WO2001036496A1

WO2001036496A1 - Solid catalyst component for olefin polymerization, catalyst for olefin polymerization and process for producing olefin polymer

Info

Publication number: WO2001036496A1
Application number: PCT/EP2000/011127
Authority: WO
Inventors: Masaki Fushimi
Original assignee: Basell Technology Company B.V.
Priority date: 1999-11-15
Filing date: 2000-11-10
Publication date: 2001-05-25
Also published as: JP2003514927A; EP1141044A1; AU1029701A

Abstract

A catalyst component for the polymerization of olefin of formula CH2=CHR where R is a C1-C20 hydrocarbon group, comprising a titanium compound and an electron donor compound of a formula specified below supported on a transition metal compound selected from Mn, Fe, Co, Ni and Zn. Said catalyst component gives a polyolefin having a broad molecular weight distribution (polydispersity index > 5.0) at good efficiency.

Description

SOLID CATALYST COMPONENT FOR OLEFIN POLYMERIZATION, CATALYST FOR OLEFIN POLYMERIZATION AND PROCESS FOR PRODUCING OLEFIN POLYMER.

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.

In particular the present invention relates to a catalyst component for the polymerization of olefins of formula CH₂=CHR where R is a C1-C20 hydrocarbon group, comprising a titanium compound and an electron donor compound of a formula specified below, and a transition metal compound selected from Mn, Fe, Co, Ni and Zn.

The use of a transition metal compound as a support for Ziegler catalyst components is known in the art.

For example, the use of an iron halogen crystal coated with molecular layer of a titanium compound is disclosed in the Japanese Patent Publication No. 12105/1964. 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. However, these catalysts are characterized by a low polymerization activity and in particular by a very low stereospecifϊcity because the amounts of isotactic polypropylene produced is extremely low, and it is far from satisfying the present industrial requirement.

Further, the use of 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 TiCl₃ 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 however, 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.

Moreover, the addition of a transition metal such as iron or the like in polymerization as disclosed in Japanese Patent Laid-Open Nos. 101104/1983, 194636/1993, 287708/1998 and

287709/1998 was also proposed. In these methods, however, the addition caused the decrease in the catalytic activity. As a consequence, the catalyst residues were so high that the resulting polymer was colored.

It would be therefore useful to have available an easily obtainable catalyst for olefin polymerization which can give a polyolefin having a broad molecular weight distribution

(polydispersity index (PI) > 5.0) at good 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.

It is therefore an object of the present invention 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):

Ri

X— ^z — Y (I)

R₂

wherein X and Y may be the same or different and each represents -CH OR₃, -COOR₃, -C R₃=O, -CHO, -CH₂OH or -CH₂OSi(R₃)₃ group, Z represents a carbon atom, a silicon atom, a methylene chain or a substituted methylene chain, R_{1 ?} R₂ and R₃ 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, and Ri or R₂ may be hydrogen. Preferably, the compound of transition metal is selected from the halides of manganese, iron, cobalt, nickel and zinc. In particular the chlorides of said metals are preferred. It is also preferable the use of those chlorides having the crystal structure of cadmium chloride. Examples of 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(OR₄)_n-pXp, where n is the valence of titanium, X is halogen, p is a number between 0 and n and R⁴ 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 TiCl₄ and TiCl₃; furthermore, also Ti- haloalcoholates can be advantageously used.

Examples of usable titanium compounds are 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. As mentioned above 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. Further, R₃ is preferably an alkyl group having 1 to 10 carbon atoms. When Ri is methyl, ethyl, propyl or isopropyl, R₂ may be ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, 2-ethylhexyl, cyclohexylmethyl, phenyl or benzyl. When Ri is hydrogen, R₂ may be ethyl, butyl, sec-butyl, tert-butyl, 2-ethylhexyl, cyclohexylethyl, diphenylme hyl, p-chlorophenyl, 1-naphthyl or 1-decahydronaphthyl. Still further, R¹ and R² may be the same, and may be ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, neopentyl, isopentyl, phenyl, benzyl or cyclohexyl.

