FR2541291A1 - CATALYTIC PROCESS FOR THE PREPARATION OF POLYOLEFINS - Google Patents

Abstract

FOR POLYMERIZATION, A CATALYST FORMED BY THE COMBINATION OF: IA SOLID SUBSTANCE RESULTING FROM THE REACTION OF A MAGNESIUM HALOGENIDE AND A TITANIUM AND OR VANADIUM COMPOUND IS USED; IIA RSI (GOLD) 4-M COMPOUND; A COMPOUND RAL (OR) 3-N, R, R, R AND R: HYDROCARBON RADICALS FROM 1 TO 24 C; OM3; 1N2; ETIVUN ORGANOMETALLIC COMPOUND. APPLICATION: CONTINUOUS PRODUCTION OF A POLYETHYLENE WITH LARGE APPARENT DENSITY WITH A NARROW MOLECULAR WEIGHT DISTRIBUTION.

Description

The present invention relates to a process for preparing

  polyolefins with a new polymerization catalyst.

  So far, in this technical field, Japanese Patent Publication No. 12105/1964 discloses a catalyst comprising a transition metal compound, such as a titanium compound, on a halide support. In addition, it is known from the Belgian patent No. 742 112, a catalyst obtained

  by the copulverisation of a magnesium halide and tetra-

titanium chloride.

  However, from the point of view of the desire that the activity of a catalyst be as high as possible for the manufacture of polyolefins, the process described in Japanese Patent Publication No. 12105/1964 is not yet satisfactory because of a low polymerization activity, whereas the polymerization activity achieved in the process of patent BE 742 112 is

  rather high, but we want a further improvement.

  In the process described in German Patent No. 2137872, the amount of magnesium halide used is substantially decreased by copulverization with tetrachloride.

  of titanium and alumina, but no increase in

  a remarkable degree of activity per unit weight of solid, which is accepted as a guideline for the indication of productivity, and

  it is desired to develop a catalyst having a higher activity.

  Furthermore, in the manufacture of polyolefins, it is also desirable, from the point of view of productivity and handling of the suspensions, that the apparent density of the resulting polymer is as high as possible. From this point of view, the process described in the aforementioned Japanese Patent Publication No. 12105/1964 is unsatisfactory, both for the density of the resulting polymer and for the polymerization activity, while in the process described in the aforementioned Belgian patent BE 742 112, the polymerization activity is high, but the density of the resulting polymer is low.

  an improvement for both processes.

  The invention can be summarized by indicating that its object consists in proposing a new polymerization catalyst and a process for homopolymerization or copolymerization of olefins using the catalyst, process and catalyst capable of overcoming the aforementioned drawbacks, of achieving high polymerization activity or yield, to give high polymers with high bulk density and to be able to

  implemented very easily in the form of continuous polymerization.

  naked. The present invention consists in particular of a process

  for preparing polyolefins by homopolymerization or copoly-

  olefin lymerization using a catalyst which comprises the combination of: a solid obtained by the reaction of at least the following two constituents: (i) a magnesium halide and (ii) a titanium compound and / or a vanadium compound; L-II 7 a compound represented by the general formula R 1 Si (OR 2) 4 m wherein R 1 and R 2 are hydrocarbon radicals having 1 to 24 carbon atoms, and O m 3; -III 7 a compound represented by the general formula

3 3 4

  R n Al (OR) 3 N wherein R and R are hydrocarbon radicals having 1 to 24 carbon atoms, and 1 N 2; and / or IV an organometallic compound, which catalyst satisfies the conditions according to which the molar ratio of the silicon of the component II to the titanium and / or the vanadium of the component I7 must be between 0.1 and 100, the report

  Molar of the constituent / III 7 aluminum to the constituent silicon

  killing / II 7 should be between 0.01 and 10, and the molar ratio

  of the constituent metal / -IV 7 to the titanium and / or vanadium of the

  It should be between 0.1 and 1000.

  Since the polymerization catalyst used in the present invention exhibits very high polymerization activity, the partial pressure of the monomer during polymerization is low and, because of the high density

  As a result of the resulting polymer, productivity can be improved.

  In addition, the amount of catalyst remaining in the resulting polymer after polymerization is so small that the manufacturing process

  polyolefin may dispense with a catechism removal step.

  this leads to a simplification of the polymer treatment step and, therefore, polyolefins can be prepared very economically. According to the process of the present invention, the amount of polymer produced per unit (volume) of polymerization reactor is large because of a large bulk density of

resulting polymer.

  The present invention is still advantageous when it is

  consider from the point of view of the size of the particles, or granu-

  the resultant polymer, the proportion of large particles and that of fine particles smaller than 50 μm being small despite a large bulk density of the polymer, and therefore,

  not only does it become easy to carry out a poly-

  continuous merger, but also the separation by centrifugal

  fugation, during the polymer treatment step, as well as the handling of the polymer particles during transport of the polymer.

powder become easy.

  According to the present invention, in addition to the large bulk density of the polyolefins obtained with the aid of the catalyst of the invention, as noted above, it can be seen that it is possible to prepare at a lower hydrogen concentration than in conventional processes of polyolefins having a desired index

  melt flow, which enables the polymer to be

  at a relatively low total pressure and contributes

  greatly improve profitability and productivity.

