FR2502629A1 - CATALYST FOR POLYMERIZATION OF OLEFINS - Google Patents

Abstract

THE OBJECT OF THE INVENTION IS AN IMPROVEMENT OF OLEFIN POLYMERIZATION CATALYSTS COMPRISING A SOLID CATALYTIC COMPONENT AND AN ORGANOMETAL COMPOUND. ACCORDING TO THE INVENTION, THE SOLID CATALYTIC COMPONENT IS A SUBSTANCE OBTAINED BY CONTACT AND REACTION OF THE FOLLOWING COMPOUNDS: 1 AT LEAST ONE COMPOUND CHOSEN FROM SILICON OXIDES AND ALUMINUM OXIDES; 2A MAGNESIUM HALOGENIDE; 3A COMPOUND REPRESENTED BY THE GENERAL FORMULA ME (OR) X IN WHICH ME IS AN ELEMENT BELONGING TO GROUPS IA IV OF THE PERIODIC CLASSIFICATION OF THE ELEMENTS, Z IS THE VALENCE OF ME, THE COEFFICIENT N SATISFIED THE RELATION OZ, X IS AN ATOM D 'HALOGEN ET R IS A CC HYDROCARBON RADICAL; 4 AT LEAST ONE COMPOUND CHOSEN FROM TITANIUM COMPOUNDS AND VANADIUM COMPOUNDS; AND 5AT AT LEAST ONE COMPOUND CHOSEN FROM THE COMPOUNDS REPRESENTED BY THE GENERAL FORMULA RSI (OR) X IN WHICH R AND R EACH REPRESENTS A CC HYDROCRABIDE RADICAL, X IS A HALOGEN ATOM, N SATISFIED THE ON4 RELATION AND M SATISFIED THE OM4 RELATIONSHIP, WITH THE ADDITIONAL OMN4 CONDITION, AND A POLYSILOXANE.

Description

The present invention relates to a novel catalyst

  for the polymerization of olefins.

  Various catalysts comprising, to date, inorganic solid magnesium compounds, such as magnesium halides, magnesium oxide and magnesium hydroxide, and transition metal compounds, such as titanium and vanadium compounds, deposited on these supports. However, if we polymerize

  olefins using these known catalysts, the density

  The resulting polymer is generally low, the average particle size is relatively small and the particle size distribution is generally large, so that the fine particles occupy a fairly large fraction, which causes serious disadvantages in the aspects of productivity and handling. . In addition, when the resulting polymer is molded, there are problems such as dust generation and decreased efficiency in the molding operation. It has therefore been strongly desired to increase the apparent density and to reduce the proportion of fine particles. Furthermore, for application to a treatment process in which a pelletizing step is suppressed and the powdered polymer is directly introduced into a processing machine, the demand of which has recently increased, it is considered that further improvements are required.

are necessary.

  The object of the invention is to remedy the drawbacks

mentioned above.

  Still another object of the invention is a novel polymerization catalyst which can provide olefin polymers having a high bulk density, a high average particle size, a narrow particle size distribution, and a high molecular weight ratio.

  remarkably low fine particles.

  Other objects and advantages of the invention

  will read the description which follows.

  The above objects of the invention are achieved by using an olefin polymerization catalyst which comprises a solid catalyst component and an organometallic compound, said solid catalyst component consisting of a substance obtained by contacting and reacting the following compounds: 1) a silicon oxide and / or an aluminum oxide, (2) a magnesium halide, (3) a compound represented by the general formula Me (OR) nXz.n wherein Me is an element belonging to groups I -IV of the Periodic Table of Elements, z is the valence of

  the element Me, the coefficient n satisfies the relation

  wherein X is a halogen atom and R is a C1-C24 hydrocarbon radical, (4) a titanium compound or a vanadium compound, and (5) a compound represented by the formula General

  R "Si (OR ') mX4 mn in which R' and R" represent

  each of which is a C -C 24 hydrocarbon radical: X is a halogen atom, n satisfies the relationship n 0 <4 and m satisfies the relation O <mc 4, with the additional condition

  0O m + n-4, and / or a polysiloxane.

  The silicon oxide used according to the invention is silica or a double oxide of silicon and at least one other

  Group I-VIII metal of the Periodic Table of Elements.

  The aluminum oxide used according to the invention is alumina or a double oxide of aluminum and at least one other metal

  groups I-VIII of the Periodic Table of Elements.

  As dual oxides of silicon or aluminum and at least one other group I-VIII metal of the Periodic Table, various natural and synthetic double oxides may be used; characteristic examples are A1203, MgO; A1203, CaO; A1203, SiO2; A1203, MgOCaO; A1203, MgOSiO2; A1203, CuO; A1203, Fe203; A1203, NiO; and SiO2, MgO. These formulas are not molecular formulas, they represent only compositions. The structure and ratio of the components of the double oxides that can

  used according to the invention are not especially limited.

  Of course, the silicon oxide and / or aluminum oxide used according to the invention can adsorb a small amount of moisture W

  and may contain small amounts of impurities.

  As magnesium halides used according to the invention,

  It is possible to use substantially anhydrous halides, for example magnesium fluoride, magnesium chloride, magnesium bromide and magnesium iodide, more particularly

magnesium chloride.

  According to the invention, these magnesium halides may have been treated by an electron donor such as an alcohol, an ester, a ketone, a carboxylic acid, an ether or an amine

or a phosphine.

