FR2517681A1 - PROCESS FOR PREPARING POLYOLEFINS WITH A NEW POLYMERIZATION CATALYST - Google Patents

Abstract

PROCESS FOR PREPARING POLYOLEFINS WITH A NEW POLYMERIZATION CATALYST; THE CATALYST CONSISTS OF AN ORGANOMETALLIC COMPOUND AND A SOLID CATALYTIC COMPONENT OBTAINED BY THE REACTION OF AT LEAST THE FOLLOWING FOUR COMPONENTS: (CF DRAWING IN BOPI) (4) A HALOGEN TITANIUM COMPOUND, OR R, R, R AND R EACH REPRESENT A RADICAL HYDROCARBON HAVING 1 TO 24 CARBON ATOMS, R, R AND R EACH REPRESENTS A HYDROCARBON RADICAL HAVING 1 TO 24 CARBON ATOMS, AN ALCOXY, A HYDROGEN OR A HALOGEN, X IS A HALOGEN, ME IS A PART OF IA GROUP VIII OF THE PERIODIC CLASSIFICATION EXCLUDING SILICON AND TITANIUM, Z IS THE VALENCY OF ME AND M, N, P AND Q ARE AS FOLLOWS: 0M2, 0N2, 0MN2, 0PZ, 1Q30.

Description

25.17681

  The present invention relates to a method for

  prepare polyolefins with a new polymerization catalyst.

  To date, in this technical field, Japanese Patent Publication No. 12 105/1964 discloses a catalyst consisting of a magnesium halide and a transition metal compound, such as a titanium compound which is fixed by Belgian Patent No. 742 112, a catalyst prepared by copulverising a halide

  of magnesium and titanium tetrachloride.

  However, in the production of polyolefins,

  It is desirable that the catalytic activity be as high as

  and from this point of view, the process described in Japanese Patent Publication No. 12 105/1964 mentioned above has only a weak polymerization activity and the process described in the aforementioned Belgian Patent No. 742 112 has a sufficient polymerization activity. high but a

  further improvement is desirable.

  In German Patent No. 2,137,872, the amount of magnesium halide is greatly reduced by sputtering with titanium tetrachloride and alumina, but a remarkable increase in activity per unit weight of solid material, which can be considered as an indication of productivity, is not

  not established and a more active catalyst is desired.

  Moreover, in the production of polyolefins,

  desirable from the point of view of productivity and manuten-

  In this regard, in the process described in Japanese Patent Publication No. 12 105/1964, the apparent density of the obtained polymer is low and the activity of the polymer obtained is as low as possible. polymerization is unsatisfactory and in the process described in the aforementioned Belgian Patent No. 742 112, the apparent density of the polymer obtained is low although the polymerization activity is high and, therefore, additional improvements

are desirable.

  One of the aims of the invention is to provide a

  new polymerization catalyst capable of overcoming

  aforementioned, exhibiting high polymerization activity, providing a high bulk density polymer with a yield of

  high and allowing the extremely easy realization of a poly-

  continuous merification, as well as a process for homopolymerization or

  copolymerization of olefins using such a polymer catalyst

  authorization. The invention relates to a process for preparing polyolefins by homopolymerization or copolymerization of olefins in the presence of a catalyst comprising a solid catalyst component and an organometallic compound, this solid catalytic component comprising a substance obtained by reaction of at least the four components. following: (1) a compound represented by the general formula: R (OR 2) ng X 2 -mn (2) a compound represented by the general formula: Me (OR 3) X p zp (3) a compound represented by general formula:

g 4 -

R 6 (s i R 7 and q R

  (4) a halogenated titanium compound.

  In these formulas, R 1, R 2, R 3 and R 3 each represent a hydrocarbon radical having 1 to 24 carbon atoms, R 4, R 5 and R 6 each represent a hydrocarbon radical having 1 to 24 carbon atoms, an alkoxy radical, a hydrogen atom or a halogen atom, X represents a halogen atom, Me represents a

  elements of groups I to VIII of the Periodic Table, under

  serve that silicon and titanium are excluded, z is the valence of Me and m, n, p and q are as follows:

  0 O m 2, O <N <2 <2, O <p, Z, 16 q <30.

  The catalyst of the invention exhibits extremely high polymerization activity and, therefore, the monomer partial pressure is kept low during polymerization. In addition, the apparent density of the obtained polymer is so high that productivity can be improved. Also, the amount of catalyst remaining in the polymer obtained at the end of the polymerization is so small that the process for producing a polyolefin may not include the stage of removal of the catalyst, which simplifies the treatment process. of the polymer and overall to prepare polyolefins so

extremely economical.

  In the process of the invention, the amount of poly-

  it is produced by polymerization reactor unit

  because of the high bulk density of the polymer.