Examples of this compound can include a diether compound in which X and Y are both - CH₂OR₃, a diester compound in which X and Y are both -COO R₃ group, a diketone compound in which X and Y are both -CR₃=O, a dinal compound in which X and Y are both - CHO, a diol compound in which X and Y are both -CH OH, a disiloxy compound in which X and Y are both -CH₂OSi(R₃)₃, an alkoxy ester compound in which X is -CH₂O R₃ and Y is - COOR₃, a keto ether compound in which X is -CH₂OR₃ and Y is -CR₃=O, and a keto ester compound in which X is -COOR₃ and Y is -CR₃=O. Of these, a diether compound, a diester compound, an alkoxy ester compound and a keto ester compound are preferable. Specific examples of 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-fluorophenyl)- 1 ,3- dimethoxypropane, 2-(l -decahydronaphthyl)-l ,3-dimethoxypropane, 2-(p-tert-butylphenyl)- 1,3-dimethoxypropane, 2,2-dicyclohexyl-l,3-dimethoxypropane, 2,2-diethyl-l,3- dimethoxypropane, 2,2-dipropyl-l ,3-dimethoxypropane, 2,2-dibutyl-l ,3-dimethoxypropane, 2-methyl-2-propyl-l,3-dimethoxypropane, 2-methyl-2-benzyl-l,3-dimethoxypropane, 2- methyl-2-ethyl-l ,3-dimethoxypropane, 2-methyl-2-phenyl-l ,3-dimethoxypropane, 2-methyl- 2-cyclohexyl-l,3-dimethoxypropane, 2,2-bis(p-chlorophenyl)-l,3-dimethoxypropane, 2,2- bis(2-cyclohexylethyl)- 1 ,3-dimethoxypropane, 2-methyl-2-isobutyl- 1 ,3-dimethoxypropane, 2- methyl-2-(2-ethylhexyl)-l,3-dimethoxypropane, 2-methyl-2-isopropyl-l,3-dimethoxypropane, 2,2-diisopropyl- 1 ,3-dimethoxypropane, 2,2-diphenyl- 1 ,3-dimethoxypropane, 2,2-dibenzyl- 1,3-dimethoxypropane, 2,2-bis(cyclohexylmethyl)-l,3-dimethoxypropane, 2,2-diisobutyl-l,3- diethoxypropane, 2,2-diisobutyl-l ,3-dibutoxypropane, 2-isobutyl-2-isopropyl-l ,3- dimethoxypropane, 2,2-di-sec -butyl- 1 ,3-dimethoxypropane, 2,2-di-tert-butyl-l,3- dimethoxypropane, 2-dineopentyl-l,3-dimethoxypropane, 2-isopropyl-2-isopentyl-l,3- dimethoxypropane, 2-phenyl-2-benzyl- 1 ,3-dimethoxypropane, 2-cyclohexyl-2- cyclohexylmethyl-1 ,3-dimethoxypropane, 2-isopropyl-3,7-dimethyloctyl-l ,3- dimethoxypropane, 2,2-diisopropyl-l,3-dimethoxypropane, 2-isopropyl-2-cyclohexyl-l,3- dimethoxypropane, 2-isopropyl-2-cyclopentyl-l ,3-dimethoxypropane, 2,2-dicyclopentyl-l ,3- dimethoxypropane, 2-heptyl-2-pentyl-l,3-dimethoxypropane and the like. Specific examples of the 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, diethyl 2-isopropyl-2-(2-cyclopentylethyl)malonate, diethyl 2- isopropyl-2-(2-cyclohexylethyl)malonate, diethyl 2-isobutyl-2-isopentylmalonate, diethyl 2- isobutyl-2-isohexylmalonate, diethyl 2-isobutyl-2-isoheptylmalonate, diethyl 2-isobutyl-2- cyclopentylmalonate, diethyl 2-isobutyl-2-cyclohexylmalonate, diethyl 2-isobutyl-2-(2- cyclopropylethyl)malonate, diethyl 2-isopentyl-2-isohexylmalonate, diethyl 2-isopentyl-2- isoheptylmalonate, diethyl 2-isopentyl-2-cyclopentylmalonate, diethyl 2-isopentyl-2-(2- cyclopentylethyl)malonate, diethyl 2-isohexyl-2-isoheptylmalonate, diethyl 2-isohexyl-2- cyclopentylmalonate, diethyl 2-isohexyl-2-(2-cyclopentylethyl)malonate, diethyl 2- cyclopentyl-2-cyclohexylmalonate, diethyl 2-cyclopentyl-2-(2-cyclopentylethyl)malonate, diethyl 2-(2-cyclopentylethyl)-2-(2-cyclohexylethyl)malonate and the like. Specific examples of the 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 2-ethoxycyclohexanecarboxylate, methyl 3- (ethoxymethyl)cyclohexanecarboxylate, methyl 3-ethoxynorbornane-2-carboxylate, butyl 2- methyl-2-isobropyl-3-ethoxypropionate, ethyl 2,2-diisoρropyl-3-methoxypropionate, ethyl 2,2-diisopropyl-3-methoxypropionate, methyl 2-isopropyl-2-isobutyl-3-methoxypropionate, ethyl 2-isopropyl-2-isobutyl-3-methoxypropionate, methyl 2-isopropyl-2-isopentyl-3- methoxypropionate, ethyl 2-isopropyl-2-isopentyl-3-methoxypropionate, ethyl 2,2-disobutyl-

3-methoxypropionate, methyl 2-cyclopentyl-2-isopentyl-3-methoxypropionate, ethyl 2,2- dicyclopentyl-3-methoxypropionate and the like.