  As a compound used according to the invention represented by the general formula Me (OR) X in which Me is an element n zn belonging to groups 1-IV of the Periodic Table such as Na, Mg, Ca, Zn, Cd, B or A1 , z is the valence of the element Me, the coefficient n obeys the relation 0 <nz, X is a halogen atom and the radicals R may be identical or different and each represent a hydrocarbon radical C1-C20 such as an alkyl, aryl or arylalkyl group, various compounds can be used, for example those represented by the following formulas: NaOR, Mg (OR) 2, Mg (OR) X, Ca (OR) 2, Zn (OR) 2, Cd (OR) 2, B (OR) 3, Al (OR) 3, Al (OR) 2X and Al (OR) X 2. More particularly, the following compounds are preferred: Mg (OC2H5) 2, Mg (OC2H5) C1, Al (OCH3) 3, Al (OC2H5) 3, Al (On-C3L) 3, Al (O1-C3H7) 3, Al (On-C 4 H 9) 3, Al (Osec-C 4 H) 3, AlI (Ot-C 4 H 9) 3, Al (OCH 3) 2 Cl,

3 7 3-14 9 33 4 9 3> 14933 -

  Al (OC2H5) 2Cl, AL (OC2H5) 2Cl2, Al (O1-C3H7) 2Cl and Al (O1-C3H7) Cl2.

  Examples of the titanium compound and / or vanadium compound used according to the invention include halides, alkoxyhalides, alkylates and halogenated oxides of titanium and / or vanadium. The preferred titanium compounds are the tetravalent titanium and trivalent titanium compounds and the preferred tetravalent titanium compounds are those represented by the general formula Ti (OR) nX 4 -n wherein R is a C 1 -C 20 alkyl, aryl or arylalkyl group, X is a halogen atom and n obeys the relation O0 nS 4; examples of these compounds are titanium tetrachloride, titanium tetrabromide, titanium tetraiodide,

  monomethoxytrichlorotitanium, dimethoxydichlorotitanium, tris-

  methoxymonochlorotitanium, tetramethoxytitanium, monoethoxytri

  chlorotitanium, diethoxydicllorotitanium, triethoxymonochloro-

2502 62 9

  titanium, tetraethoxytitanium, monoisopropoxytrichlorotitanium, diisopropoxydichlorotitanium, triisopropoxymonochlorotitanium,

  tetraisopropoxytitanium, monobutoxytrichlorotitanium, dibutoxy-

  dichlorotitan, monopentoxytrichlorotitanium, monophenoxy-

  trichlorotitanium, diphenoxydichlorotitanium, triphenoxymono-

  chlorotitan and tetraphenoxytitanium.

  Examples of trivalent titanium compounds include

  titanium trihalides obtained by reduction of the tetra-

  halides of titanetels titanium tetrachloride and tetra-

  titanium bromide, hydrogen, aluminum, titanium or

  organometallic compound of a Group I-III metal of Class

  Periodic acidification, as well as trivalent titanium compounds obtained by reduction of tetravalent titanium alkoxyhalides of the general formula Ti (OR) mX4.m wherein R is a C1-C20 alkyl, aryl or arylalkyl group, X is an atom of halogen and m obeys the relationship O <m 4, by an organometallic compound of a metal of groups I-III of the Periodic Table. Examples of vanadium compounds are tetravalent vanadium compounds

  such as vanadium tetrachloride, vanadium tetrabromide, tetra

  vanadium iodide and tetraethoxyvanadium, vanadium compounds

  pentavalent such as vanadium oxytrichloride, ethoxydichlorovan

  dyl, triethoxyvanadyl and tributoxyvanadyl and trivalent vanadium compounds such as vanadium trichloride and triethylate

of vanadium.

  To make the catalyst of the invention more efficient, the titanium compound and the vanadium compound are often used together and in this case the molar ratio V / Ti is preferably

from 2/1 to 0.01 / 1.

  As a compound used according to the invention and represented by the general formula R "nSi (OR ') mX4mn in which R' and R" nm 4-m-nanlauleRet "each represent a hydrocarbon radical such as an alkyl or aryl group or C 1 -C 24 arylalkyl, X is a halogen atom, n is 0 to n <4, m is 0K mf 4, and m and n are 0 <m + n C 4; can use by

  the following compounds: monomethyltrimethoxysilane, mono-

  methyltriethoxysilane, monomethyltri-n-butoxysilane, monomethyl-

  tri-sec-butoxysilane, monomethyltriisopropoxysilane, monomethyl-

250oZ62 Y

  tripentoxysilane, monomethyltrioctoxysilane, monomethyltristearoxy

  silane, monomethyltriphenoxysilane, dimethyldimethoxysilane, dimethyl

  diethoxysilane, dimethyldiisopropoxysilane, dimethyldiphenoxysilane,

  trimethylmonomethoxysilane, trimethylmonoethoxysilane, trimethyl

  monoisopropoxysilane, trimethylmonophenoxysilane, monomethyldimethoxy-

  monochlorosilane, monomethyldiethoxymonochlorosilane, monomethyl

  monoethoxydichlorosilane, monomethyldiethoxymonochlorosilane, mono-

  methyldiethoxymonobromosilane, monomethyldiphenoxymonochlorosilane, dimethylmonoethoxymonochlorosilane, monoethyltrimethoxysilane,

  monoethyltriethoxysilane, monoethyltriisopropoxysilane, monoethyl-

  triphenoxysilane, diethyldimethoxysilane, diethyldiethoxysilane,

  diethyldiphenoxysilane, triethylmonomethoxysilane, triethylmono-

  phenoxysilane, monoethyldimethoxymonochlorosilane, monoethyldiethoxy-

  monochlorosilane, monoethyldiphenoxymonochlorosilane, monoisopropyl-

  trimethoxysilane, mono-n-butyltrimethoxysilane, mono-n-butyltriethoxy-

  silane, mono-sec-butyltriethoxysilane, monophenyltriethoxysilane,

  diphenyldiethoxysilane, diphenylmonoethoxymonochlorosilane, mono-

  methoxytrichlorosilane, monoethoxytrichlorosilane, monoisopropoxy-

  trichlorosilane, mono-n-butoxytrichlorosilane, monopentoxytrichloro

  silane, monooctoxytrichlorosilane, monostearoxytrichlorosilane, monophenoxytrichlorosilane, mono-p-methylphenoxytrichlorosilane,

  dimethoxydichlorosilane, diethoxydichlorosilane, diisopropoxy-

  dichlorosilane, di-n-butoxydichlorosilane, dioctoxydichlorosilane,

  trimethoxymonochlorosilane, triethoxymonochlorosilane, triisopropoxy-

  monochlorosilane, tri-n-butoxymonochlorosilane, tri-sec-butoxymono-

  chlorosilane, tetracoxysilane and tetraisopropoxysilane.

