 10 was repeated with the only difference that 13.0 g of tetraethoxysilane were used. On the basis of the analysis (33.5 weight % of tetraethoxysilane and 29.6 weight % of iron atom) the chemical formula of the solid obtained is
  • Example 10 The procedure of Example 10 was repeated by using the above prepared adduct and with the only difference that 0.55 g of 2,2-diisobutyl-l,3-dimethoxypropane was used.
  • Example 10 The procedure of Example 10 was repeated with the only difference that 10.0 g of tetrabutoxysilane (Si/Fe molar ratio was 0.2) were used.
  • the chemical formula of the adduct was is FeC12-0.11(Si (OC4H9) calculated from the values of 21.7 weight % of tetrabutoxysilane and 34.9 weight % of iron atom therein.
  • Example 10 The procedure of Example 10 was repeated by using the above prepared adduct and with the only difference that 0.63 g of 2,2-diisobutyl-l,3-dimethoxypropane was used.
  • Example 10 The procedure of Example 10 was repeated by using the above prepared adduct and with the only difference that 0.41 g of 2,2-diisobutyl-l,3-dimethoxypropane were used.
  • Example 13 The procedure of Example 13 was repeated with the only difference that 23.7 g of tetramethoxysilane instead of tetraethoxysilane were used.
  • the chemical formula of this adduct was FeCl 2 *0.4Si (OCH 3 ) 4 calculated from the values of 32.2 weight % of tetramethoxysilane and 30.2 weight % of iron atom therein.
  • Example 10 The procedure of Example 10 was repeated by using the above prepared adduct and with the only difference that 0.56 g of 2-isopropyl-2-isopentyl-l,3-dimethoxypropane was used.
  • the polymerization was carried out according to the procedure disclosed in Example 1 using 8 mg ofthe solid substance obtained as mentioned above, 91 mg of triethylaluminum and 16 mg of thexyltrimethoxysilane and then added were 340 g of propylene and 0.03 g of hydrogen. As a result, 23 g of a polypropylene powder was obtained having XI of 99.1%, and PI of 9.4.
  • Example 10 The procedure of Example 10 was repeated with the only difference that 0.66 g of 3-ethoxy-3- tert-butylpropionate were used instead of 2,2-diisobutyl-l,3-dimethoxypropane.
  • Example 10 The procedure of Example 10 was repeated with the only difference that 0.85 g of diethyl 2,2- diisobutylmalonate were used instead of 2,2-diisobutyl-l,3-dimethoxypropane.
  • Example 10 12 mg ofthe solid substance obtained in Example 10, 91 mg of triethylaluminum and 18.2 mg of dicyclopentyldimethoxysilane. As a result, 22 g of a polypropylene powder was obtained having XI of 98.1%, and PI of 7.8.
  • Example 10 The procedure of Example 10 was repeated with the only difference that twenty (20) g of manganese chloride anhydride (II) purchased from Aldrich were used instead of ferrous chloride.
  • the chemical formula of the so obtained adduct was MnCl 2 *0.16Si(OC 2 H 5 ) 4 calculated from the values of 20.9 weight % of tetraethoxysilane and 34.5 weight % of manganese atom therein.
  • Example 10 The procedure of Example 10 was repeated using the adduct obtained as described above. Polymerization
  • Example 10 The procedure of Example 10 was repeated with the only difference that twenty (20) g of cobalt chloride anhydride (II) purchased from Aldrich were used instead of ferrous chloride.
  • the chemical formula of this solid substance is CoCl 2 '0.11Si(OC H 5 ) 4 calculated from the values of 14.9 weight % of tetraethoxysilane and 38.8 weight % of cobalt atom therein.
  • Example 10 The procedure of Example 10 was repeated using the adduct obtained as described above.
  • the polymerization was carried out according to the procedure disclosed in Example 1 using 5 mg of the above-obtained solid catalyst component (A), 5 mg of the above-obtained solid catalyst component (B), 91 mg of triethylaluminum and 16 mg of texyltrimethoxysilane.
  • Example 6 The polymerization was carried out according to the procedure disclosed in Example 1 using 13 mg of the above-obtained solid catalyst component, 5 mg of the solid catalyst component (A) of Example 20, 91 mg of triethylaluminum and 16 mg of texyltrimethoxysilane. Consequently, 66.3 g of a polypropylene powder was obtained having a XI of 96.4%, a MFR value of 7.0, and the PI value of 3.5. Comparative Example 6 Preparation of a solid catalyst component