  The invention also has the advantage that as regards the size of the particles of the polymer obtained the proportion of large particles and fine particles measuring less than 50 / um is low despite the high bulk density and that, therefore,

  it becomes not only easy to carry out a polymerization reaction

  continued, but also to manipulate the polymer particles,

  for example during centrifugal separation in the treatment process.

  polymer and in the powder transport.

  Another advantage of the invention is that the poly-

  The olefins prepared by use of the catalyst of the invention have a high bulk density as previously indicated and those having a desired melt index can be obtained with a lower hydrogen concentration than in conventional processes, which allows the pressure to be set. total to a relative value

  low during the polymerization and, therefore, improve

  economy and productivity.

  Moreover, in the polymerization of olefins, with the catalyst of the invention, the olefin absorption rate does not decrease much over time and, therefore,

  carry out the polymerisation for a prolonged period with a quantity

lower catalyst content.

  Also, the polymers obtained by the use of

  The invention has an extremely narrow molecular weight distribution and hexane extraction is low, reflecting the minimization of formation as low quality polymer by-products. For example, to obtain products suitable for the preparation of films having good quality and superior by their property of low contact adhesion

and others.

  The invention provides a novel catalytic system which

  Having many of these characteristics and capable of overcoming the aforementioned drawbacks of the prior art. It is very surprising that such characteristics can easily be obtained by

  use of the catalyst of the invention.

  The preferred embodiments of the invention will

now be described.

  The compounds of formula R (OR 2) Mg X 2 mn used in the m N 2 -m-n the invention consist essentially of the compounds responding

  to this formula where R 1 and R 2 each represent a hydrogen radical

  carbon containing 1 to 24 carbon atoms, but it is particularly preferred

  and those R 1 and R 2 each represent an alkyl radical.

  Examples of such compounds include diethyl magnesium, diisopropyl magnesium, dibutyl magnesium, di-sec-butyl magnesium, methyl magnesium chloride, ethyl magnesium chloride, ethyl magnesium bromide, ethyl magnesium iodide,

  propyl magnesium, butyl magnesium chloride, butyl bromide

  magnesium, sec-butylmagnesium chloride, phenyl chloride

  magnesium, decylmagnesium chloride, methoxychloride

  magnesium, ethoxymagnesium chloride, isopropoxy

  magnesium, butoxymagnesium chloride, octyloxy chloride

  magnesium, methylmagnesium methylate, ethylmethylate

  magnesium, butylmagnesium ethoxide, sec-butyl ethylate

  magnesium and decylmagnesium ethoxide A complex formed with a trialkylaluminum, for example a complex, can also be employed.

  of dibutylmagnesium and triethylaluminum.

  As compounds of general formula Me (OR) p Xzp used p Z-P in the invention, there may be mentioned various compounds such as:

3 3 3 3 3 3

  Na OR, Mg (OR 3) 2 'Mg (OR) X, Ca (OR 3) 2> Zn (OR 3) 2' Zn (OR) X, Cd (OR) 2 '

3 3 333 3 3 3 3

  Al (OR) y Al (OR), Xe B (OR);, B (OR X Ga (OR) 3 Ge (OR) 4, Sn (OR, 4, P (OR) 3 'Cr (OR) 2' Mn (OR) 2 'Fe (OR) 2 Fe (OR) 3, Co (OR) 2 and Ni (OR) 2,

  in these formulas, R can essentially be a hydrophilic radical

  any carbon having 1 to 24 carbon atoms, although the radicals

  Particularly preferred examples of such compounds include: NaOC 2 H 5, NaOC 4 H 9, Mg (OCH 3) 2, Mg (OC 2 HY) 2, Mg (OC 3 H 5) 2, and the like. , Ca (OC 2 H 5) 2, Zn (OC 2 H 5) 2, Zn (OC 2 H 5) Cl, Al (OC 3) 3 Al (OC 2 H 5) 3, Al (OC 2 H 5) Cl, Al (OC 3 H 7) 3, Al (OC 4 H 9) 3, Al (OC 6 H 5) 3, B (OC 2 H 5) 3,

  B (OC 2) 2 Cl, P (O 2 H 5) 3 P (OC 6 H 5) 3 and Fe (OC 4 H 9).

  In the present invention, the compounds represented by the general formulas: Mg (OR 3) pX 2 _p, Al OR 3) p X 3 _p and B (OR 3) p X 3 _, it is particularly preferred that R 3 represents a C 1 -C 4 alkyl radical or

a phenyl radical.

  In the compounds of general formula: R 4 R R 6 if 7) R R S -4Si-O 4 R qi

  R 4, R 5 and R 6 can essentially be used in the invention.

  each of which may contain any one of the hydrocarbon radicals having 1 to 24 carbon atoms, an alkoxy radical, a hydrogen atom or a halogen atom, but an alkyl or aryl radical is preferred

  or alkoxy or a halogen atom and R 7 can essentially represent

  any of the hydrocarbon radicals having 1 to 24 atoms

  of carbon, although alkyl and aryl radicals are preferred.