Specific examples ofthe 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-

(isopropionyl)propionate, allyl 3-(isopropionyl)propionate, cyclohexyl 3-

(isopropionyl)propionate, ethyl 3-neopentanoylpropionate, butyl 3-n-laurylpropionate, methyl

3-(2,6-dimethylhexanoyl)propionate and the like.

The solid catalyst component ofthe invention can be prepared with different methods some of whose are disclosed below.

One ofthe preferred methods is that in which 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). For example 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 TiCl₄ at a temperature between 80 and 135°C. This treatment is followed by washings with hydrocarbon solvents until chloride ions disappeared.

In general 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

(a) and (b). In this method, the use of an organic compound in step (a) is preferred. As organic compounds can be used hydrocarbon compounds halogenated hydrocarbons and silicon organic compound. The use of silicon organic compounds is most preferred. In particular it is 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:

MX₂.qSi(R₄)_r(OR₅)_4-r (II) wherein 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 R₅ 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.

Specific examples of such an organic silicon compound as a component of the adduct mentioned above include tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetrabutoxysilane, methyltrimethoxysilane, ethyltrimethoxysilane, propyltrimethoxysilane, isopropyltrimethoxysilane, tert-butyltrimethoxysilane, methyltriethoxysilane, ethyltriethoxysilane, propyltriethoxysilane, isopropyltriethoxysilane, tert-butyltriethoxysilane, methyltributoxysilane, ethyltributoxysilane, propyltributoxysilane, isopropyltributoxysilane, tert-butyltributoxysilane, dimefhyldimethoxysilane, diethyldimethoxysilane, dipropyldimethoxysilane, diisopropoxydimethoxysilane, dibutyldimethoxysilane, dimethyldiethoxysilane, diethyldiethoxysilane, dipropyldiethoxysilane, diisopropoxydiethoxysilane, dibutyldiethoxysilane, dimethyldibutoxysilane, diethyldibutoxysilane, dipropyldibutoxysilane, diisopropoxydibutoxysilane, dibutyldibutoxysilane, trimethylmethoxysilane, triefhylmethoxysilane, tripropylmethoxysilane, tributylmethoxysilane, trimefhylethoxysilane, triethylethoxysilane, tripropylethoxysilane, tributylethoxysilane, trimethylbutoxysilane, triethylbutoxysilane, tripropylbutoxysilane, tributylbutoxysilane, dicyclopentyldimethoxysilane, dicyclopentyldiethoxysilane, cyclohexylmethyldimethoxysilane, cyclohexylethyldimethoxysilane, cyclohexylmethyldiethoxysilane, thexyltrimethoxysilane, thexyltriethoxysilane, thexyltripropoxysilane and thexyltributoxysilane.

The contact between the transition metal compound and the organic silicon compound in order to prepare the adduct can occur under different conditions. For example, 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. As an example of the use of said technique it can be said that by using 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.

In order to prepare the above disclosed adduct, 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. Generally, it is preferably that 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.

As explained above 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.

As the organoaluminum compound used in the catalyst for olefin polymerization of the invention, particularly preferred are those represented by the formula A1R⁶ _SX₃-_S where R is a hydrocarbon group having from 1 to 20 carbon atoms, X is halogen and s is from 1 to 3. Moreover, also preferred are the cyclic or linear organoaluminum compounds containing the repeating unit:

R7

(Al— O)u where R⁷ has the same meaning as R.

Especially preferred 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 AlEt₂Cl and Al₂Et₃Cl₃. Also alkylalumoxanes can be used.

In the production ofthe olefin polymer, 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.

In a particular embodiment, 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. Preferably said solid catalyst component B also contains an electron donor compound (D2). In a particularly preferred aspect 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. Especially preferred are the catalyst components (B) in which the Ti compound is TiCl₄ 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. Preferably, it is selected from esters of organic mono or bicarboxylic acids in particular benzoates, phthalates and succinates, and from the class of diethers disclosed above. 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 TiCl₄ at a temperature between 80 and 135°C. This treatment is followed by washings with hydrocarbon solvents until chloride ions disappeared. According to a further method, 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. 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 TiCl₄ comprising the electron donor compound in solution at a temperature of about 80 to 120°C. According to a preferred method, the solid catalyst component can be prepared by reacting a titanium compound of formula Ti(OR₄)_n-pX_p, where n is the valence of titanium, X is halogen, p is a number between 0 and n and R⁴ has the same meaning of R, preferably TiCl₄, 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 TiCl₄ (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 TiCl₄ can be carried out one or more times. The succinate of formula (I) can be added during the treatment with TiCl₄. 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.