  It is also possible to use according to the invention the

  open-chain or cyclic polysiloxanes resulting from condensation

  of the above compounds, having repeating units Y represented by the formula - 4 - Si - O -) - in which Y and Z z

  each represents R ", (OR ') or a halogen.

  Compounds represented by the general formula

  If (OR ') mX4.m are particularly preferred according to the invention.

  The order and the method of contact and reaction of the compounds 1 to 5 according to the invention are not particularly limited but, preferably, the components 1, 2, 3 and 4 are first reacted and then reacted. the components with the resulting product or the component 4 is reacted with the product of

  reaction of components 1, 2, 3 and 5.

  In the first process, that is, in the case where the component 5 is reacted with the reaction product of the components 1, 2, 3 and 4, the order and the reaction process of the components 1, 2 , 3 and 4 are not specifically limited. For example, the reaction can be carried out by contacting components 1 and 2, then contacting component 3 (or component 4) with the resulting product and then contacting the remaining component with the product obtained. The components 2 and 3 are preferably reacted in advance and the reaction product thus obtained is used as the components 2 and 3. More particularly, the oxide is contacted and reacted with

  silicon and / or aluminum oxide 1, the reaction product (hereinafter

  after referred to as component 2-3) of the magnesium halide 2 and the compound 3 of the general formula Me (OR) nXzn wherein Me is an element of the groups I to IV of the Periodic Table, z is the valence of the element lie, the coefficient n obeys the relation

  - <n _ z. X is a halogen atom and R is a hydrocarbon radical;

  C1-C20 bure and the titanium compound and / or the vanadium compound 4.

  For the contacting order, the above operation can be performed by contacting the component 1 and the component 2-3 and then contacting the component 4 with

  the resulting product, or by first contacting the

  1 and 4 and then contacting the component 2-3 with the resulting product, or by first contacting the component 2-3 and the component 4 and then contacting the component 1 with the. resulting product. Preferably, the components 1 and 23 are brought into contact and then the component 4 is brought into contact with

the resulting product.

  The contacting method is not especially limited, i.e., two techniques can be adopted. In the case of contacting the components 1 and 2-3, or in the case of contacting the component 2-3 with the product of implementation

250262 Y

  contact of the components 1 and 4, or in the case of contacting the component 1 with the contacting product of the components 2-3 and 4, it is possible to apply a co-spray treatment at a temperature of from 0 to 2000 ° C. 30 minutes to 50 hours, or mixing and heating at 50 ° -300 ° C.

  from 1 minute to 48 hours in an organic solvent such as a hydro-

  inert carbide, an alcohol, an ether, a ketone or an ester, followed by removal of the solvent. In addition, in the case of contacting

  components 1 and 4, or in the case of bringing the component into contact with

  4 with the contacting product of the components 1 and 2-3 or in the case of contacting the components 2-3 and 4, a co-spraying treatment can be carried out at a temperature of 0-200 ° C. for 30 minutes to 50 hours, or mixing and heating at 50-300 ° C for 5 minutes to 10 hours in the presence or absence of an inert solvent, followed by removal of the titanium and / or vanadium compound

  unreacted by washing with an inert solvent.

  The reaction process between the magnesium halide and the compound of the general formula Me (OR) nXz-n is not especially

  limit. The two compounds can be reacted by mixing and heating.

  for 5 minutes to 10 hours at a temperature of 20 to 4000C, preferably 50 to 300 ° C, in an organic solvent such as

  inert hydrocarbon, an alcohol, an ether, a ketone or an ester.

  The two components can also be reacted by a treatment

co-spray.

  The application of a co-spray treatment is particularly preferred according to the invention. The apparatus to be used for the co-spraying treatment is not especially limited but usually a roller mill is used as a vibratory mill, a roller mill or a hammer mill. The conditions for copulverisation treatment, such as temperature and co-spray time, can be determined easily by man

  of art according to the co-spray system that is adopted. Gene-

  the co-spray temperature is in the meantime

  from 0 to 2000C, preferably from 20 to 100 ° C, and the duration of co-spraying.

  It is in the range from 30 minutes to 150 hours, preferably from 1 to 3 hours. It goes without saying that the operation must be carried out in an inert gas atmosphere and that moisture should be avoided

as much as possible.

  The reaction ratio of the magnesium halide to the compound of the general formula Mle (OR) nXz n is in the range of 1: 0.01 to 1: 10, preferably 1: 0.1 to 1: 5, expressed

by the atomic ratio Mg / Me.

  The amount of component 2-3 to be used according to the invention

  The amount of component 4 is preferably from 0.01 to 5 g, preferably from 0.1 to 2 g per gram per gram per gram, so that the amount of titanium and / or or vanadium of the resulting solid component is in the range of 0.5 to 20% 7. by weight, in particular from 1 to 10% by weight, to achieve a well-balanced activity by titanium and / or

vanadium and by solid.

  The preferred order and method of contacting

  components 1, 2-3 and 4 according to the invention are as follows.

  Component 2-3 is first reacted, which is the reaction product of the magnesium halide and

  general formula Me (OR) nXzn and component 1 at O-300'C, of

  Preferably 10-200 ° C, and more preferably 20-100 ° C for 1 minute to 48 hours, preferably 2 minutes to 10 hours, in a solvent that dissolves component 2-3. Examples of solvents include alcohols, ethers, ketones and amines. Preferred examples of such solvents are: methanol, ethanol, isopropanol, butanol, pentanol, hexanol, octanol, benzyl alcohol, 2-methoxyethanol, 2-ethoxyethanol, methyl formate, ethyl formate, methyl acetate, ethyl acetate, butyl acetate, vinyl acetate, methyl acrylate, methyl methacrylate, octyl butyrate, ethyl laurate, octyl laurate, methyl benzoate, ethyl benzoate, octyl para-hydroxybenzoate, dibutyl phthalate, dioctyl phthalate, dimethyl malonate, dimethyl maleate, diethyl maleate, dimethyl ether, diethyl ether, diisopropyl ether, dibutyl ether, ether

  diamine, tetrahydrofuran, dioxane, anisole, acetone, methyl-

  ethyl ketone, methyl isobutyl ketone, ethyl butyl ketone, dihexyl ketone,

  acetophenone, benzophenone, cyclohexanone, diethylamine, triethyl

  amine, tetramethylenediamine, aniline, N, N-dimethylaniline and

250,262 9

  pyridine. Ethanol, tetrahydrofuran and ethyl acetate are preferred. In this case, the components 1 and 2-3 are brought into contact in a ratio of 0.01 to 5 grams, preferably 0.1 to 2 grams, of the component 2-3 per gram of the component 1. After the reaction , the solvent is removed to obtain the reaction product of the components

l and 2-3.