  • Example 21 The polymerization was carried out according to the procedure disclosed in Example 1 using 14 mg ofthe above-obtained solid catalyst component, 91 mg of triethylaluminum and 16 mg of thexyltrimethoxysilane. Consequently, 33.6 g of a polypropylene powder was obtained having a XI of 93.4%, a MFR value of 24.0, and a PI value of 3.7.
  • Example 21
  • Example 2 A polymerization test was carried out according to the procedure disclosed in Example 1 using 7 mg of the solid catalyst component (B) and 4 mg of the solid catalyst component (A) as obtained in Example 20, 91 mg of triethylaluminum and 16 mg of texyltrimethoxysilane. Consequently, 26 g of a polypropylene powder was obtained having a XI of 97.1%, a MFR value of 8.3, and a PI value of 6.6.
  • Example 2 A polymerization test was carried out according to the procedure disclosed in Example 1 using 5 mg of the solid catalyst component (B) and 5 mg of the solid catalyst component (A) as obtained in Example 1, 91 mg of triethylaluminum and 22 mg of dicyclopentyldimethoxysilane. Consequently, 31 g of a polypropylene powder was obtained having a XI of 97.4%, a MFR value of 7.0 and a PI value of 6.9.
  • Example 20 The procedure disclosed in Example 20 for the preparation of the catalyst component A was repeated with the difference that thirty grams of anhydrous iron (II) chloride (made by
  • Example 2 The polymerization was carried out according to the procedure disclosed in Example 1 using 5 mg of the solid catalyst component (B) obtained in Example 20, 5 mg of the above-obtained solid catalyst component (A), 91 mg of triethylaluminum and 16 mg of thexyltrimethoxysilane. Consequently, 34 g of a polypropylene powder was obtained.
  • Example 20 for the preparation of the catalyst component A was repeated with the difference that thirty grams of anhydrous iron (II) chloride ( by Aldrich) and
  • Example 2 The polymerization was carried out according to the procedure disclosed in Example 1 using 5 mg of the solid catalyst component (B) obtained in Example 20, 5 mg of the above-obtained solid catalyst component (B), 91 mg of triethylaluminum and 16 mg of texyltrimethoxysilane.
  • Example 20 for the preparation of the catalyst component A was repeated with the difference that thirty grams of anhydrous iron (II) chloride ( by Aldrich) and
  • Example 2 The polymerization was carried out according to the procedure disclosed in Example 1 using 5 mg of the solid catalyst component (B) obtained in Example 20, 5 mg of the above-obtained solid catalyst component (A), 91 mg of triethylaluminum and 16 mg of texyltrimethoxysilane.
  • Example 20 The procedure disclosed in Example 20 for the preparation of the catalyst component A was repeated with the difference that twenty grams of anhydrous manganese chloride and 5.1 g of
  • the polymerization was carried out according to the procedure disclosed in Example 1 using 5 mg of the above-obtained solid catalyst component (A), 5 mg of the solid catalyst component
  • Anhydrous magnesium chloride (7.14 g), 37.5 ml of decane and 35.1 ml of 2-ethylhexyl alcohol were mixed, and heated at 130°C for 2 hours to form a uniform solution.
  • To this uniform solution was added 1.4 g of 2,2-dipropyl-l,3-dimethoxypropane, and the mixture was further stirred at 130°C for 1 hour, and dissolved.
  • the resulting uniform solution was cooled to room temperature, and the total amount thereof was added dropwise to 200 ml of titanium tetrachloride held at -20°C for 1 hour. After the dropwise addition, the temperature of the resulting solution was raised to 110°C over a period of 4 hours, and then stirred at 110°C for 2 hours.
  • Example 2 The polymerization was carried out according to the procedure disclosed in Example 1 using 5 mg of the above-obtained solid catalyst component (A), 5 mg of the above-obtained solid catalyst component (B), 91 mg of triethylaluminum and 16 mg of texyltrimethoxysilane. Consequently, 79 g of a polypropylene powder was obtained having a XI of 97.0%, a MFR value of 5.4, and a PI value of 8.7.