Further, 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).

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). In particular 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. Among them, 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 ⁸R_b ⁹Si(OR¹⁰)_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; R⁸, R⁹, and R¹⁰ are C1-C18 hydrocarbon groups optionally containing heteroatoms.

Specific examples of the organosilicon compound having the alkoxy group 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-butylisopropyldimethoxysilane, tert-butyl-n- butyldimethoxysilane, tert-butylisobutyldimethoxysilane, tert-butyl-(sec- butyl)dimethoxysilane, tert-butylamyldimethoxysilane, tert-butylhexyldimethoxysilane, tert- butylheptyldimethoxysilane, tert-butyloctyldimethoxysilane, tert-butylnonyldimethoxysilane, tert-butyldecylmethoxysilane, tert-butyl(3,3,3-trifluoromethylpropyl)dimethoxysilane, tert- butyl(cyclopentyl)dimethoxysilane, tert-butyl(cyclohexyl)dimethoxysilane, dicyclopentyldimethoxysilane, bis(2-methylcyclopentyl)dimethoxysilane, bis(2,3- dimefhylcyclopentyl)dimethoxysilane, diphenyldimethoxysilane, phenyltriethoxysilane, mesityltrimethoxysilane, ethyltrimethoxysilane, n-propyltrimethoxysilane, isopropyltrimethoxysilane, butyltrimethoxysilane, isobutyltrimethoxysilane, tert- butyltrimethoxysilane, sec-butyltrimethoxysilane, amyltrimethoxysilane, isoamyltrimethoxysilane, cyclopentyltrimethoxysilane, cyclohexyltrimethoxysilane, norbornanetrimethoxysilane, indenyltrimethoxysilane, 2-methylcyclopentyltrimethoxysilane, cyclopentyl(tert-butoxy)dimethoxysilane, isopropyl(tert-butoxy)dimethoxysilane, tert- butyl(isobutoxy)dimethoxysilane, tert-butyl(tert-butoxy)dimethoxysilane, tert-butyl(2,6- dimethylpiperidyl)dimethoxysilane, tert-butyl(3,3,3-trifluoropropyl)dimethoxysilane, thexyltrimethoxysilane, thexyl(isopropoxy)dimethoxysilane, thexyl(tert- butoxy)dimethoxysilane, thexyl(pyrrolidyl)dimethoxysilane, thexyl(2,6- dimethylpiperidyl)dimethoxysilane and the like.

Specific examples of the nitrogen-containing compound 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. 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).

In practicing the polymerization, 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 value of a polydispersity index (PI) of the polymer produced with the above catalyst system is generally higher than 5.0. 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. When the polymerization is carried out in gas-phase the operating pressure is generally between 0.5 and 10 MPa, preferably between 1 and 5 MPa. In the bulk polymerization 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.

Moreover, with respect to the prepolymerization, the type of the polymerization reactor, the method for controlling the polymerization, the post-treatment method and the like, all of known methods can be applied without any peculiar limitation in the present catalyst system.

The invention is illustrated more specifically below by referring to Examples.

EXAMPLES

In Examples, compounds (organic solvent, olefin, hydrogen, titanium compound, transition metal halogen compound, silicon compound and the like) used in the production of a solid catalyst component and in the polymerization were all substantially free of water.

Further, 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

25°C. 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

Chem. Eng., Montreal, Can., 1981.

Example 1

Preparation of a solid catalyst component

Anhydrous manganese chloride (30 g) and 5.1 g of 2-isopropyl-2-isopentyl-l,3- diemethoxypropane were charged into a 1 -liter cylindrical container filled with magnetic balls

10 mm in diameter with an apparent volume of 50%, and co-pulverized for 12 hours with a vibration mill having an amplitude of 9 mm.

Separately, 120 ml of toluene and 120 ml of titanium tetrachloride were added to a flask having an internal volume of 500 ml, reacted, and heated at 60°C. The co-pulverized solid material was charged in this solution, and the mixture was stirred at 110°C for 2 hours. The contents ofthe flask were washed three times with 200 ml of toluene, and dried at 30°C under reduced pressure.