  In addition, in the polymerization of one or more olefins using the catalyst of the present invention, the rate of absorption of the olefin (s) does not decrease much even

  when time runs out and, therefore, we can conduct the polymerization

  for a long time using a small amount of the catalyst. In addition, the polymers prepared using the catalyst of the present invention have a narrow molecular weight distribution and their extraction rate by hexane is very low,

254 29 Â

  which reflects a minimized production of by-products formed by low quality polymers. For example, in film quality, these polymers can produce

  good quality and even have a superior characteristic

  resistance to accidental adhesion. We will now describe in more detail various aspects

  preferred embodiments of the invention.

  Examples of the magnesium halide used in the present invention include magnesium fluoride, magnesium chloride, magnesium bromide, substantially anhydrous magnesium iodide, and mixtures thereof.

  magnesium being the most preferred halide.

  Examples of the titanium compound and / or vanadium compound used in the present invention include halides, alkoxyhalides, alkoxides and halogenated oxides, titanium and / or vanadium. As preferred examples of the titanium compound, mentioning compounds of tetravalent titanium and trivalent titanium As the tetravalent titanium compounds, those represented by the general formula Ti (OR) X 4 _r (in which R represents an alkyl, aryl or aralkyl group having 1 to 24 carbon atoms) are preferred. , X is a halogen atom and r is such that O r <4), such as titanium tetrachloride, titanium tetrabromide,

  Titanium triiodide, monomethoxytrichlorotitanium, dimethoxy-

  dichlorotitanium, trimethoxymonochlorotitanium, diethoxydichloro

  titanium, tetramethoxytitanium, monetethoxytrichlorotitanium, triethoxymonochlorotitanium, tetrafthoxytitanium (or t 9

  titanium), monoisopropoxytrichlorotitanium, diisopropoxydichloro

  titanium, trisopropoxymonochlorotitanium, tetraisopropoxytitanium,

  monobutoxytrichlorotitanium, dibutoxydichlorotitanium, mono-

  pentoxytrichlorotitanium, monophenoxytrichlorotitanium, diphenoxydi-

  chlorotitanium, triphenoxymonochlorotitanium and tetraphenoxytitanium.

  As trivalent titanium compounds, it is possible to use, for example, titanium trihalides obtained by reduction of titanium tetrahalides such as titanium tetrachloride and titanium tetrabromide using hydrogen, aluminum, titanium or titanium. an organometallic compound derived from a metal selected from groups I to III of the Periodic Table, as well as trivalent titanium compounds obtained by reducing, using an organometallic compound derived from a metal selected from groups I to III of the Periodic Table, trivalent alkoxytitanium halides of general formula Ti (OR) s X 4 _s (wherein R represents an alkyl, aryl or aralkyl group having 1 to 24 carbon atoms, X is a halogen atom and S is such that O <S 4) Examples of the vanadium compound include tetravalent vanadium compounds such as vanadium tetrachloride, vanadium tetrabromide, vanadium tetraiodide and tetraethoxy vanadium (or vanadium tetraethoxide); pentavalent vanadium compounds such as vanadium oxytrichloride,

  ethoxytrichlorovanadyl, triethoxyvanadyl and tributoxy-

  vanadyl; and trivalent vanadium compounds such as vanadium trichloride and vanadium triethylate. Titanium compounds

  tetravalent are the most interesting in the present invention.

  To make the present invention more efficient, the titanium compound and the vanadium compound are often used together. In this case, it is preferable that the molar ratio

V / Ti is between 2/1 and 0.01 / 1.

  The process for obtaining the catalyst component by reacting the magnesium halide (i) with the titanium compound and / or the vanadium compound (ii) is not especially limited in the present invention. react (i) and (ii) by contacting them usually for 5 min to 20 h with

  heating at a temperature between 20 and 400 C, preferably

  In the alternative, the reaction can be carried out by a copulverization treatment. The latter is preferable in the present invention. The inert solvent which can be used to prepare the catalyst component is not especially limited. Hydrocarbons and / or their derivatives which do not inactivate Ziegler catalysts are usually used.

  are various saturated aliphatic hydrocarbons, aromatic hydrocarbons

  and alicyclic hydrocarbons such as propane, butane, pentane, hexane, heptane, octane, benzene, toluene, D 4 t 29 t xylene and cyclohexane, as well as alcohols, ethers and the like. esters such as ethanol, diethyloxide, tetrahydrofuran,

  ethyl acetate and ethyl benzoate.

  The apparatus to be used for co-spraying is not subject to any special limitations. Usually, a ball mill, a vibrating bowl mill, a tumbler or a centrifugal mill is used. Those skilled in the art can establish and easily apply, according to the co-spraying process used, the conditions for this copulverization 9 such as temperature and time In general, the copulverization is carried out at a temperature between 0 and 200 C, preferably between 20 and 10 C, for a period of between half an hour and 50 hours, preferably between 1 and 30 hours. Of course, the copulverization operation should be carried out in an inert gas atmosphere and

to avoid humidity.

  It is best to adjust the ratio between the magnesium halide and the titanium compound and / or the vanadium compound reacted so that the amount of titanium and / or vanadium contained in the catalyst component LI 7 is between

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

  particularly preferred for obtaining a well-balanced activity per unit weight of titanium and / or vanadium and per unit weight

solid.