  Component 4, i.e., the titanium compound and / or the vanadium compound, is then blended by heating with the above reaction product components 1 and 2-3 at a temperature of 20 to 3000C. preferably from 50 to 1500C for minutes to 10 hours in the presence or absence of an inert solvent such as hexane or heptane to obtain the titanium compound and / or the vanadium compound supported on the reaction product of the components 1 and 2-3. In this case, the amount of component 4 is adjusted so that the content of titanium compound and / or vanadium compound in the resulting solid component is in the range of 0.5 to 20% e, preferably 1 to 10% by weight. After the

  reaction, the titanium compound and / or the vanadium compound are removed.

  dium unreacted washing several times with an inert solvent vis-à-vis the Ziegler catalysts, then evaporated under pressure

  reduced to obtain a solid powder.

  The resulting reaction product (hereinafter referred to as component I) of components 1, 2-3 and 4 is then reacted with the component of general formula R "nSi (OR) mX4-mn

  to obtain the solid catalytic component of the invention.

  The reaction technique between component I and component 5 is not especially limited. Both components can be reacted by the co-spray treatment; or in the presence or absence of an inert solvent at a temperature of 20 to 4000C, preferably 50 to 300C for 5 minutes at

hours.

  Components I and 5 are reacted in a ratio of 0.05 to 50 grams, preferably 0.1 to 30 grams of component 5 per 100 g of component I. In the case where component 4 is reacted with the reaction product of components 1, 2, 3 and 5, the order and the

  The reaction process of components 1, 2, 3 and 5 is not particularly

  limited, but we prefer to react in advance

  poses 2 and 3, or components 2 and 5, or components 2, 3 and 5.

  More specifically, the reaction can be carried out by contacting the reaction product of components 2 and 3 with component 1 and then contacting component 5 with the resulting product, or by contacting the reaction product with components 2 and 5 with component 1 and then contacting component 3 with the resulting product, or

  well by contacting the component 1 with the reaction product

components 2, 3 and 5.

  Bringing into contact between the components 2 and 3, between the components 2 and 5 or between the components 2, 3 and 5,

  can be carried out in an organic solvent such as a hydrocarbon

  inert, an alcohol, an ether, a ketone or an ester, but

  preferably it is carried out by the co-spray treatment.

  The contacting of the component 1 with the reaction product of the components 2 and 3, with the reaction product of the components 2 and 5 or with the reaction product of the components 2, 3 and 5, can be carried out by the treatment of co spray, but preferably it is carried out in an organic solvent, such as an inert hydrocarbon, an alcohol, an ether, a ketone or a

  will have a temperature of -50 to 3000C for 1 minute to 48 hours.

  In the case where the component 5 is brought into contact with the product resulting from the contact of the reaction product of the components 2 and 3 with the component 1, or in the case where the component 3 is brought into contact with the product resulting from the contact of the reaction product of the components 2 and 5 with the component.

  can let the reaction occur by the co-pulp treatment

  verification, or in the presence or absence of an inert solvent.

  With regard to the molar ratios in the contacting of the components 1, 2, 3 and 5, the component 1 / component 2 ratio is in the range of 1: 0.01 to 1: 5, preferably 1: 0.1 to 1: 2, the component 2 / blister 3 ratio is in the range ck 1: 0.01 to 1:10, preferably 1: 0.1 to 1: 5 and the ratio component 2 / component 5 is in the range of 1: 0.1 to 1:10, preferably

from 1: 0.1 to 1: 5.

  The contacting of the component 4 with the product of

  The reaction of components 1, 2, 3 and 5 can be effected by

  co-spray, but the compound is preferably

  4 with the reaction product of components 1, 2, 3 and 5 in the presence or absence of an inert solvent such as hexane or heptane and the reaction is allowed to proceed at a temperature of from 20 to 300 ° C. 5 to 10 hours. The amount of component 4 is adjusted so that its content in the resulting solid component is

  in the range of 0.5 to 20%, preferably 1 to 10% by weight.

  As an organometallic compound used according to the invention

  metal organometallic compounds of groups I-IV of the Periodic Table, known as one of the

  components of the Ziegler catalysts, preferably organic compounds

  aluminum compounds and organozinc compounds, for example

  aluminum of general formulas R3A1, R2AlX, RA1X2, R2AlOR, RA1 (OR) X and R3A12X3, wherein R is a C1-C20 alkyl or arylalkyl group and the radicals R can be the same or different and X is a halogen atom , and organozinc compounds of the general formula R2Zn wherein R is a C1-C20 alkyl group and

  R residues may be the same or different, such as triethylaluminum

  minium, triisopropylaluminum, triisobutylaluminum, tri-sec-butyl-

  aluminum, tri-tert-butylaluminum, trihexyl aluminum, trioctylaluminum, diethylaluminum chloride, chloride

  of diisopropylaluminum, ethyl aluminum sesquichloride, diethyl

  zinc, and mixtures thereof. The amount of the organometallic compound is not especially limited, but the organometallic compound can ordinarily be used in an amount of 0.1 to 1000 moles per mole

  titanium compound and / or vanadium compound.

  It is also preferred according to the invention to use the organometallic component in the form of a mixture or an addition compound of the organometallic compound listed above and an ester.

of organic acid.