  Examples of such compounds include: mono-

  methyltrimethoxysilane, monomethyltriethoxysilane, monomethyl

  tributoxysilane, monomethyltri-sec-butoxysilane, monomethyl-

  triisopropoxysilane, monomethyltripentoxysilane, monomethyl

  trioctyloxysilane, monomethyltristearyloxysilane, monomethyl

  triphenoxysilane, dimethyldimethoxysilane, dimethyldiethoxy-

  silane, dimethyldiisopropoxysilane, dimethyldiphenoxysilane,

  trimethylmonomethoxysilane, trimethylmonoethoxysilane, triethyl

  methylmonoisopropoxysilane, trimethylmonophenoxysilane, mono-

  methyldimethoxymonochlorosilane, the monomethyldiethoxymonochloro-

  silane, monomethylmonoethoxydichlorosilane, monomethyldiethoxy-

  monochlorosilane, monomethyldiethoxymonobromosilane, monoethyl-

  diphenoxymonochlorosilane, dimethylmonoethoxymonochlorosilane,

  monoethyltrimethoxysilane, monoethyltriethoxysilane, mono-

  ethyltriisopropoxysilane, monoethyltriphenoxysilane, diethyl

  dimethoxysilane, diethyldiethoxysilane, diethyldiphenoxy-

  silane, triethylmonomethoxysilane, triethylmonoethoxysilane, triethylmonophenoxysilane, monoethyldimethoxymonochlorosilane,

  monoethyldis thoxymonochlorosilane, mono-Glyyldiphenoxymonochloro-

  silane S monoisopropyltrimethoxysilane, monoobutyltrimethoxy-

  Lilane, mono-butyltriethoxysilane, mono-sec-butyltriethoxy?

  silane, monophenyltriethoxysilane, diphenyldiethoxysilane, diphenylmonoe thoxymonochlorosilane, monomethoxytrichlorosilane, monoethoxytrichlorosilane, monoisopropoxytrichlorosilane, monobutoxytrichlorosilane, monopentyloxytrichlorosilane, halfoctyloxvtrichiorosilane, monostearyloxytrichlorosilane, monobutyronitrile L 1 year, o-pwmethylph 4 nouxytrichloroeilane,

  O, dimethoxydichlorosilane, 4-ethoxydichlorosil Ane, diiso-

  propoxydichlorogilane, dibutoxcydichlorosilane, octyloxy-

  diclilorosilane, trimethoxymonochlorosilanel, triethoxymone-

  chlorosilane> l triisopropoxymonochlorosilane, tributoxymond-

  chlorosilane, tri-sec-butoxymonochlorosilane, tetraethoxysilane, tetraisopropoxysilane and linear or cyclic polysiloxanes having units represented by the formula: R 4

  obtained by condensation of the above compounds.

  As the halogenated titanium compounds used in the invention, mention may be made of the titanium halide and alkoxyhalogenide halide. As titanium compound, the tetravalent and trivalent titanium compounds are used.

  tetravalent are those represented by the general formula Ti (OR) r X 4-

  R is an alkyl, aryl or aralkyl radical having 1 to 24 carbon atoms, XC is a halogen atom and r is 0, r <4, such as titanium tetrachloride, tetrabromide of t: itanei, totratodide; of titanium, monomethoxychlorotitanium, dimethoxydichlorotane,

  trimethoxymonochlorotitanium, monoethoxytrichlorotitanium, diethoxy-

  dichlorotitanium, triethoxymonochlorotitanium, monoisopropoxytri

  chlorotitanium, triproxydichlorotitanium, triisopropoxymono-

  chlorhydrate, monobutoxytrichlorotitanium, dibutoxydichlorotitanium, monopentyloxytrichlorotitanium, monophenoxytrichlorotitanium, diphenoxydichlorotitanium, and triphenoxymonochlorotitanium. As trivalent titanium titanium trihalides, titanium trihalides obtained by reduction of titanium tetrahalogenides, such as tetrachloride, can be mentioned. titanium and titanium tetrabromide by hydrogen, aluminum, titanium or an organometallic compound of a metal of Groups I to III of the Periodic Table, and

  that the trivalent titanium compounds obtained by reduction of halo-

  tetravalent alkoxytitanium genides of general formula Ti (OR) X 4 s with an organometallic compound of a group I to III metal of the periodic table where R represents an alkyl, aryl or aralkyl radical having 1 to 24 carbon atoms, X represents a halogen atom and S is O <s <4.

  in the invention titanium compounds tetravalent.