  In addition, to prepare the catalyst component of the present invention, it is also preferable to use as constituent (ce), in addition to the magnesium halide (i) and the titanium compound and / or or vanadium (ii), one or more members of the group consisting of compounds of the general formula Me (OR) X (wherein Me is a member selected from groups I to VIII of the Periodic Table (at exclusion of titanium and vanadium), R is a hydrocarbon radical having 1 to 24 carbon atoms, X is a halogen atom, z is the valence of Me and pet t O (p <z), halides organic, halogenating agents, phosphoric esters, electron donors

  and polycyclic aromatic compounds.

  killing (c) in an amount of 0.01 to 5 moles, preferably

  0.05 to 2 moles per mole of the magnesium halide (i).

  Examples of compounds having the general formula Me (OR) X Zp, which can be used in the present invention, include the following compounds: Na OR, Mg (OR) 2, Mg (OR) X, Ca (OR ) 2, Zn (OR) 2, Zn (OR) X, Cd (OR) 2, Al (OR) 3, Al (OR) 2 X, B (OR) 3, B (OR) 2 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. The following compounds may be further preferred: Na OC 2 H 5, Na OC 4 H 9, Mg (OCH 32, Mg (OC 2 H 5) 2, Mg (OC 3 H 7) 2, Ca (OC 2 H 5) 2, Zn (OC 2 H 5) 2, Zn (OC 2 H 5) C 1, Al (OCH 3) 3, Al (OC 2 H 5) 3, Al (OC 2 H 5) 2 Cl, Al (OC 37) 3, Al (OC 4 H 9) 3, Al (OC 6 H 5) 3, B (OC 2 H 5) 3, B (OC 2 H 5) 2 c 1, P (OC 2 H 5) 3, P (OC 6 H 5) 3 and Fe (OC 4 H 9) 3 In particular, the compounds represented by

  the general formulas Mg (OR) X 2 -p, Al (OR) X 3 -p and B (OR) p X 3 -p.

  As the substituent R, C 1 to C 4 alkyl groups are preferred and

the phenyl group.

  The organic halides that can be used in the present invention are saturated or unsaturated aliphatic and aromatic hydrocarbons containing halo substituents, which include mono-, di- and tri-substituted compounds. The halogen, or each halogen, can be chosen independently among fluorine,

chlorine, bromine and iodine.

  Examples of such organic halides include methylene chloride, chloroform, carbon tetrachloride, bromochloromethane, dichlorodifluoromethane,

  1-bromo-2-chloroethane, chloroethane, 1,2-dibromo-1,1-dichloroethane

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

  1,1,2,2-tetrafluoroethane, hexachloroethane, pentachloroethane,

  1,1,1,2-tetrachloroethane, 1,1,2,2-tetrachloroethane, 1,1,1-

  trichloroethane, 1,1,2-trichloroethane, 1-chloropropane, 2chloropropane, 1,2-dichloropropane, 1,3-dichloropropane, 2,2dichloropropane, 1,1,1,2,2,3 , 3-heptachloropropane,

  1,1,2,2,3,3-hexachloropropane, octachloropropane, 1,1,2-trichloro-

  porpane, 1-chlorobutane, 2-chlorobutane, 1-chloro-2-

  methylpropane, 2-chloro-2-methylpropane, 1,2-dichlorobutane, 1,3dichlorobutane, 1,4-dichlorobutane, 2,2-dichlorobutane, 1chlorodecane, vinyl chloride, 1,1-dichlorobutane, -dichlorethylene, 1,2-dichloroethylene, tetrachlorethylene, 3-chloro-1-propene, 1,3dichloropropene, chloroprene, diolyl chloride, chlorobenzene, chloronaphthalene, benzyl chloride, benzylidene chloride, chloroethylbenzene , dichloride

styrene and chlorocumene.

  Examples of halogenation which can be used in the present invention include halides of non-metallic elements such as sulfur chloride, PC 13, PC 15 and SiC 14, as well as oxyhalides of non-metallic elements such as POC. 13

COC 12, NOC 12, SOC 12 and 502 C 12.

  The phosphoric esters which can be used in the present invention are compounds represented by the general formula / OR P OR, in which the R symbols, which are identical or different,

O OR

  each of these compounds are triethyl phosphate, tri-n-butyl phosphate, triphenyl phosphate, tribenzyl phosphate, trioctyl phosphate, tricresyl phosphate, tritolyl phosphate, trixylyl phosphate

  and diphenylixylenyl phosphate.

  Examples of electron donors for use in the present invention are alcohols, ethers, ketones, aldehydes, organic acids, organic acid esters, acid halides, acid amides, amines, and the like.

nitrites.

  As alcohols, it is possible to use, for example, those having 1 to 18 carbon atoms such as methyl alcohol, ethyl alcohol,

  propyl alcohol, isopropyl alcohol, allyl alcohol

  liquefied natural butyl alcohol, isobutyl alcohol, secondary butyl alcohol, tert-butyl alcohol, normal amyl alcohol, normal hexyl alcohol, cyclohexyl alcohol, decyl alcohol, and the like. lauryl alcohol, myristyl alcohol, cetyl alcohol, stearyl alcohol, oleyl alcohol, benzyl alcohol, naphthyl alcohol, and also phenol and cresol ethers. for example, those having 2 to 20 carbon atoms, such as dimethyl ether, diethyl ether, dibutyl oxide, isoamyl oxide, anisole, phenetole, diphenyl ether, phenyl ether

and allyl and benzofuran.