Polymerization

A 1.5-liter stainless steel autoclave was charged with 12 mg of the above-obtained solid catalyst component, 91 mg of triethylaluminum and 16 mg of texyltrimethoxysilane. Then,

340 g of propylene and 0.03 g of hydrogen were charged. The autoclave was heated, and the inner temperature was kept at 70°C. After 1 hour, the gases therein were released to complete the polymerization. Consequently, 26 g of a polypropylene powder was obtained having a XI of97.2% and a PI of 9.8.

Comparative Example 1 Preparation of a solid catalyst component

The procedure disclosed in Example 1 was repeated with the only difference that anhydrous magnesium chloride was used instead of MnCl₂.

Polymerization

The polymerization was carried out according to the procedure disclosed in Example 1 using

13 mg of the above-obtained solid catalyst component. 91 mg of triethylaluminum and 16 mg of texyltrimethoxysilane. 52 g of a polypropylene powder was obtained having a XI of 96.9% and a PI value of 3.8.

Comparative Example 2

Preparation of a solid catalyst component

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-

2-isopentyl-l,3-dimethoxypropane were charged into the vibrating mill.

Polymerization

10 mg of the above-obtained solid catalyst component, 91 mg of triethylaluminum and 16 mg of texyltrimethoxysilane. Consequently, 41 g of a polypropylene powder was obtained having a XI of 95.1% and a PI value of 4.1.

Example 2

Preparation of a solid catalyst component

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.

Polym erization

15 mg of the above-obtained solid catalyst component, 91 mg of triethylaluminum and 16 mg of texyltrimethoxysilane. Consequently, 21 g of a polypropylene powder was obtained having a XI of 96.4% and a PI value of 10.3.

Example 3

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

96.7% and a PI value of 10.8.

Example 4

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.

Example 5

Preparation of a solid catalyst component

Five g of anhydrous iron(II) chloride (by Aldrich), 0.85 of 2-isopropyl-2-isopentyl-l,3- dimethoxypropane and 25 ml of methyl chloride were charged into a 300 ml flask dried fully under a stream of nitrogen. After being stirred for 1 hour, this suspended solution was transferred to titanium tetrachloride in the 200-ml flask by a method of high pressure. The temperature of this solution was gradually raised to 110°C. Then, this solution was reacted at

110°C for 2 hours under stirring. After the completion of the reaction, the solid portion was filtered, and washed three times with 200 ml of n-decane at 110°C. The solid portion was added to 200 ml of titanium tetrachloride, and reacted at 120°C for 2 hours. After the completion of the reaction, the solid portion was washed with n-hexane at room temperature.

This washing was conducted until the chlorine ion was not detected in the washed solution.

Polymerization

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

XI of 98.1 % and a PI value of 8.7.

Example 6

Preparation of a solid catalyst component

The procedure disclosed in Example 5 was repeated with the only difference that 1.06 g of

2,2-diisopentylmalonate were used instead of 2-isopropyl-2-isopentyl-l,3-dimethoxypropane. Polymerization

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

XI of 97.3% and a PI value of 10.8.

Example 7

Preparation of a solid catalyst component

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 .

Polymerization

8 mg of the above-obtained solid catalyst component, 91 mg of triethylaluminum and 16 mg of texyltrimethoxysilane. Consequently, 67 g of a polypropylene powder was obtained. XI of this polypropylene powder was 98.2 %. The PI value was 10.5.

Example 8

Preparation of a solid catalyst component

The procedure disclosed in Example 5 was repeated with the only difference that 0.62 g of 3-

(isopropyl) ethyl propionate were used instead of 2-isopropyl-2-isopentyl-l,3- dimethoxypropane.

Polym erization

11 mg of the above-obtained solid catalyst component, 91 mg of triethylaluminum and 16 mg of texyltrimethoxysilane. Consequently, 49 g of a polypropylene powder was obtained having a XI of 97.1 % and a PI value of 9.6.

Example 9

Preparation of a solid catalyst component

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 The 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.

Example 10

Preparation ofthe adduct

Twenty (20) g of 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

Hz. Then, the contents were washed 6 times with 200 ml of hexane for each time at the temperature of 60°C followed by a vacuum drying.

A solid substance was thus obtained containing 19.6 weight % of tetraethoxysilane and 35.8 weight % of iron atom therefore corresponding to the formula FeCl₂ ^»0.15(Si(OC₂H5)₄).