  In the case where the compound is mixed

  organometallic acid and the organic acid ester, the usual

  the organic acid ester in an amount of 0.1 to 1 mole, preferably

  0.2 to 0.5 moles per mole of the organometallic compound. In the case where the organometallic compound and the organic acid ester are used in the form of an addition compound, the molar ratio of the organometallic compound to the organic acid ester is preferably

in the range of 2: 1 to 1: 2.

  The organic acid ester is an ester of a saturated or unsaturated C 1 -C 24 mono- or dicarboxylic acid with a C 1 -C 30 alcohol. Examples of these organic acid esters are the following: methyl formate, ethyl acetate, amyl acetate, phenyl acetate, octyl acetate, methyl methacrylate, ethyl stearate, methyl benzoate, benzoate of ethyl, n-propyl benzoate, isopropyl benzoate, butyl benzoate, hexyl benzoate, cyclopentyl benzoate, cyclohexyl benzoate, phenyl benzoate, 4-tolyl benzoate, methyl salicylate, ethyl salicylate methyl p-hydroxybenzoate, ethyl hydroxybenzoate, phenyl salicylate, cyclohexyl p-hydroxybenzoate, benzyl salicylate, ethyl a-resorcinate, methyl anisate, ethyl anisate, phenyl anisate, benzyl anisate, ethyl omethoxybenzoate, methyl p-ethoxybenzoate, methyl p-toluate, ethyl p-toluate, phenyl p-toluate, ethyl o-toluate, ethyl methacrylate, methyl p-aminobenzoate, p-toluene ethyl aminobenzoate, vinyl benzoate, allyl benzoate, benzoate benzyl, methyl naphthoate and ethyl naphthoate. Particularly preferred are the alkyl esters, especially the methyl and ethyl esters of benzoic acid,

  o- or p-toluic acid and p-anisic acid.

  The polymerization of olefins using the catalyst

  according to the invention may be carried out in the form of a polymer.

  suspension, solution polymerization or vapor phase polymerization. In particular, the catalyst according to

  the invention is suitable for vapor phase polymerization.

  The polymerization reaction is carried out in the same manner as in the conventional olefin polymerization reaction using a Ziegler type catalyst; in other words, the reaction is carried out substantially away from oxygen and water and in the presence or

  in the absence of an inert hydrocarbon. The conditions for the poly-

  olefins are available at temperatures ranging from 120 OC to 50 0C and the pressures varying from

  atmospheric pressure at 70 bar, preferably from 2 to 60 bar.

  The molecular weight can be adjusted to a certain extent by

  While maintaining the polymerization conditions, such as polymerization temperature and molar ratio of the catalyst, the addition of hydrogen in the polymerization system is more effective for this purpose. Of course, two or more stages of polymerization reactions can be carried out without difficulty using the catalyst of the invention under different polymerization conditions.

  such as hydrogen concentrations and poly-temperatures

different merit.

  The invention can be applied to the polymerization of all olefins which are polymerizable with Ziegler catalysts, preferably C2-C12 α-olefins. For example, the present invention is suitable for homopolymerization of α-olefins such as ethylene, propylene, butene-1, hexene-1 and 4-methylpentene-1, copolymerization of ethylene and propylene, ethylene and butene-1, ethylene and hexene-1, propylene and butene-1 and the copolymerization of ethylene with two or

several other α-olefins.

  The copolymerization with dienes for the modification

  The cation of the polyolefins is also preferable. Examples of dienes used in this copolymerization are butadiene,

  1,4-hexadiene, ethylidenenorbornene and dicyclopentadiene.

  By using the catalyst according to the invention, a polyolefin having a high average particle size, a narrow particle size distribution and a reduced proportion of fine particles is obtained with high activity and the apparent density of the polyolefin is high, which is very high. advantageous for the polymerization operation. The polyolefin thus obtained can be molded only in the form of pellets or pellets, but also directly in the form of powder, as this causes little discomfort in the molding operation. We can therefore prepare very

advantageously polyolefins.

  The polymer obtained using the catalyst of the invention is further characterized by a very narrow molecular weight distribution and that the smaller the hexane extraction, the more. low-quality polymer formation as a by-product. Thus, if the polyolefin having a narrow molecular weight distribution obtained using the catalyst according to the invention is used for forming a film, the resulting film has many advantages, for example

  example, high strength, high transparency and

  high anti-blocking and heat sealing properties.

  The present invention provides a novel catalyst system that has many valuable features and overcomes the previous disadvantages associated with the prior art. It is quite surprising that the advantages mentioned above can be easily achieved by

  using the catalyst according to the invention.

  The following examples illustrate the invention without

however, limit its scope.

Example 1

  (a) Preparation of the solid catalyst component.

  10 g of a commercial anhydrous magnesium chloride and 4.2 g of aluminum triethylate are placed in a stainless steel container with a capacity of 400 ml containing 25 stainless steel balls 12.7 mm in diameter and the mixture was bead milled for 16 hours at room temperature under a nitrogen atmosphere to obtain a reaction product. A three-necked flask equipped with a stirrer and a reflux condenser was then purged with nitrogen, in which 5 g of the above reaction product and 5 g of SiO 2 (Fuji-Davison No. 952), which had been calcined at 600oC. then 100 ml of tetrahydrofuran are added and the reaction is carried out at C for 2 hours and then dried at 1200C under reduced pressure to remove tetrahydrofuran. Then, after adding 50 ml of hexane and stirring, 1.1 ml of titanium tetrachloride is added and the reaction is carried out for 2 hours with refluxing hexane to obtain a solid powder A which contains 40 mg of titanium per gram . The powder A is added to 50 ml of hexane, then 1 ml of tetraethoxysilane is added and the reaction is carried out for 2 hours with reflux of hexane to obtain the solid catalyst component. (b) Vapor phase polymerization A stainless steel autoclave was used as the vapor phase polymerization apparatus and a circuit was formed with a blower, a flow control device and a dry cyclone. The temperature of the autoclave is adjusted by the passage of water

warm in an envelope.