  As ketones, it is possible to use, for example, those having 3 to 18 carbon atoms, such as acetone or methyl ethyl ketone.

  methyl isobutyl ketone, methyl phenyl ketone, ethyl phenyl ketone.

and diphenylketone.

  As aldehydes, it is possible to use, for example, those

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

  dehyde, octylaldehyde, benzaldehyde and naphthaldehyde.

  As organic acids, it is possible to use, for example, those having 1 to 24 carbon atoms, such as formic acid, acetic acid, propionic acid, butyric acid, valeric acid, pivalic acid, caprylic acid, caprylic acid, stearic acid, oxalic acid, malonic acid, succinic acid, adipic acid or methacrylic acid, benzole, toluic, anisic, oleic, linoleic

and linolenic.

  As organic esters it is possible to use, for example, those having 2 to 30 carbon atoms, such as methyl formate, methyl acetate, ethyl acetate, propyl acetate and octyl acetate, ethyl propionate, methyl butyrate, ethyl valerate, methyl methacrylate, methyl benzoate, ethyl benzoate, propyl benzoate, benzoate

  of octyl, phenyl benzoate, benzyl benzoate, ethoxy-

  butyl benzoate, methyl toluylate, ethyl toluylate, ethyl ethyl benzoate, methyl salicylate, phenyl salicylate, methyl naphthoate, ethyl naphthoate and

ethyl anisate.

  As acid halides, for example, those having 2 to 15 carbon atoms such as acetyl chloride, benzoyl chloride, toluoyl chloride, and anisoyl chloride may be used. As amides, it is possible to use, for example, acetamide,

benzoylamide and toluoylamide.

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

  amine, ethylamine, diethylamine, tributylamine, piperidine,

  tribenzylamine, aniline, pyridine, picoline and tetra-

diamine.

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

  nitrile, benzonitrile and tolunitrile.

  Examples of polycyclic aromatic compounds which can be used in the present invention include naphthalene, phenanthrene, triphenylen, chrysene, 3,4-benzophenanthrene, 1,2-benzochrysene, picene, anthracene, Tetraphen, 1,2,3,4-dibenzanthracene, pentaphene, 3,4-benzopentaphene, tetraene, 1,2-benzotetracene, hexaphene, heptaphene, diphenyl, fluorine Rne, biphenylene, perylene, corona, bisantene, ovalene, pyrene and perinaphthene,

  as well as their halogenated and alkylated derivatives.

  The catalyst component L / -I 7 thus obtained can be placed on a support consisting of an oxide of a metal selected from Groups II to IV of the Periodic Table. This embodiment is also preferred in the present invention. In this case, not only Group II to IV metal oxides can be used in isolation, but also double oxides of these metals and their mixtures can be used. Examples of such oxides of

  metals are MgO, CaO, ZnO, BaO, SiO 2, SnO 2, A 1203, MgOA 1203, SiO 2.

  At 1203, MgO.sub.2 SiO.sub.2, MgO.sub.2 Ca.sub.2O.sub.201, and A 1203.Ca.sub.O.

  If O 2, A 1203, If O 2 A 1203 and Mg O A 1203.

  The method of disposing the catalyst component on a support of a Group II to IV metal oxide of the Periodic Table has no special limits, but a preferred method may be mentioned. wherein components (i) and (ii), and component (O) are reacted under heating if necessary, for example in ether as a solvent in the presence of said metal oxide and then the liquid is removed. Examples of the compound of general formula R Si (OR 2 M 4-m

  that are used in the present invention include mono-

  methyltrimethoxysilane, monomethyltriethoxysilane, monomethyl-

  tri-n-butoxysilane, monomethyl tri-sec-butoxysilane, monomethyl

  triisopropoxysilane, monomethyltripentoxysilane, monomethyl

  trioctoxysilane, monomethyltristearoxysilane, monomethyl

  triphenoxysilane, dimethyldimethoxysilane, dimethyldiethoxy-

  silane, diméthyldiisopropoxysilane of diméthyldiphénoxysilane of triméthylmonométhoxysilane of triméthylmonodthoxysilane of triméthylmonoisopropoxysilane of-triméthylmonophénoxysilane of monogthyltriméthoxysilane of monoethyltriithoxysilane of monoéthyltriisopropoxysilane of monoithyltriphdnoxysioane of digthyldiméthoxysilane of didthyldidthoxysilane of diethyl

  diphenoxysilane, triethylmonomethoxysilane, triethylmonoethoxy-

  silane, triethylmonophenoxysilane, monoisopropyltrimethoxy-

  silane, mono-n-butyltrimethoxysilane, mono-n-butyltriethr

  silane, mono-sec-butyltriethoxysilane, monophyllyltriethoxy-

  silane, diphinyldiethoxysilane, tetragthoxysilane and tetraisopropoxysilane. If the amount of the compound of the general formula R m Si (OR) 4 m used in the present invention is too large or too small, it can not be expected that this compound will play its role of Usually, its amount is between 0.1 to 100 moles, preferably 0.3 to 20 moles, per mole of the titanium compound and / or the vanadium compound present in the constituent

CI 7 of the catalyst.