Preparation of a solid catalyst component

Five (5.0) g of the solid substance thus obtained, 50 ml of toluene and 30 ml of titanium tetrachloride were introduced into a flask having an inner volume of 200 ml and underwent reaction during 2 hours at the temperature of 100°C. After the cooling of the content in the flask to room temperature, 0.65 g of 2,2-diisobutyl-l,3-dimethoxypropane was added. The solid substance was filtered after the stirring under heating during 2 hours at 100°C. The so obtained solid was washed 5 times with (5x100 ml) toluene at 60°C, then washed (3 x 100 ml) with hexane at room temperature followed by a drying under a reduced pressure.

Polymerization

11 mg of the solid substance obtained as mentioned above, 91 mg of triethylaluminium and

16mg of thexyltrimethoxysilane. As a result, 24 g of a polypropylene powder was obtained having an XI of 99.2%, and PI of 9.7.

Example 11

Preparation ofthe adduct

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

FeC12O.31Si(OC₂H₅)₄.

Preparation of a solid catalyst component

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.

Polymerization

10 mg ofthe solid substance obtained as mentioned above, 91 mg of triethylaluminium and 16 mg of thexyltrimethoxysilane. As a result, 31 g of a polypropylene powder was obtained having XI of 98.7%, and PI of 10.8

Example 12

Preparation ofthe adduct

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.

Preparation of a solid catalyst component

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.

Polymerization

11 mg of the solid substance obtained as mentioned above, 91 mg of triethylaluminum and 16 mg of thexyltrimethoxysilane. As a result, 25 g of a polypropylene powder was obtained having XI of 98.6%, and PI of 11.8.

Example 13

Preparation ofthe adduct

Ten (10) g of ferrous chloride anhydride (II) purchased from Aldrich, 16.3 g of tetraethoxysilane (Si/Fe molar ratio was 1.0) and 100 ml of toluene were introduced into a double-inlet flask equipped with a Dimroth condenser having an inner volume of 200 ml, and then heated with flux for 2 hours. The solid substance was filtered down to room temperature, then the contents were washed 6 times with 100 ml of hexane for each time at the temperature of 60°C, followed by a vacuum drying to obtain the adduct. The chemical formula of this solid substance is FeC12»0.6(Si (OC2H5)4) calculated from the values of 49.4 weight % of tetraethoxysilane and 22.5 weight % of iron atom therein.

Preparation of a solid catalyst component

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.

Polymerization

The polymerization was carried out according to the procedure disclosed in Example 1 using 9 mg ofthe solid substance obtained as mentioned above, 91 mg of triethylaluminum and 16 mg of thexyltrimethoxysilane. As a result, 24 g of a polypropylene powder was obtained having

XI of 99.0%, and PI of 9.5.

Example 14

Preparation ofthe adduct

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 FeCl₂*0.4Si (OCH₃)₄ calculated from the values of 32.2 weight % of tetramethoxysilane and 30.2 weight % of iron atom therein.

Preparation of a solid catalyst component

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.

Polymerization

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 15

Preparation of a solid catalyst component

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.

Polymerization

11 mg of the solid component obtained as mentioned above, 91 mg of triethylaluminum and 16mg of thexyltrimethoxysilane. As a result, 31 g of a polypropylene powder was obtained having XI of 98.8%, and PI of 12.8.

Example 16

Preparation of a solid catalyst compound

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.

Polymerization

10 mg of the solid substance obtained as mentioned above, 91 mg of triethylaluminum and

16mg of thexyltrimethoxysilane As a result, 32 g of a polypropylene powder was obtained having XI of 98.4%, and PI of 8.4.

Example 17

Polymerization

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 18

Preparation ofthe adduct

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 MnCl₂*0.16Si(OC₂H₅)₄ calculated from the values of 20.9 weight % of tetraethoxysilane and 34.5 weight % of manganese atom therein.

Preparation of a solid catalyst component

The procedure of Example 10 was repeated using the adduct obtained as described above. Polymerization

22 mg of the solid substance obtained as mentioned above, 91 mg of triethylaluminum and

16mg of thexyltrimethoxysilane. As a result, 20 g of a polypropylene powder was obtained having a XI of 98.2% and a PI of 10.3.

Example 19

Preparation ofthe adduct

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 CoCl₂'0.11Si(OC H₅)₄ calculated from the values of 14.9 weight % of tetraethoxysilane and 38.8 weight % of cobalt atom therein.

Preparation of a solid catalyst component

The procedure of Example 10 was repeated using the adduct obtained as described above.

Polymerization

15 mg of the solid substance obtained as mentioned above, 91 mg of triethylaluminum and

16mg of thexyltrimethoxysilane. As a result, 20 g of a polypropylene powder was obtained having a XI of 98.3%, and a PI of 6.8.