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

Abstract

L'invention concerne un composant catalyseur pour la polymérisation d'oléfines de formule CH2=CHR dans laquelle R représente un groupe hydrocarbure C1-C20, comportant un composé de titane et un composé donneur d'électrons représenté par une formule spécifiée, lesdits composés étant supportés sur un composé de métal de transition choisi parmi Mn, Fe, Co, Ni et Zn. Ledit composant catalyseur produit une polyoléfine à répartition des poids moléculaires large (indice de polydispersité > 5,0), avec une bonne efficacité.
EP00971440A 1999-11-15 2000-11-10 Composant catalyseur solide pour la polymerisation d'olefines, catalyseur pour la polymerisation d'olefines et procede de production de polymere olefinique Withdrawn EP1141044A1 (fr)

Applications Claiming Priority (7)

Application Number Priority Date Filing Date Title
JP32421199 1999-11-15
JP32420999 1999-11-15
JP32422599A JP2001139622A (ja) 1999-11-15 1999-11-15 オレフィン重合用固体触媒成分、オレフィン重合用触媒及びオレフィン重合体の製造方法
JP32422599 1999-11-15
JP32421199A JP2001139618A (ja) 1999-11-15 1999-11-15 オレフィン重合用固体触媒成分、オレフィン重合用触媒及びオレフィン重合体の製造方法
JP32420999A JP2001139621A (ja) 1999-11-15 1999-11-15 オレフィン重合用固体触媒成分、オレフィン重合用触媒及びオレフィン重合体の製造方法
PCT/EP2000/011127 WO2001036496A1 (fr) 1999-11-15 2000-11-10 Composant catalyseur solide pour la polymerisation d'olefines, catalyseur pour la polymerisation d'olefines et procede de production de polymere olefinique

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EP1141044A1 true EP1141044A1 (fr) 2001-10-10

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EP1943281B1 (fr) 2005-10-14 2017-09-20 Basell Polyolefine GmbH Systèmes de catalyseurs hybrides supportés sur halogénure de magnésium
CN102803311B (zh) * 2009-04-23 2014-07-02 陶氏环球技术有限责任公司 具有金刚烷的前催化剂组合物和方法
SG177665A1 (en) 2009-07-15 2012-02-28 China Petroleum & Chemical Spherical magnesium halide adduct, catalyst component and catalyst for olefin polymerization prepared therefrom
JP2013082812A (ja) * 2011-10-11 2013-05-09 Sumitomo Chemical Co Ltd オレフィン重合用固体触媒成分の製造方法
SG11201509854SA (en) * 2013-06-03 2015-12-30 Lummus Novolen Technology Gmbh High performance ziegler-natta catalyst systems, processes for producing such catalyst systems, and use thereof
CN104761664A (zh) * 2015-03-13 2015-07-08 北京肯佰恩科技发展有限公司 用于烯烃聚合的催化剂组合物及其应用

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IT1037112B (it) * 1975-03-28 1979-11-10 Montedison Spa Catalizzatori per la polimerizzazione delle olfine
US4387200A (en) * 1980-10-01 1983-06-07 The Dow Chemical Company Process for polymerizing olefins employing a catalyst prepared from organomagnesium compound; oxygen- or nitrogen- containing compound; halide source; transition metal compound and reducing agent
US4814314A (en) * 1986-09-26 1989-03-21 Mitsubishi Petrochemical Company Limited Catalyst for olefin polymerization
JPH09208615A (ja) * 1995-11-28 1997-08-12 Mitsui Petrochem Ind Ltd 固体状チタン触媒成分の調製方法、触媒およびオレフィンの重合方法

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