  As examples of the compound of the general formula R n Al (OR 4) 3 N which is used in the present invention, it is possible to

  mention the following compounds: dimethylaluminum monoethylate

  aluminum dimethylaluminium monoisopropylate, dimethylaluminum mono-n-butylate, dimethylaluminum secondary butylate,

  dimethylaluminum monophenate, diglycyl

  aluminum, didethylaluminum monoethylate, diethylaluminum monoisopropylate, digethylaluminum normal monobutylate, diethylaluminum secondary butylate, monophenyl

  diethylaluminum, diethylaluminum monooctylate, mono-

  diethylaluminum stdarylate, diisobutylaluminum monodthylate

  nium, dimethyl methylaluminum ethoxide, methyl diethylate,

  aluminum, dimethylethylaluminum ethylate, ethyl diethylate,

  aluminum, ethylaluminium diisopropylate, ethylaluminum normal dibutylate, ethylaluminum phenate, dimethylate

  of isobutylaluminum and isobutylaluminum diethylate.

  For the compound of the general formula R 4 Al (OR 4) 3 N which is used in the present invention, both a too large amount used in the present invention, both too much and too little risk to not be effective

  proportion of this compound is between 0.01 and 10 moles, preferably

  0.05 to 2 moles, per mole of the silicon compound present in

the L-II component 7 of the catalyst.

  As examples of the organometallic compound used in the present invention, mention may be made of organometallic compounds derived from metals of groups I to IV of the Table.

  Periodical, which is known as the constituents of

  Ziegler-type lytic agents, but organoaluminum compounds of organoaluminium, for example organoaluminum compounds of the general formula R 3 Al R 2 A 1 X, RAX 2 and R 3 A 12 X 3, are particularly preferred. R, identical or different, each represents an alkyl or aryl group having 1 to 20 carbon atoms and X is a halogen atom, and the organic compounds of

  zinc, of the general formula R 2 Zn, in which the R symbols, identical to

  different or different, each represents an alkyl group having

  1 to 20 carbon atoms, such as triethylaluminum, triisopropyl-

  aluminum, triisobutylaluminum, tri-sec-butylaluminum, tritertiobutylaluminum, trihexylaluminum, trioctylaluminum, tridecylaluminum, diethylaluminum chloride, diisopropylaluminum chloride, ethylaluminum sesquichloride, diethylzinc and mixtures thereof With these organometallic compounds, carboxylic acid esters such as ethyl benzoate, ethyl toluylate and ethyl anisate can be used. The organometallic compound can be used in an amount of from 0.1 to 1000 moles per mole of the titanium and / or vanadium compound

component / -I 7 of the catalyst.

  The polymerization of the olefin (s) using the catalyst of the present invention can be carried out by suspension polymerization, solution polymerization or vapor phase polymerization. Suspension polymerization and vapor phase polymerization are particularly preferred. the polymerization reaction in the same way as in the case of the conventional olefin polymerization reaction using a Ziegler-type catalyst That is to say that the reaction is carried out by operating on substances substantially without oxygen or water and operating in the presence or absence of an inert hydrocarbon The polymerization conditions of the one or more olefins comprise temperatures of between 20 and 120 ° C., preferably between 50 ° C. and 100 ° C., and pressures lying between the pressure. atmospheric and 70 bars, preferably between 2 and 60 bars can be adjusted to some extent the polymerization conditions such as the polymerization temperature and the molar ratio of the catalyst components, but the addition of hydrogen to the polymerization system is more effective for this purpose. Of course, using the catalyst of the In the present invention, polymerization reactions can be carried out in two or more stages with different polymerization conditions, such as different concentrations of hydrogen and different polymerization temperatures, without any

difficulty.

  The process of the present invention is applicable to the polymerization of all polymerizable olefins using a Ziegler type catalyst. In particular, olefins having from 2 to 12 carbon atoms are preferred. The present invention is suitable for the homopolymerization of olefins-c such as ethylene, propylene, butene-1, hexene-1, 4-methylpentene-1 and octene-1, copolymerization of ethylene and propylene, ethylene and butene-1, ethylene and hexene-1, ethylene and 4-methylpentene-1, ethylene and

  octene-1, and propylene and butene-1, as well as copoly-

  Ethylene and two or more other olefins are also preferred. Copolymerization with dienes is also preferred for the modification of the polyolefins. As dienes, for example, butadiene, 1,4-hexadiene, ethylidene norbornene

and dicyclopentadiene.

  The following examples are given for illustrative purposes

  but not limiting of the present invention.

Example 1

  (a) Preparation of solid catalyst component (I)

  10 g of an anhydrous magnesium chloride are

  2.3 g of aluminum triethylate and 2.5 g of titanium tetrachloride in a stainless steel container having a capacity of 400 ml and containing 25 stainless steel balls of 1.27 cm in diameter. , and grinding is carried out for 16 hours using the beads, at room temperature in a nitrogen atmosphere, to obtain a constituent (I) of solid catalyst containing

  41 mg of titanium per gram of constituent.