Example 20

Preparation of a solid catalyst component (A)

Thirty grams of anhydrous iron (II) chloride (made by Aldrich) and 5.1 g of 2-isopropyl-2- isopentyl-1,3- were charged into a 1 -liter cylindrical container filled with ceramic balls 10 mm in diameter with an apparent volume of 50%, and co-pulverized for 12 hours with a vibration mill having an amplitude of 9 mm.

Preparation of a solid catalyst component (B) Twenty grams of anhydrous magnesium chloride and 5.9 g of di-n-butyl phthalate were charged into a 1 -liter cylindrical container filled with ceramic ball 10 mm in diameter with an apparent volume of 50%, and co-pulverized for 12 hours with a vibration mill having amplitude of 9 mm.

Separately, 120 ml of toluene and 120 ml of titanium tetrachloride were added to a flask having an internal volume of 500 ml, reacted, and heated at 60°C The co-pulverized solid material was charged in this solution, and the mixture was stirred at 1 10°C for 2 hours. The contents of the flask were washed three times with 200 ml of toluene, and dried at 30°C under reduced pressure.

Polymerization

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, 30 g of a polypropylene powder was obtained having XI of 97.1%, a MFR value of 5.6, and the PI value of 8.6.

Comparative Example 3

15 mg of the solid catalyst component (B) obtained in Example 20, 91 mg of triethylaluminum and 16 mg of texyltrimethoxysilane. Consequently, 63 g of a polypropylene powder was obtained having XI of this polypropylene powder was 97.0%, a MFR value of

15.0, and a PI value of 4.0.

Comparative Example 4

Preparation of a solid catalyst component

The procedure disclosed in the preparation of the catalyst component (A) of Example 20 was repeated with the difference that anhydrous magnesium chloride (9.4 g), 12.8 g of anhydrous iron (II) chloride (by Aldrich) and 5.6 g of di-n-butyl phthalate were used as starting components.

Polymerization

15 mg of the above-obtained solid catalyst component, 91 mg of triethylaluminum and 16 mg of thexyltrimethoxysilane. Consequently, 54.0 g of a polypropylene powder was obtained. XI of this polypropylene powder was 96.2%, the MFR value was 4.0 and the PI value was 4.7. Comparative Example 5 Preparation of a solid catalyst component

The procedure disclosed in the preparation of the catalyst component (B) of Example 20 was repeated with the difference that twenty grams of anhydrous magnesium chloride, 3.1 g of din-butyl phthalate and 3.0 g of 2-isopropyl-2-isopentyl-l,3-dimethoxypropane were charged in the mill. Polymerization

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

The procedure disclosed for the preparation ofthe catalyst component (A) of Example 20 was repeated with the difference that anhydrous magnesium chloride (9.4 g), 12.8 g of anhydrous iron (II) chloride ( by Aldrich), 2.8 g of di-n-butyl phthalate and 2.7 g of 2-isopropyl-2- isopentyl-l,3-dimethoxypropane were charged into the vibrating mill. Polymerization

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

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 22

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 23

Preparation of a solid catalyst component (A)

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

Aldrich) and 3.6 g of ethyl 3-methoxy-3-tert-butylpropionate were charged the vibrating mill.

Polymerization

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.

XI of this polypropylene powder was 97.2%. The MFR value was 9.1, and the PI value was

8.6.

Example 24

Preparation of a solid catalyst component (A)

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 ( by Aldrich) and

7.1 g of diethyl 2,2-diisopentylmalonate were charged into the vibrating mill.

Polymerization

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.

Consequently, 33 g of a polypropylene powder was obtained having a XI of 96.9%, a MFR value of 8.0, and a PI value of 8.1. Example 25

Preparation of a solid catalyst component (A)

4.4 g of butyl 3-propionylpropionate were charged into a vibrating mill.

Polymerization

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.

Consequently, 27 g of a polypropylene powder was obtained having a XI of 97.0%, a MFR value of 7.6, and a PI value of 9.2.

Example 26

Preparation of a solid catalyst component (A)

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

2,2-isobutyl-l,3-dimethoxypropane were charged into the vibrating mill.

Polymerization

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

(B) obtained in Example 20, 91 mg of triethylaluminum and 16 mg of texyltrimethoxysilane.

Consequently, 34 g of a polypropylene powder was obtained having a XI of 97.3%, a MFR value of 8.4, and the PI value of 8.5.