  In the invention, the process for obtaining the solid catalytic component by reaction of (1) a compound of the general formula R m (OR 2) n X 2 mn (2) a compound of the general formula 4e (OR 3) XR 4

6 '

  (3) a compound of the general formula R -Si O -R and (4) a R compound of halogenated titanium has no particular limitation The components (1) - (4) can be reacted at a temperature of in the range of from 20 to 4000 ° C, preferably from 50 to 300 ° C, for a period of time in the range of 5 min to h in the presence or absence of an inert solvent, or they may be

  react by copulverisatian treatment or combination

  The order of reaction of the components (1) (4) does not have any particular limitation either. The four components can be reacted simultaneously or three of them can be reacted and then the remaining component or to make react

  two of them, then react one of the two components

  then react with the remaining component.

  The inert solvents which can be used in the above reaction are not especially limited. Hydrocarbon compounds and / or their derivatives which do not inactivate Ziegler catalysts can be used. Examples of such solvents include various saturated aliphatic hydrocarbons, aromatic hydrocarbons and alicyclic hydrocarbons such as propane, butane, pentane, hexane, heptane, octane, benzene, toluene, xylene and cyclohexane, as well as alcohols, ethers and esters such as ethanol, ethyl ether,

  tetrahydrofuran, ethyl acetate and ethyl benzoate.

  The apparatus used for copulverisati Dn is not specifically limited, but generally a ball mill, vibratory mill, rod mill or impact mill is employed. Conditions such as temperature and the spray time can easily be determined by those skilled in the art according to the spray method adopted.

  spray temperature is between 0 and 200 ° C, preferably

  preferably between 1 and 30 hours. Of course, the copulverisation operation must be carried out in a gaseous atmosphere.

  inert and moisture should be kept to a minimum.

  The process in which the components (I) - (4) are reacted in solution or the method in which the components (I) - (3) are reacted in solution is preferably used in the invention and copulverises and is react the reaction product with

the component (4).

  With regard to the report to use compo-

  sants (1) and (2), too low or too high amounts of the compound

  of general formula 14 (OR) X p tend to reduce the activity of poly-

  To prepare a very active catalyst, it is desirable to

  that the molar ratio Mg / Me is in the range of 1 / 0.001 to 1/20, preferably 1 / 0.01 to 1/1 and more preferably 1 / 0.05 to

1 / 0.5.

  The ratio to use components (1) and (3) is such that the amount of component (3) is in the range of 0.1 to

  300 g, and preferably 0.5 to 200 g per 100 g of the component (1).

  It is particularly preferable to adjust the amount of the halogenated titanium compound so that the amount of titanium contained in the solid catalyst component is in the range of

  0.5 to 20% by weight The range of 1 to 10% by weight is particularly

  desirable to obtain a well-balanced activity

  titanium and / or vanadium and relatively to the solid.

  In the preparation of the solid catalyst component, it is also preferable to use as component (5) one or more members of the group consisting of organic halides, halogenating agents, phosphoric esters, electron donors, and the like. polycyclic aromatic compounds in addition to the components (1) - (4) The reaction method in the case where the component (5) is used is not particularly limited. The method in which the solution is reacted in solution is preferably used.

  components (1) - (5) or the process in which the solution is reacted

  components (1), (2), (3) and (5) and co-spray the product

  reaction with component (4).

  In the case where component (5) is used, its amount is between 0.01 and 5 mol, preferably between 0; 05 and 2 mol, per mole of the component (1) The organic halides which can be used as component (5) are aliphatic hydrocarbons

  saturated or unsaturated hydrocarbons and aromatic hydrocarbons which are

  The halogen may be fluorine,

chlorine, bromine or iodine.

  Examples of such organic halides include

  methylene chloride, chloroform, carbon tetrachloride, bromochloromethane, dichlorodifluoromethane, 1-bromo-2-chloroethane, chloroethane, 1,2-dibromo-dichloro-1, ethane,

  dichloro-1,1 ethane, 1,2-dichloroethane, 1,2-dichloroetetrachloride,

  fluoro-1,2,2 ethane, hexachloroethane, pentachloroethane,

  1,1,2-tetrachloroethane, 1,1-tetrachloroethane, 12.2 ethane,

  chloro-1,1,1-ethane, 1,1-trichloroethane, 1-chloropropane, 2-chloropropane, 1,2-dichloropropane, 1,3-dichloropropane,

  2,2-dichloropropane, heptachloro-1,1,2,2,23,3 propane,

  chloro-1,1,2,2,3,3 propane, octachloropropane, trichloro-1,2,1-propane, chloro-1-butane, 2-chlorobutane, chloro-1-methyl-2-propane , 2-chloro-2-methyl-propane, 1,2-dichloro-butane, 1,3-dichloro-butane, 1,4-dichloro-butane, 2,2-dichloro-butane, 1-chloro-pentane, chlorine hexane, chloro-1 heptane, chloro-1-octane, chloro-1 nonane, chloro-1 decane, vinyl chloride, dichloro-1, ethylene, 1,2-dichloroethylene, tetrachlorethylene, 3-chloropropene-1,3-dichloropropene,

  chloroprene, oleyl chloride, chlorobenzene, chloro

  naphthalene, benzyl chloride, benzylidene chloride,

  chloroethylbenzene, styrene dichloride and a-chlorocumene.