  (b) Polymerization A stainless steel autoclave of 2 was purged with nitrogen, equipped with an induction stirrer, and then 1000 ml of hexane were introduced.

  then 1 millimole of triethylaluminum, 0.05 millimole of diethyl-

  diethoxysilane, 0.01 millimole of diethylaluminum monoethylate and 10 mg of the above solid catalyst component (I), and the temperature is raised with stirring up to 90 OC With the pressure

  of hexane, the system is pressurized

  metric of the order of 2 bars is then introduced hydrogen to a total pressure of 4.8 bar and then ethylene to a total pressure of 10 bar is then allowed to begin polymerization and it continues during

  I hour, while maintaining the pressure at 10 bar

  internal metric in the autoclave The polymer slurry was then transferred to a beaker and the hexane was removed under reduced pressure to give 175 g of a white polyethylene having a melt flow index of 1, 1 and a bulk density of 0.38 g / cm 3, the catalytic activity is 82 100 g of polyethylene / g

  Ti C 2 H 4 pressure relief.

  3,370 g of polyethylene / g of solid h pressure unit

of C 2 H 4.

  The value of the ratio between the fusion indices of the poly-

  the ethylene thus obtained is 7.5. The molecular weight distribution is therefore extremely narrow in comparison with the example

comparative 1 next.

  (It is known that the ratio between the melt indices represents the extent of the molecular weight distribution and this ratio is calculated as follows: melt index under 10 kg of ratio between melt indexes melt index under 2.16 kg The melt index (or melt flow) is

measurement according to ASTM D-1238 ,.

  Comparative Example 1 Polymerization of ethylene was carried out in the same manner as in Example 1, except that no diethylaluminum monoethylate was used, and 140 g of a white polyethylene were obtained.

  having a bulk density of 0.33 and a melt index of 1.0.

  The catalytic activity is 65,700 g of polyethylene / g of Ti h.

  pressure unit of C 2 H 4 and 2700 g of polyethylene / g of solid.

  h pressure unit of C 2 H 4 o The value of the ratio between the indices

  The polyethylene melting point is 8.0.

Example 2

  Ethylene polymerization is carried out in the same manner as in Example 1, except that 0.05 millimole of monoethyltriethoxysilane is used instead of diethyldiethoxysilane and the amount of 0.02 millimol is diglycylaluminum monoethylate is thus obtained 163 g of a white polyethylene

  having a melt index of 0.9 and a bulk density of 0.41.

  The catalytic activity is 76,500 g of polyethylene / g of Ti h. pressure value of C 2 H 4 3 130 g of polyethyline / g of solid h pressure unit of C 2 H 4 o The value of the ratio between the melting indices of the

  polyethylene thus obtained is 7.4. The molecular weight distribution

  is therefore extremely narrow compared to the example

comparative 2 next.

  Comparative Example 2 Polymerization of ethylene is carried out in the same manner as in Example 2, except that diethylaluminum monoethylate is not used. 121 g of a white polyethylene having a melting of 1.1 and a bulk density of 0.32 g / cm 3 The catalyst activity is 56,800 g of polyethylene / g of Ti h pressure unit of C 2 H 4, 2,330 g of polyethylene / g of solid h pressure unit of C 2 H 4 The value of the ratio between

  Melting index of polyethylene is 8.1.

Example 3

  Ethylene polymerization was carried out in the same manner as in Example 1, except that 0.1 millimole of diphenyl dimethoxysilane and 0.02 millimole of ethylaluminum diphenate were used instead of didthyldigthoxysilane and sodium monodylate. Thus, 181 g of a white polyethylene having a melt index of 1.3 and an apparent density of 0.39 are obtained. The catalytic activity is 84,900 g of polydthylene / g of

  Ti.h pressure unit of C 2 H 4, 3,480 g of polyethylene / g of solid.

  h C 2 H 4 pressure unit The value of the ratio between the polyethylene melt indexes is 7.5 The molecular weight distribution is extremely narrow compared to that of

the following comparative example 3.

  Comparative Example 3 Ethylene polymerization is carried out in the same manner as in Example 3, except that no ethylaluminum diphinate is used. 133 g of a white polyethylene are thus obtained. The melt index is 1.0% and the apparent density is 0.33. The catalytic activity is 62,400 g of polydthylene / g of Ti h pressure unit of C 2 H 4, 2,560 g of polyethylene / g of solid H unit pressure C 2 H 4 The value of the ratio between

  polyethylene melting index is 8.0.

Example 4

  (a) Preparation of solid catalyst component 10 g of a commercially available magnesium chloride and 4.2 g of aluminum triglyceride are placed in a stainless steel jar with a capacity of 400 ml and containing 25 stainless steel balls 1.27 cm in diameter each, and grinding is carried out using these beads for 16 hours at room temperature.

  in a nitrogen atmosphere to obtain a reaction product.

  A three-necked flask equipped with a stirrer and a reflux condenser is then purged with nitrogen and 5 g of the above reaction product and 5 g of silica (Fuji-Davison product no. )

  which was calcined at 600 ° C. Then 100 ml of tetrahydro-

  furan and the reaction is allowed to proceed at 600 ° C. for 2 hours.

  The tetrahydrofuran is then removed by drying at 120 ° C. under reduced pressure. Then 50 ml of hexane are added and, after stirring, 1.1 ml of titanium tetrachloride is added and the reaction is allowed to proceed for 2 hours with reflux of hexane to give a solid powder (A) containing 40 mg of titanium per gram of this powder. The solid powder (A) is introduced into 50 ml of hexane, then 1 ml of tetraethoxysilane is added and the reaction is allowed to proceed for 2 hours with reflux of hexane, which gives a

  solid component / catalyst.