  In the autoclave maintained at 80 ° C., the

  above, and triethylaluminum at rates of 250 mg / h and 50 mmol / h, respectively, and butene-1, ethylene, and hydrogen are fed in such a way. that the molar ratio of butene-1 / ethylene in the vapor phase in the autoclave is 0.27 and the concentration of hydrogen

  17% of the total pressure and the polymerization is carried out by recycling.

  gas in the system using the blower. The resulting ethylene copolymer is a powder having an average particle size of 750 ", not containing particles of less than 150% and having a bulk density of 0.42, a melt index (MI) of 1.0 and a density of 0.9208 The catalyst activity is 100,000 g

of copolymer / g of Ti.

  The index FR, represented by the ratio of the melt index MI2, 16 of the copolymer under a load of 2.16 kg to the melt index MI10 under a load of 10 kg, both at 190 ° C. according to the standard ASTM-D1238-65T, is 7, 2 and the molecular weight distribution

so is very narrow.

  A film is formed with this copolymer and extracted in boiling hexane for 10 hours; we find that the extract

  is 0.8% by weight and the extraction is very low.

  Comparative Example 1 The following vapor phase polymerization is carried out

  using the apparatus described in Example 1.

  The autoclave maintained at 80 ° C. with the solid powder A obtained in Example 1 and triethylaluminium at a flow rate of 250 mg / h and 50 mmol / h, respectively, is charged and butene-1 is introduced. ethylene and hydrogen by adjusting in such a way that

  the molar ratio of butene-1 / ethylene in the vapor phase in the

  toclave of 0.25 and the hydrogen concentration of 15% of the total pressure, and the polymerization is carried out under a total pressure of 10 bars by recycling the ga z inside the system by means of the blower . The resulting ethylene copolymer is a powder having an average particle size of 700, not containing particles of less than 150, and having an apparent density of 0.41, a melt index of 1, 2 and a density of 0.9210. The catalytic activity is 112,000 g of copolymer per

gram of Ti.

  The F.R. index of this copolymer is 7.6 and the

  molecular weight distribution is therefore broader than the

ple 1.

  A film is formed with this copolymer and extracted with boiling hexane for 10 hours; we find that the extraction

with hexane is 1.1% by weight.

Example 2

* (a) Preparation of the solid catalyst component 10 g of anhydrous magnesium chloride and 4.2 g of t4traethoxysilane are placed in the ball mill container described in Example 1 and ground for 16 hours at room temperature.

  under a nitrogen atmosphere to obtain a reaction product.

  5 g of the reaction product and 5 g of SiO 2, which has been calcined at 600 ° C., are then placed in the three-necked flask described in Example 1, then 100 ml of tetrahydrofuran are added and the reaction is carried out at 60 ° C. for 2 hours, then dried at 120 ° C. under reduced pressure to remove tetrahydrofuran. Then, after adding 50 ml of hexane and stirring, 1.1 ml of titanium tetrachloride is added and the reaction is carried out for 2 hours under reflux of hexane to obtain a solid powder B which contains 40 mg of titanium per

g of powder.

  The powder B is added in 50 ml of hexane, then 1 ml of tetraethoxysilane is added and reacted for 2 hours.

  with reflux of hexane to obtain the solid catalyst component.

  (b) Polymerization in the vapor phase.

  The following polymerization is carried out in phase

  steam using the apparatus described in Example 1.

  The autoclave maintained at 80 C is charged with the

  above, and triethylaluminum at rates of 250 mg / hr and 50 mmol / hr respectively, and butene-1 of ethylene and hydrogen are introduced therein by adjusting such that the ratio of molar butene-1 / ethylene in the vapor phase in the autoclave of 0.28 and the hydrogen concentration of 17% of the total pressure, and the polymerization is carried out in

  recycling the gases inside the system using the blower.

  The resulting ethylene copolymer is a powder having a

  average particle size of 750, u, not containing particles less than 150 y, and having a bulk density of 0.38, an index

  MI melting point of 1.1 and a density of 0.9250. Catalyst activity

  It is 100,000 g of copolymer / g of Ti.

  The F.R index of the copolymer is 7.2. When forming a film with this copolymer and extracting it in boiling hexane for 10 hours, it is found that the extraction with hexane

is 0.8% by weight.

  Comparative Example 2 The following polymerization is carried out in phase

  steam using the apparatus described in Example 1.

  The autoclave maintained at 80 ° C. with the solid powder B obtained in Example 2 and triethylaluminium at a flow rate of 250 mg / h and 50 mmol / h respectively are charged and ethylene butene-1 is introduced into it. and hydrogen by adjusting such that the butenal / ethylene molar ratio in the vapor phase in the autoclave is 0.28 and the concentration

  15% of the total pressure, and the poly-

  Merification under a total pressure of 10 bar by recycling the gases inside the system using the blower. The resulting ethylene copolymer is a powder having an average particle size of 750 a particle-free of less than 150 and having a bulk density of 0.38, a melt index MI of 1.0 and a density of 0. , 9180. The activity of the catalyst is

000 g of copolymer / g of Ti.

  The F.R index of the copolymer is 8.0 and the distribution

  The molecular weight reduction is therefore wider than in Example 2.

  A film is formed from this copolymer and extracted into boiling hexane for 10 hours; extraction

with hexane is 2.0% 7. in weight.

Example 3

  (a) Preparation of the solid catalyst component.

  10 g of anhydrous magnesium chloride and 4.2 g of alumina triethylate are placed in the roller mill container described in Example 1 and grinding is carried out for 16 hours at room temperature in a nitrogen atmosphere to obtain a reaction product. 5 g of the reaction product and 5 g of SiO 2, which was calcined at 600 ° C. in the three-necked flask described in Example 1, were then placed, then 100 ml of ethyl acetate was added and reacted at 60 ° C. for 2 hours. hours and dried at 120 ° C under reduced pressure to remove ethyl acetate. Then, after addition of 50 ml of hexane and stirring, 1.1 ml of titanium tetrachloride are added and reacted for 2 hours to obtain a powder.

  solid C which contains 40 mg of titanium per gram.