  Examples of halogenating agents that can be

  component (5) include non-metal halides

  such as sulfur chloride, PC 13, P C 15 and Si C 14 and oxy-

  non-metallic halides such as POC 13, COC 12, NO C 11, SO C 12 and

502 C 12.

  Examples of electron donors that can be used as component (5) include alcohols, esters, ketones, aldehydes, organic acids, ovaic acid esters, acid halides, amides, and the like. , amines and

nitrites.

  As alcohols, for example, alcohols having 1 to 18 carbon atoms such as methyl alcohol, ethyl alcohol, propyl alcohol, isopropyl alcohol, alcohol may be used.

  allyl, butyl alcohol, isobutyl alcohol, dry alcohol,

  butyl alcohol, tert-butyl alcohol, pentyl alcohol, hexyl alcohol, cyclohexyl alcohol, decyl alcohol, lauryl alcohol, myristyl alcohol, cetyl alcohol, stearyl alcohol, oldyl alcohol, benzyl alcohol, alcohol

  naphthyl, phenol and cresol.

  As ethers, it is possible to use, for example, ethers having 2 to 20 carbon atoms, such as dimethyl ether, diethyl ether, dibutyl ether or isopentyl ether.

  anisole, phenetole, diphenyl ether, phenylally-ether

  For example, those having 3 to 18 carbon atoms such as acetone, methyl ethyl ketone, methyl isobutyl ketone, methyl phenyl ketone, ethyl phenyl ketone,

and diphenylketone.

  As aldehydes, we can use as examples

  having 2 to 15 carbon atoms such as acetaldehyde, propional-

  dhyde, octylaldehyde, benzaldehyde and naphthadehyde.

  As organic acids, it is possible, for example, to use

  those having 1 to 24 carbon atoms such as formic acids,

  tick, propionic, butyric, valeric, pivalic, caproic, caprylic, stearic, oxalic, malonic, succinic, adipic, methacrylic, benzoic, toluic, anisic, oleic, linoleic

and linolenic.

17681

  As organic acid esters, there may be used, for example, those having 2 to 30 carbon atoms such as methyl formate, methyl acetate, ethyl acetate, propyl acetate, acetate. octyl, ethyl propionate, methyl butyrate, ethyl valerate, methyl methacrylate, methyl benzoate, ethyl benzoate, propyl benzoate, octyl benzoate, benzoate of phenyl, benzyl benzoate,

  ethyl o-methoxybenzoate, butyl p-ethoxybenzoate, p-ethoxybenzoate,

  methyl toluylate, ethyl p-toluylate, ethyl p-ethylbenzoate, methyl salicylate, phenyl salicylate,

  methyl naphthoate, ethyl naphthoate and ethyl anisate.

  As acid halides, it is possible to use

  for example, those having 2 to 15 carbon atoms, such as acetylene chloride,

  tyl, benzoyl chloride, toluoyl chloride and chloride

anisoyl.

  As amides, it is possible to use, for example, acetamide,

benzamide or toluamide.

  As amines, it is possible to use, for example, methyl

  amine, ethylamine, diethylamine, tributylamine,

  ridin, tribenzylamine, aniline, pyridine, picoline and

tetramethylenediamine.

  As nitriles, it is possible, for example, to use aceto

  nitrile, benzonitrile and tolunitrile.

  The phosphoric esters which can be used as component (5) are those represented by the general formula:

P OR

GOLD

  o the symbols R which may be similar or different represent

  hydrocarbon radicals having 1 to 24 carbon atoms.

  Examples of such compounds include triethyl phosphate, tributyl phosphate, triphenyl phosphate, tribenzyl phosphate, trioctyl phosphate, tricresyl phosphate, tritolyl phosphate, trixylyl phosphate and phosphate

diphenyl and xylenyl.

  Examples of polycyclic aromatic compounds which can be used as component (5) include naphthalene,

  phenanthrene, triphenylene, chrysene, benzo-3,4-phenylene

  threne, benzo-l, chrysene, picene, anthracene, tetraphene, 1,2,3,4-dibenzo-anthracene, pentaphene, 3,4-benzo pentaphene, tetracene, benzo-l , 2 tetracene, hexaphene, heptaphene, diphenyl, fluorene, biphenylene, perylene, coronene, bisantene, ovalene, pyrene, perinaphthene and their derivatives

halo and alkyl-substituted.