  (b) Polymerization A stainless steel autoclave of 21, equipped with an induction stirrer, is purged with nitrogen, and 1000 ml of hexane and then 1 millimole of triethylaluminum, 0.05 millimole, are introduced into it. of

  dimethyldiethoxysilane, 0.01 millimole diethyl monoethylate

  aluminum and 10 mg of solid catalyst component CI 7

  The temperature is raised to 90 ° C. With the vapor pressure of the hexane, the system is controlled to a pressure of 2 bar. Then hydrogen is introduced to a pressure of total of 4.8 bar, then ethylene up to a total gauge pressure of 10 bar. Polymerization is then allowed to begin and continues for

  However, the pressure at 10 bar

  Internal Metric of the Autoclave The polymer suspension was then transferred to a beaker and the hexane was removed under reduced pressure to give 60 g of a white polyethylene having a melt index of 0.7 and a density. 0.42 catalytic activity is 28,800 g of polyethylene / g of Ti h pressure unit of C 2 H 4, 1,150 g of polyethylene / g of solid h pressure unit of C 2 H 4 The value The ratio of the melt indexes of this polyethylene is 7.4. The molecular weight distribution is extremely narrow, compared with the following Comparative Example 4. In addition, the polymer particles exhibit superior fluidity and particle size. way is to

730 / m.

  Comparative Example 4 The polymerization of ethylene is carried out in the same manner as in Example 4, except that no diethylaluminum monoethylate is used. 48 g of a polyethylene having a melt index are thus obtained. 0.9 and a bulk density of 0.34. The catalytic activity is 23,100 g polyethylene / g Ti h. pressure unit of C 2 H 4, 920 g of polyethylene / g of solid h pressure unit of C 2 H 4 The value of the ratio of the melting indices of

this polyethylene is 8.1.

Example 5

  (a) Preparation of Solid Catalyst Compound 10 g of a commercial anhydrous magnesium chloride, 2.0 g of titanium tetrisopropylate and 1.7 g of isopropyl chloride are placed in a jar. stainless steel having a capacity of 400 ml and containing 25 stainless steel balls of 1.27 cm diameter each, and grinding is carried out using these beads for 16 hours at room temperature in an atmosphere of nitrogen to give an IC 7 solid catalyst component containing 25 mg

  titanium per gram of this catalyst.

  (b) Polymerization A 2-liter stainless steel autoclave equipped with a stirrer was purged with nitrogen and 1 000 ml of hexane and 1 millimol of trigthylaluminum, 0.1 millimole

Diphenyldiethoxysilane, 0.05 millimole of diethyl monodthylate

  aluminum and 10 mg of the solid catalyst component

  above, and the temperature is raised while stirring the temperature up to 900 C. With the vapor pressure of hexane, the system is put under a pressure of 2 bar manomdtric Then hydrogen is introduced up to at a total pressure of 4.8 bar, then of ethylene up to a total manomitric pressure of 10 bar. Polymerization is then started and continued for 1 hour while the total pressure is maintained at 10 bar. The polymer suspension is then transferred to a beaker and the hexane is removed under reduced pressure to give 44 g of a white polyethylene having a melt index of 1.1 and a bulk density of 0.38. The catalytic activity is 3,700 g of

  polyethylene / g Ti H pressure unit C 2 H 4, 850 g poly-

  ethylene / g of solid H pressure unit of C 2 H 4 The value of the ratio of the melt indexes is 7.6, and thus the molecular weight distribution is narrow. Comparative Example 5 Polymerismation of ethylene is carried out in the same manner as in Example 5, except that diethylaluminum monoethylate is not used. 35 g of a polyethylene having

  a melt index of 0 9 and an apparent density of 0.31 o

  The catalytic value is 26,800 g of polyethylene / g of Ti C 2 H 4 pressure, 670 g of polyethylene / g of solid H pressure unit of C 2 H 4 The value of the ratio between the melt indexes is

of 8.2.

Example 6

  A vapor phase polymerization is carried out using

  reading the solid catalyst component I7 obtained in Example 1.

  As a vapor phase polymerization apparatus, a stainless steel autoclave is used and a loop comprising

  a fan, a flow control device and a dry cyclone.

  The temperature of the autoclave is adjusted by passing water

hot in his envelope.

  In the autoclave adjusted to 80 C, the

  killing solid catalyst obtained in Example 1, diethyl-

  diethoxysilane, diethylaluminum monoethylate and triethyl

  aluminum at flow rates of 50 mg / h, 0.25 mmol / h, 0.05 mmol / h and 5 mmol / h, respectively. Hydrogen and ethylene are also introduced while adjusting the obtain a molar ratio hydrogen / ethylene of 0.45 in the vapor phase of the autoclave At the same time, the gases are circulated by means of the fan in the system to maintain the pressure

total pressure at 10 bar.

  Polymerization was carried out under these conditions to give polyethylene having a bulk density of 0.36 and a melt index of 0.9. The catalytic activity was 384,000 g polyethylene / g Ti. the indices of

merger is 7.6.