Example 27

Preparation of a solid catalyst component (A)

Anhydrous iron (II) chloride (9.3 g) and 50 ml of decane were mixed, and heated at 130°C for

2 hours to form a slurry solution. To this slurry solution was added 1.4 g of 2,2-diisopropyl-

1,3-dimethoxypropane, and the mixture was further stirred at 130°C for 1 hour. The resulting slurry solution was cooled to room temperature, and the total amount thereof was then 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. After the completion of the reaction for 2 hours, the solid portion was recovered through heat filtration. This solid portion was suspended in 275 ml of titanium tetrachloride, and then reheated at 110°C for 2 hours. After the completion of the reaction, the solid portion was recovered through heat filtration, and washed at 110°C using decane and hexane. This washing was conducted until the titanium compound was not detected in the wash solution, and the solution was then dried at 30°C under reduced pressure. Preparation of a solid catalyst component (B)

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.

After the completion of the reaction for 2 hours, the solid portion was recovered through filtration. This solid portion was suspended in 275 ml of titanium tetrachloride, and then reheated at 110°C for 2 hours. After the completion of the reaction, the solid portion was recovered through filtration, and washed at 110°C using decane and hexane. This washing was conducted until the titanium compound was not detected in the wash solution, and the solid portion was then dried under reduced pressure. Polymerization

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.

Claims

1. A solid catalyst component (A) for olefin polymerization comprising a titanium compound, an electron donor compound (Dl), and a compound of a transition metal selected from Mn, Fe, Co, Ni and Zn, said electron-donor compound (Dl) being selected from those of formula (I) :

X— Z _γ (I)

R₂ wherein X and Y may be the same or different and each represents -CH₂OR₃, -COOR₃, -

C R₃=O, -CHO, -CH₂OH or -CH₂OSi(R₃)₃ group, Z represents a carbon atom, a silicon atom, a methylene chain or a substituted methylene chain, R_{l s} R₂ and R₃ 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, and Ri or R₂ may be hydrogen.

2. A catalyst component according to claim 1 in which the compound of transition metal is selected from the halides of manganese, iron, cobalt, nickel and zinc.

3. A catalyst component according to claim 2 in which the halides are chlorides.

4. A catalyst component according to claim 1 in which the titanium compound is selected from those of formula Ti(OR )_n-pX_p, where n is the valence of titanium, X is halogen, p is a number between 0 and n and R₄ is a C1-C20 hydrocarbon group.

5. A catalyst component according to claim 1 in which Z is a carbon atom, Ri and R₂ are hydrogen or alkyl group and X and Y are both CH₂OR₃ groups

6. A catalyst component according to claim 1 in which Z is a carbon atom, Ri and R are hydrogen or alkyl group and X and Y are both -COOR₃ groups.

7. A catalyst component according to claim 1 in which Dl is an alkoxy ester compound.

8. Catalyst component according to claim 1 obtained by contacting a titanium halide with the solid obtained by co-milling the transition metal halide and an electron-donor compound (Dl).

9. Catalyst component according to claim 1 obtained by (a) contacting the transition metal compound with one or more organic or inorganic compounds, and then (b) contacting the resulting product with a titanium halide; the electron-donor compound (Dl) being present in at least one ofthe steps (a) and (b).

10. Catalyst component according to claim 9 in which the organic compound is a silicon organic compound.

11. Catalyst component according to claim 9 which is obtained by (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.

12. Catalyst component according to claim 11 in which the adduct has the formula: MX₂.qSi(R₄)_r(OR₅)_4-r (II) wherein M represents a manganese, an iron, a cobalt, a nickel or a zinc atom, X represents a halogen atom, R_t and R₅ may be same or different, each represents a hydrocarbon group having 18 or less 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.

13. Catalyst component according to claim 1 which is contacted with another solid catalyst component (B) comprising Ti, Mg, and halogen as essential elements.

14. Catalyst component according to claim 13 in which the catalyst component (B) also contains an electron donor compound (D2).

15. Catalyst component according to claim 14 in which the solid catalyst component (B) comprises a titanium compound having at least one Ti-halogen bond and an the electron donor compound (D2) supported on a Mg halide.

16. Catalyst component according to claim 15 in which (D2) is selected from ethers, ketones, amines and esters of organic mono or bicarboxylic acids.

17. Catalyst component according to claim 16 in which (D2) is selected from phthalates, benzoates, glutarates, and succinates.

18. Catalyst for the (co)polymerization of olefins of formula CH₂=CHR where R is a C1-C20 hydrocarbon group comprising a solid catalyst component according to any of preceding claims and an organoaluminum compound.

19. Catalyst according to claim 18 in which the organo aluminum compound has the formula A1R⁶ _SX_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.

20. Catalyst according to claim 19 in which the organoaluminum compound is an aluminum trialkyl.

21. Process for the (co)polymerization of olefins of formula CH₂=CHR where R is a C1-C20 hydrocarbon group.