  The powder C is added to 50 ml of hexane, then 0.5 ml of tetraethoxysilane is added and reacted for 3 hours with

  reflux of hexane to obtain the solid catalyst component.

  (b) Polymerization in the vapor phase The following polymerization is carried out in phase

  steam using the apparatus described in Example 1.

  The autoclave maintained at 80 ° C is charged with the compound

  above, and triethylaluminum at rates of 250 mg / hr and 50 mmol / hr respectively, and butene-1, ethylene, and hydrogen are fed therein by adjusting to have a molar ratio of butene-1 / ethylene in the vapor phase in the autoclave of 0.27 and a concentration of hydrogen of 17% of the total pressure, and the polymerization is carried out by recycling

  the gases inside the system by means of the blower. The copo-

  The resulting ethylene amine is a powder having an average particle size of 600 u, which does not contain particles of less than 150 and having a bulk density of 0.39, a MII melt index of 1.5 and a density of of 0.9200. Catalytic activity

  is 90,000 g of copolymer / g of Ti.

  The F.R index of the copolymer is 7.5. We form a

  film from this copolymer and extracted with hexane

  lante for 10 hours; the extraction with hexane is 0.9%

in weight.

Example 4

  (a) Preparation of the solid catalyst component 10 g of anhydrous magnesium chloride and 4.1 g of triethyl borate are placed in the roller mill container described in Example 1 and the milling is carried out for 16 hours at room temperature. under a nitrogen atmosphere to obtain a reaction product. 5 g of the reaction product and 5 g of SiO 2, which has been treated at 600 ° C., are placed in the three-necked flask described in Example 1, then 100 ml of tetrahydrofuran are added and the reaction is carried out for 2 hours at 60 ° C. then dried at 120 ° C under pressure to remove tetrahydrofuran. Then, after adding 50 ml of hexane and stirring, 1.1 ml of titanium tetrachloride is added and the reaction is carried out for 2 hours with reflux of hexane to obtain a solid powder D which contains 40 mg of

titanium per gram.

  The powder D is added to 50 ml of hexane, then 1 ml of tetraethoxysilane is added and the reaction is carried out for 2 hours with refluxing hexane to obtain the solid catalyst component.

  (b) Polymerization in the vapor phase.

  The following polymerization is carried out in the vapor phase

  using the apparatus described in Example 1.

  The above solid catalyst component and triethylaluminum are introduced into the autoclave maintained at 80 ° C. at flow rates of 250 mg / h and 50 mmol / h, respectively, and butene-1 and ethylene are introduced therein. hydrogen by setting a butene-1 / ethylene molar ratio in the 0.27 autoclave vapor phase and a 17% hydrogen concentration of the total pressure, and the polymerization by recycling the gases inside the system by means of the blower. The resulting ethylene copolymer is a powder having an average particle size of 500 u and no particles of less than 44 p and having an apparent density of 0.42, a melt index MI of 1.3 and a

  density of 0.9205. The catalytic activity is 70,000 g of copper

lymere / g of Ti.

  The F.R index of the copolymer is 7.4. A film is formed with this copolymer and extracted into boiling hexane

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  for 10 hours; the extraction with hexane is 0.9% by weight.

Example 5

  (a) Preparation of the solid catalyst component.

  10 g of anhydrous magnesium chloride and 4.2 g of magnesium diethylate are placed in the roller mill container described in Example 1 and grinding is carried out for 16 hours at room temperature under a nitrogen atmosphere to obtain a reaction product. 5 g of the reaction product and 5 g of SiO 2, which has been calcined at 600 ° C., are placed in the three-necked flask described in Example 1, then 100 ml of tetrahydrofuran are added and the mixture is reacted at 60 ° C. for 2 hours then it is dried at 120 ° C. under reduced pressure in order to eliminate tetrahydrofuran. Then, after adding 50 ml of hexane and stirring, 1.1 ml of titanium tetrachloride is added and the mixture is reacted for 2 hours with refluxing hexane to obtain a solid powder E which contains

mg of titanium per gram.

  The powder E is added to 50 ml of hexane, then 1 ml of tetraethoxysilane is added and the mixture is reacted for 2 hours.

  with reflux of hexane to obtain the solid catalyst component.

  (b) Polymerization in the vapor phase.

  The following polymerization is carried out in phase

  steam using the apparatus described in Example 1.

  The solid catalytic component

  above and triethylaluminum in the autoclave maintained at 80 C at flow rates of 250 mg / h and 50 mmol / hrespectively and introduced butelen, ethylene and hydrogen by adjusting so as to see a report molar butene-1 / ethylene in the vapor phase

  in the autoclave 0.27 and a hydrogen concentration of 17% 7.

  of the total pressure and the polymerization is carried out by recycling

  the gases inside the system by means of the blower. The copo-

  The resulting ethylene amine is a powder having an average particle size of 600> u and not containing particles of less than 100 u and having a bulk density of 0.40, an MI melt index of 0.5 and a density of 0.9250. Catalytic activity

  is 100,000 g copolymer / g Ti.

  The F.R copolymer index is 7.5. We form a

  film of this copolymer and extracted in boiling hexane

  10 hours; the extraction with hexane is 0.4% by weight.

Example 6

  (a) Preparation of the solid catalyst component. 10 g of commercial anhydrous magnesium chloride and 4.2 g of aluminum triethylate are placed in a stainless steel container with a capacity of 400 ml and containing 25 stainless steel balls 12.7 mm in diameter each. we perform

  grinding for 16 hours at room temperature under atmospheric pressure.

  nitrogen to obtain a reaction product. A three-necked flask equipped with a stirrer and a reflux condenser is then purged with nitrogen, in which 5 g of the above reaction product and 5 g of SiO 2 (Fuji-Davison No. 952), which was calcined at 600 ° C., then 100 ml of tetrahydrofuran was added and reacted at 60 ° C. for 2 hours, then dried at 120 ° C. under reduced pressure in order to remove the tetrahydrofuran. Then, 50 ml of hexane and 2 ml of tetraethoxysilane are added and reacted at 50 ° C. for 2 hours, then 1.1 ml of titanium tetrachloride are added and the mixture is reacted for 2 hours under reflux with hexane. obtain the solid catalyst component which contains 38 mg of titanium per gram.