  The solid catalytic component thus obtained can be

  fixed on oxides of metals of groups II to IV of the classifica-

  In this case, not only the oxides of the metals isolated from groups II to IV of the periodic table, but also the double oxides of these metals and their mixtures can be employed. such metal oxides include: MgO, CaO, ZnO, BaO, SiO 2, SnO 2 'A 1203, Mg OA 1203, SiO 2 -A 1203, MgO SiO 2, MgO CaO 2 3 and AI 203 Ca O, and Si O 2, A 1203, SiO 2 A 1203 and

Mg O to 1203.

  The method of fixing the solid catalyst component to the metal oxide of Groups II to IV of the Periodic Table is not particularly limited. As a preferable example, a method may be adopted in which the components (1 )

  (2) and (3) as well as component (5) if it is necessary, using

  solvent, an ether, in the presence of the metal oxide, then the liquid phase is removed by washing, drying or other suitable method, then the component (4) is added and reacted with

  a hydrocarbon such as hexane to obtain a catalytic component

  lytic solid fixed on a support.

  As the organometallic compound used in the invention, mention may be made of the organometallic compounds of the metals of groups I to IV of the periodic table which are known as components

  Ziegler catalysts, of which it is particularly preferred

  particularly organoaluminium compounds and organo-

  Examples of such compounds include organoaluminium compounds of the general formula I R 3 A 1, R 2 A 1 X, R Al X 2, R 2 A 1 OR, RA 1 (OR) X and R 3 A 12 X 3 where R symbols which may be the same or different represent alkyl, aryl or aralkyl radicals having 1 to 24 carbon atoms and X is a halogen atom, and organozinc compounds of the general formula R 2 Zn o the R symbols which may be similar or different represent alkyl radicals having 1 to 24 carbon atoms, such as triethylaluminum,

  triisopropylaluminum, triisobutylaluminum, tri-sec-butyl-

  aluminum, tri-tert-butylaluminum, trihexylaluminum, tris-

  octylaluminum, diethylaluminum chloride, diiso-

  propylaluminium, ethylaluminium sesquichloride, diethylzinc, and mixtures thereof With these organometallic compounds, organic carboxylic acid esters, such as ethyl benzoate, ethyl o-p-toluylate and The amount of the organometallic compound to be used is not especially limited. It can generally be between 0.1 and 1000 moles per mole of the titanium compound and / or

composed of vanadium.

  The polymerization of the oldfines with the catalyst of the invention can be carried out by suspension polymerization, solution polymerization, or vapor phase polymerization.

  vapor phase polymerization being particularly suitable.

  The polymerization reaction is carried out in the same way as a

  conventional reaction of polymerization of olefins with a catalyst

  Ziegler type; the reaction is therefore carried out substantially in the absence of oxygen and water and in the presence or absence of an inert hydrocarbon. The polymerization conditions include temperatures in the range of 20 to 1200 C, preferably 50 at * C, and pressures between atmospheric pressure and 70 bar, preferably 2 to 60 bar. The molecular weight can be adjusted to a certain extent by modifying the polymerization conditions such as the polymerization temperature and the molar ratio of the catalyst. but the addition of hydrogen in the polymerization system is more effective for this purpose Of course, when using the catalyst of the invention, it is possible to perform polymerization reactions in two or more without difficulty.

  several stages comprising different polymerization conditions.

  rents, such as different concentrations of hydrogen and

  different polymerization temperatures.

  The method of the invention can be applied to the poly-

  all olefins which can be polymerized with a

Ziegler-type catalyst and are particularly preferred

  For example, it is suitable for the homopolymerization of α-olefins such as ethylene, propylene, butene-1, hexene-1, methyl-4-pentene, and the like. 1 and octene-1, the copolymerization of ethylene and propylene, ethylene and butene-1, ethylene and hexene-1, ethylene and methyl-4 pentene-1, ethylene and octene-1 and propylene and butene-1, and copolymerization of ethylene with two

or several other "-olefins.

  It is also possible to carry out the copolymerization with dienes to modify the polyolefins. Examples of dienes that can be used in this copolymerization include

  butadiene, 1,4-hexadiene, ethylidene-norbornene and dicyclo

pentadiene.

  The invention is illustrated by the nonlimited examples

following.

EXAMPLE 1

  (a) Preparationof a solid catalytic cosant

  In a 500 ml three-necked flask equipped with a

  200 ml of ethanol, 20 g of tethoxy chloride are introduced into the

  magnesium (molar ratio Mg / C 1 0.8 i) obtained by treatment of

  magnesium diethylate with hydrochloric acid, 15 g tri-sec-

  aluminum butylate and 20 g of tetraethoxysilane, and the reaction is allowed to proceed for 3 h with refluxing ethanol.

  the ethanol is removed and then 200 ml of hexane and 5 ml of tetra-

  titanium chloride and reacted for 2 hours under reflux of hexane.

  Then, the supernatant liquid is removed to obtain a solid catalytic component which is washed three times with hexane.

  Catalystic solid is found to contain 25 mg of titanium / g.