Example 7

  (a) Preparation of the Solid Catalyst Component-I 7 6.5 g of a commercially available anhydrous magnesium chloride, 1.5 g of boron triethylate and 1.5 g of titanium tetrachloride are placed in a jar. stainless steel with a capacity of 400 ml and containing 25 stainless steel balls each

  1.27 cm in diameter, and it is carried out for 16 hours at

  At room temperature, ball milling under a nitrogen atmosphere gives a solid catalyst component containing

mg of titanium per gram.

  (b) Polymerization The polymerization of ethylene is carried out in the same way as in Example 1, except that 10 mg of the constituent is used.

  Solid catalyst prepared just as described above.

  166 g of a white polyethylene having a melt index of 1.3 and a bulk density of 0.30 are thus obtained. The catalytic activity is 79,800 g of polyethylene / g of Tioh unit of pressure of C 2 H 4. , 3 190 g of polyethylene / g of solid h unit of pressure of C 2 H 4 o The value of the ratio between the melt indexes

polyethylene is 7.6.

Example 8

  In the pot of a ball mill of the same type as that described in Example 7, 10 g of a commercial anhydrous magnesium chloride, 2.2 g of magnesium diethylate and 2.3 g of tetrachloride are introduced. Titanium The mixture was bead milled for 16 hours at room temperature in a nitrogen atmosphere and a catalyst component was obtained.

  solid content 40 mg of titanium per gram.

  Ethylene polymerization is carried out in the same manner as in Example 1 except that 10 mg of the component is used.

  Solid catalyst prepared as described just above.

  88.4 g of a white polyethylene having

  a melt index of 0.95 and a bulk density of 0.28.

  The catalytic activity is 42,500 g of polyethylene / g of Ti h unit pressure of C 2 H 4, 1700 g of polygthylene / g of solid h unit of pressure of C 2 H 4 The value of the ratio between the indices fusion

of this polyethylene is 7.6.

Claims (11)

  Process for the preparation of a polyolgine by polymer   at least one oldfine with the aid of a catalyst, characterized in that said catalyst comprises the combination of: a solid obtained by the reaction of at least the two following constituents: ) a magnesium halide and (ii) a titanium compound and, optionally or alternatively, a vanadium compound; II-II a compound represented by the general formula R) Si (OR 2) 4, R '2 W -m wherein R and R are hydrocarbon radicals having 1 to 24 carbon atoms and O m <3; / LIII 7 a compound represented by the general formula R 3 n Al (OR 4) 3 ns wherein R and R represent hydrocarbon radicals having 1 to 24 carbon atoms, and 1 N 2; and -Iv 7 an organometallic compound, the molar ratio of silicon of the constituent II / II to titanium and, optionally or alternatively, to the vanadium of the constituent / I 7 being between 0.1 and 100, the molar ratio of the aluminum component / IIIIII to silicon of the constituent / CII 7 lying between 0.01 and 10, and the molar ratio of the metal of the constituent / CIV 7 to titanium and, optionally or alternatively, to the vanadium of   constituting -I 7 ranging between 0.1 and 1000.   Process according to Claim 1, characterized in that the catalyst component CI 7 comprises a substance obtained by the reaction of component (i), component (ii) and one or more additional constituents (a) chosen from compounds of general formula Me (OR) p Xzp, wherein Me is a member selected from groups I to VIII of the Periodic Table, excluding titanium and vanadium; R represents a hydrocarbon radical having 1 to 24 carbon atoms; X is an atom   halogen; z is the valence of Me and p is such that O <p Rz.   Process according to Claim 1, characterized in that the component / I 7 of the catalyst comprises a substance obtained by the reaction of component (i), component (ii) and one or more other constituents (c X) chosen from halogens   organic and halogenating agents.   Process according to Claim 1, characterized in that the catalyst component (I) comprises a substance obtained by the reaction of component (i), component (ii) and one or more additional constituents (a) selected from phosphoric esters. Process according to Claim 1, characterized in that the constituent CI 7 of the catalyst comprises a substance obtained by the reaction of component (i), component (ii) and U of one or more additional constitutions (oi) chosen from electron donors.   Process according to claim 1, characterized in that component I 7 of the catalyst comprises a substance obtained by the reaction of component (i), component (ii) and one or   several additional constituents (Oc) selected from the polycyclic aromatic salts.   Process according to claim 2, characterized in that the constituent (), represented by the general formula Me (OR) XP, p x- * p is selected from the group consisting of Al (OR) X 3 p, B (OR) ) X 3 and Mg (OR) p X 2 p the symbols R, X and p having the claim 2.   Process according to Claim 1, characterized in that the constituent I 7 of the catalyst is arranged on a support formed by an oxide of a metal chosen from groups II to IV of the Table Periodic.   Process according to claim 1, characterized in that   the magnesium halide is a magnesium halide anhydrous.   Process according to Claim 1, characterized in that the titanium compound is selected and, optionally or   Alternatively, the vanadium compound among halides, alkoxides,   halides, alcoholates and halogenated oxides of titanium and,   optionally or alternatively, vanadium.   Process according to claim 1, characterized in that the organometallic compound is an organoaluminum compound or an organotin compound.   Method according to claim 1, characterized in that   olefin is an olefin having 2 to 12 carbon atoms.   13 Process according to claim 1, characterized in that the polymerization reaction is carried out at a temperature between 20 C and 120 C and at a pressure between atmospheric pressure and 70 bar.