  (b) Polymerization in the vapor phase.

  The polymerization in the vapor phase of the

  following way using the apparatus described in Example 1.

  The solid catalyst component above and triethylaluminium are introduced into the autoclave maintained at 80 ° C. at flow rates of 250 mg / h and 50 mmol / h respectively, and butene-1, ethylene and hexane are introduced. hydrogen, by adjusting to a molar ratio of butene-1 / ethylene in the vapor phase in the autoclave of 0.28 and a hydrogen concentration of 17% of the total pressure, and the polymerization is carried out.

  recycling the gases inside the system using the blower.

  The resulting ethylene copolymer is a powder having a

  an average particle size of 730, u, containing no particles less than 150, and having a bulk density of 0.40, an MI melt index of 1.0, and a density of 0.9221. The activity

  The catalyst is 135,000 g copolymer / g Ti.

  The F.R index of the copol-mother is 7.2. A film of this copolymer is formed and extracted with boiling hexane for 10 hours; the extraction with hexane is 0.9% by weight.

Example 7

  (a) Preparation of the solid catalyst component.

  10 g of anhydrous magnesium chloride are placed

  4.2 g of aluminum triethylate and 3 g of monomethyl

  triethoxysilane in a stainless steel container having a capacity of 400 ml and containing 25 stainless steel balls with a diameter of 12.7 mm each, and grinding is carried out for 16 hours at room temperature under a nitrogen atmosphere for obtain a reaction product. A three-necked flask equipped with a stirrer and a reflux condenser was then purged with nitrogen, in which 5 g of the above reaction product and 5 g of SiO 2 (Ftji-Davison No. 952), which had been added, were charged. calcined at 600 ° C., then 100 ml of tetrahydrofuran are added and the mixture is reacted at 60 ° C. for 2 hours and then dried at 120 ° C. under reduced pressure to remove the tetrahydrofuran. Then, after adding 1 ml of hexane and stirring, 1.1 ml of titanium tetrachloride are added and the mixture is reacted for 2 hours with refluxing hexane to obtain a solid powder A which contains 40 mg of titanium per gram. .

  (b) Polymerization in the vapor phase.

  A stainless steel autoclave is used as the vapor phase polymerization apparatus and a circuit with a blower is formed to a flow control device and a dry cyclone. The temperature of the autoclave is controlled by passage

lukewarm water in a shirt.

  The solid catalytic component

  above and triethylaluminum in the autoclave maintained at 80 ° C

  at flow rates of 250 mg / h and 50 mmol / h respectively, and

  of butene-1, ethylene and hydrogen by controlling to have a butene-1 / ethylene molar ratio in the

  vapor phase in the O027 autoclave and a concentration of

  17% of the total pressure gene, and the polymerization is carried out

  by recycling the gases inside the system with the help of

  flante. The resulting ethylene copolymer is a powder having a

  average particle size of 710 u, not containing any

  cules less than 150 Pet having a bulk density of 0.40, an MI melt index of 0.8 and a density of 0.9210. The activity

  Catalyst is 130,000 g copolymer / g Ti.

  The F.R index is 7.1. A film of this copolymer is formed and extracted with boiling hexane for 10 hours;

  the extraction with hexane is 0.8% by weight.

  It is understood that the invention is not limited

  to the preferred embodiments described above as illus-

  tration and that the person skilled in the art may make various modifications and changes thereto without departing from the framework and the spirit.

of the invention.

REVEIDICATIONS

  1. In a catalyst of polymerization of the oldfines com-

  taking a solid catalytic component and an organometallic compound, the improvement characterized in that said solid catalytic component is a substance obtained by contacting and reacting the following compounds: (1) at least one compound chosen from silicon oxides and oxides of aluminum, (2) a magnesium halide, (3) a compound represented by the general formula (OR) nXzn wherein le is an element

  belonging to groups I to IV of the Classifica-

  Periodic Periodic Elements, z is the valence of Me, the coefficient n satisfies the relationship Os nz, X is a halogen atom and R is a C 1 -C 20 hydrocarbon radical, (4) at least one compound selected from the titanium compounds and the vanadium compounds, and (5) at least one compound selected from the compounds represented by the general formula

  R "nSi (OR ') mX4I mn in which R' and R" represent

  each is a C1-C24 hydrocarbon radical, X is a halogen atom, n satisfies the relation O <n <4 and m satisfies the relation 0 <m! 4, with the additional requirement

0 <m + nr 4, and a polysiloxane.

  Catalyst according to claim 1, characterized in

  what said silicon oxide is silica.

  Catalyst according to claim 1, characterized in

  what said aluminum oxide is alumina.

  Catalyst according to Claim 1, characterized in

  that said magnesium halide is magnesium chloride.

  Catalyst according to claim 1, characterized in

  that Me is Na, Mg, Ca, Zn, Cd, B or Al.

  Catalyst according to Claim 1, characterized

  in that said titanium compound is a titanium tetra-

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  are represented by the general formula Ti (OR) nX4.n wherein R is a C 1 -C 20 alkyl, aryl or arylalkyl group, X is a halogen atom and O t n 4, or a trivalent titanium compound

  obtained by reducing said tetravalent titanium compound.

  7. Catalyst according to claim 1, characterized in that said solid catalytic component is obtained by reacting said components (2) and (3) in advance and bringing into contact and reaction of said components (1), (4) and ( 5) with the product of

  resulting reaction in a desired order.

  Catalyst according to Claim 1, characterized in that the component (1) / component (2) ratio is between

1: 0.01 and 1: 5.

  9. Catalyst according to claim 1, characterized in that the ratio component (2) / component (3) is between

1: 0.01 and 1:10.

  10. Catalyst according to claim 1, characterized in that the ratio component (2) / component (5) is between

1: 0.01 and 1:10.