(b) go lm_ isaon

  A stainless steel autoclave is used as

  vapor phase polymerization and a loop is formed with

  insufflator, a flow regulator and a dry cyclone The temperature of the autoclave is adjusted by passing hot water through

a shirt.

  In the autoclave whose temperature is adjusted to

   C, the solid catalyst component prepared below is introduced

  above and triethylaluminum at flow rates of 50 mg / h and 5 mmol / h, respectively, and ethylene, butene-1 and hydrogen gas are introduced by adjusting to obtain a butene-1 / ethylene molar ratio of 0. , 27 in the vapor phase of the autoclave and a hydrogen concentration of 15% of the total pressure.

  performs the polymerization by recycling the gases from the system through

  sufflator to maintain a total pressure of 9.8 bar

  The ethylene copolymer thus prepared has a density of

  0.28, a melt index (MI) of 1.2 and a density of 0.9203. The catalytic activity is 254,000 g of copolymer / g

of Ti.

  After 10 hours of continuous operation, the autoclave is opened and the interior is inspected. It can be seen that the inside wall of the autoclave and the stirrer are clean without

polymer adhesion.

  The FR (FR = IF 10 / IF 2.16 which is the ratio of the melt index IF 10 of the copolymer determined under a load of 10 kg to its melt index IF 2 16 determined under a load of 2.16 kg in both cases at 1900 C according to the method defined by standard ASTM-D 1238-65 T, is 7.2 and the weight distribution

  The molecular weight of the copolymer is therefore very narrow.

  A film was formed from the copolymer and extracted into boiling hexane for 10 hours; extraction

  with hexane is 1.3% by weight, which is very low.

  Comparative Example 1 A solid catalyst component is prepared as in

  Example 1, except that tetraethoxysilane is not added.

It contains 21 mg of titanium / g.

  A continuous vapor phase polymerization of ethylene and butene-1 was carried out in the same manner as in Example 1, except that the solid catalyst component prepared above was introduced at a rate of 50 mg / h The copolymer

  of ethylene thus prepared has a bulk density of 0.25, a den-

  sity of 0.9213 and a melt index of 1.2 The activity of

  catalyst is 186,000 g of copolymer / g of Ti.

  The F R of the copolymer is 8.2. A film is formed from the copolymer and extracted into boiling hexane for 10 hours; the extraction with hexane is 4.2% 2

in weight.

EXAMPLE 2

  (a) Preparation of a solid catalyst component A solid catalyst component is prepared as in Example 1, except that 15 g of boron triethylate are used instead of 15 g of tri-sec-butylate. aluminum It contains 27 mg of titanium / g (b) Polymerization

  Continuous polymerization is carried out in a continuous phase.

  ethylene and butene-1 as in Example 1 except that the solid catalyst component prepared above is introduced at a flow rate of 50 mg / h. The ethylene copolymer thus prepared has a

  apparent density of 0.27, a density of 0.9195 and a fluid

  The activity of the catalyst is 223,000 g of copolymer / g

Ti, which is very high.

  After 10 hours of continuous operation, you open the auto-

  clave and we inspect the interior We see that the inner wall

  autoclave and stirrer are clean without adhesion of poly-

mother.

  The F R of the copolymer is 7.3.

  of the copolymer and extracted in boiling hexane for h; the extraction with hexane is 1.5% by weight, which is

very weak.

EXAMPLE 3

  (a) Prearation of a solid catalytic component -

  A solid catalyst component is prepared as in Example 1 except that 20 g of a pentamare of tetraethoxysilane is used instead of 20 g of tetraethoxysilane. It contains

21 mg of titanium / g.

  (b) Polymerization A continuous vapor phase polymerization of ethylene and butane-1 is carried out as in Example 1, except that the solid catalyst component prepared above is introduced at a rate of 50. mg / h The ethylene copolymer thus prepared has a bulk density of 0.34, a density of 0.9200 and a melt index of 1.0. The catalyst activity is 332,000 g of copolymer / g of Ti which is very high.

  After 10 hours of continuous operation, you open the auto-

  clave and inspect the inside of it.

  clave and stirrer are clean without polymer adhesion.

  The F R of the copolymer is 7.2.

  of the copolymer and extracted in boiling hexane for h; the extraction with hexane is 1.3% by weight, which is

very weak.

EXAMPLE 4

  (a) Preparation of a solid catalyst component

  In a 500 ml three-necked flask equipped with a

  200 ml of normal hexane, 20 g of

  butylmagnesium, 15 g of aluminum triethylate and 20 g of

  ethoxymonochlorosilane and allow the reaction to take place during

  3 hours with reflux of the hexane. Then, the supernatant liquid is removed.

  and drying the reaction product to obtain a substance

white solid.

  10 g of the solid substance prepared above and 1.2 g of titanium tetrachloride are then placed in a stainless steel pot having a capacity of 400 ml and containing 25 stainless steel balls 12.7 mm in diameter and it is ground for 6 hours at room temperature under a nitrogen atmosphere to obtain a

  solid catalyst component containing 27 mg of titanium / g.

  (b) Polymerization A continuous vapor phase polymerization of ethylene and butene-1 is carried out as in Example 1 except that the solid catalyst component prepared above is introduced at a flow rate of 50 mg. The ethylene copolymer thus prepared has an apparent density of 0.31, a density of 0.9205 and a melt index of 1.1. The activity of the catalyst is 248,000 g of copolymer / g of Ti,

which is very high.

  After 10 hours of continuous operation, you open the auto-

  clave and inspect the interior.

  autoclave and agitator are clean without adhesion

of polymer.

  The F R of the copolymer is 7.5. A film of the copolymer is formed and extracted in boiling hexane for h; the extraction with hexane is 1.4% by weight, which is

very weak.

EXAMPLE 5

  A 2 l stainless steel autoclave equipped with an induction stirrer was purged with nitrogen and then 1000 ml of hexane was charged and 1 mmol of triethylaluminum and 20 mg of the solid powder were added.

  obtained in Example 1 and the temperature is raised to 90 ° C with stirring.

  The vapor pressure of the hexane brings the pressure of the system to 1.96 bar gauge. Hydrogen is introduced until the total pressure is 4.70 bar gauge and then introduced.

  ethylene to maintain the total pressure at 9.80 bar

  metric and allow the polymerization to proceed for 1 hour. Then, the polymer slurry was transferred to a beaker and the hexane removed under reduced pressure to obtain 183 g of a white polyethylene having a melt index of 1.3 and a density

  The activity of the catalyst is 71,800 g of poly-

  ethylene / g of Ti h pressure of C 2 H 4 or 1,800 g of polymer / g of

solids h pressure C 2 H 4.

  The F R of the polyethylene is 8.2 and the molecular weight distribution is very narrow Extraction with hexane

  is 0.15 X by weight, which is very low.

  Of course, various modifications can be

  provided by those skilled in the art to the devices or processes which come

  to be described solely as non-limiting examples,

  without departing from the scope of the invention.

Claims (10)

CLAIMS V D-I C-A-T-I-O   A process for preparing a polyolefin by polymerizing at least one olefin in the presence of a catalyst, characterized in that said catalyst comprises a solid catalyst component and an organometallic compound, said catalytic component comprising a substance obtained by reaction of at least one the following four components: (1) a compound is represented by the general formula R m (OR) n Mg x mn N 2 -mn (2) a compound represented by the general formula: Me (OR 3) X p zp (3) a compound represented by the general formula: R 4 6 7 R (o - + R q R   (4) a halogenated titanium compound, 1 23 7   R 1, R 2, R and R each represent a hydrocarbon radical having 1 to 24 carbon atoms, R 5, R 5 and R 6 each represent a hydrocarbon radical having 1 to 24 carbon atoms, an alkoxy radical, a hydrogen atom or hydrogen or a halogen atom, X represents a halogen atom, Me represents an element of groups I to VIII of the periodic table excluding silicon and titanium, z is the valence of Me and m, n , p and q are as follows: O m <2, Let <2, O <m + n <2, O (p z, 1 q <30.   Method according to claim 1, characterized in that said components (1) and (2) are used in a report   molar Mg / Me between 1 / 0.001 and 1/20.   Process according to claim 1, characterized in that said components (1) and (3) are used in a ratio such that the amount of said component (3) is in the range of 0.1   at 300 g per 100 g of said component (1).   4 Process according to claim 1, characterized in that said component (4) is used in an amount such that the amount of titanium contained in the solid catalytic component is included between 0.5 and 20% by weight.   Method according to claim 1, characterized in that   that Me is Na, Mg, Ca, Zn, Al, B, P or Fe.   Process according to claim 1, characterized in that said halogenated titanium compound is a titanium halide or a titanium alkoxy halide. Process according to Claim 1, characterized in that the said solid catalytic component comprises a substance obtained by reaction of the said components (1) to (4) with a component (5), the said component (5) comprising at least one component of the compound group. by organic halides, halogenating agents, phosphoric esters, electron donors and compounds polycyclic aromatic compounds.   Process according to Claim 7, characterized in that the said component (5) is used in a proportion of 0.01 to 5 moles per mole of said component (1).   Process according to Claim 1, characterized in that the said solid catalytic component is attached to an oxide of a   Group II to IV metal of the Periodic Table.   Process according to Claim 1, characterized in that the said organometallic compound is an organoaluminium compound or an organozinc compound.   11 Process according to claim 1, characterized in that the polymerization reaction is carried out at a temperature between 20 and 120 C and under a pressure of between aerospheric pressure and 70 bar.   Process according to claim 1, characterized in that said olefin is a "-olefin having 2 to 12 carbon atoms,