NL8201252A - CATALYST. - Google Patents

Description

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YO 3257 -1-

Olefin polymerization catalysts

The invention relates to a new catalyst for the polymerization of olefins.

Various catalysts are known in the art, which include solid inorganic magnesium compounds such as magnesium halides, magnesium oxide and magnesium hydroxide as carriers, and transition metal compounds supported thereon, such as titanium compounds and vanadium compounds. However, if olefins are polymerized with these known catalysts, the bulk density of the polymer obtained is usually low, the average particle size is relatively small, and the particle deposition distribution is generally broad, so that a fine particle fraction can occupy a relatively large part, with the result that the. productivity and manageability deteriorate sharply. When the resulting polymer is molded, further problems such as dust generation and reduced effectiveness of shaping arise. Thus, it is particularly desirable to increase the mass density and reduce the fraction of fine particles. Also, in order to adapt to a processing method in which a particulate molding step is omitted and powdered polymer is fed directly to the processing machine, which has gained significance in recent times, further improvements are needed.

It is an object of the present invention to overcome the above drawbacks.

It is another object of the invention to provide a novel polymerization catalyst that can provide high bulk density olefin polymers, a large average particle size, a narrow particle size distribution, and a remarkably small fraction of fine particles.

Other objects and advantages of the present invention will become apparent from the following description.

The aforementioned objects of the invention can be achieved by using an olefin polymerization catalyst comprising a solid catalyst component and an organometallic compound, which solid catalyst component contains a material obtained by contacting and reacting the following compound: 8201252 \ '\ \ \ -2- / (1.) a silica and / or an alumina (2) a magnesium halide, (3) a compound represented by the general formula Me (0R) QX 2, wherein Me is an element belonging to the groups 5 I-IV of the Periodic Table, z the valence of the element

Me is, n is CKn ^ -z, X is a halogen atom and R is a hydrocarbon group with 1-2¾ carbon atoms, t (¾) a titanium compound and / or a vanadium compound, (5) a compound represented by the general formula R "Si (0RT) X], wherein R 'and Rn are each a hydrocarbon or group nm 4-mn having 1-2¾ carbon atoms, X is a halogen atom, n is 0 <$ n <y and m is 0 <m ^ , with the limitation that 0 4.m + n ^ and / or a silicone.

The silicon oxide used in the present invention is silica 15 or a double oxide of silicon and at least one other metal of groups I-VIII of the Periodic Table.

The aluminum oxide used in the present invention is alumina or a double oxide of aluminum and at least one other metal of groups I-VIII of the Periodic System.

As the double oxide of silicon or aluminum and at least one other metal of groups I-VIII of the Periodic System, various natural and synthetic double oxides can be used, examples of which are AlgO ^ .MgO, AlgO ^ .CaO, AlgO ^ -SiO ^ , AlgO ^ .MgO.CaO, AlgO ^ .MgO.SiOg, AlgO ^ .CuO, AlgO ^ .Fe ^ O ^, Al ^ O ^ .HiO and SiO ^ .MgO. These formulas are not molecular formulas and only indicate compositions. The structure and component ratio of the double oxides that can be used in the present invention are not particularly critical. In fact, the silica and / or aluminum oxide used in the invention may have adsorbed a small amount of moisture and may contain small amounts of impurities.

As the magnesium halide used in the present invention, substantially anhydrous halides can be used, for example, magnesium fluoride, magnesium chloride, magnesium bromide, and magnesium iodide, with magnesium chloride being particularly preferred.

According to the invention, these magnesium halides can be treated with an electron donor, such as an alcohol, an ester, a ketone, a carboxylic acid, an ether, an amine or a phosphine.

8201252. * * -3-.

Compound used in the invention represented by the general formula Me (OR) X, wherein Me is an element belonging to the n zn groups I-IY of the Periodic Table such as Na, Mg, Ca, Zn, Cd, B or Al, z is the valency of the element Me, n is 0 ^ n4z, X is a halogen atom and R, which may be the same or different, is a hydrocarbon group of 1-20 carbon atoms, such as an alkyl, aryl or aralkyl group, various compounds can be used, for example, those represented by the following formulas: NaOR, Mg (0R) 2, Mg (0R) X, Ca (0R) 2, Zn (0R) g, Cd (0R) 2, B (0R ) ^, Al (OR) ^, AlORjgX, Al (0R) X2 · More particularly, the following compounds are preferred: Mg (0C2H ^) 2, Mg (0C2H ^) Gl, AliOCH ^) Al (0C2Hr-) 3, AUQn-C ^^, A1 (Oi-C3H7) 3, AKOn-C ^ H ^, AlCOsec-C ^ ÏÏ ^, AliOt-C ^ H ^, ai (och3) 2ci, ai (oc2h5 ) 2ci, ai (oc2h5) ci2, ai (oi-c3ht) 2ci, Ai (oi-c3sT) ci2.

Examples of the titanium compound and / or vanadium compound used in the invention include halides, alkoxy halides, alkoxides and halogenated oxides of titanium and / or vanadium. The preferred titanium compounds are tetravalent and trivalent titanium compounds and preferred ravalent titanium compounds are those represented by the general formula Τχ (θβ) ^ Χ ^ where R is an alkyl, aryl or aralkyl group of 1-20 carbon atoms, X is a halogen atom and n is 04n4 ^ 5 examples 20 are: titanium tetrachloride, titanium tetrabromide, titanium tetraiodide, mono- methoxytrichloortitaan, dimethoxydichloortitaan, trimethoxymonochloortitaan, tetramethoxytitanium, nonoëthoxytrichloortitaan, diëthoxydichloort itaan, triëthoxyminochloortitaan, tetraethoxy titanium, monoisopropoxytrichloortitaan, dixsopropoxydichloortitaan, trixsopropoxyminochloortitaan, tetraxsopropoxy-25 titanium, monobutoxytrichloortitaan, dibutoxydichloortitaan , monopentoxy-trichlorotitanium, monophenoxytrichlorotitanium, diphenoxydichlorotitanium, triphenoxymonochlorotitanium and tetraphenoxytitanium.

Examples of trivalent titanium compounds include titanium trihalides obtained by reducing titanium tetrahalides, such as titanium tetrachloride and tetrabromide with hydrogen, aluminum, titanium or an organometallic compound of a metal of groups I-III of the Periodic Table, as well as trivalent titanium compounds obtained by reducing tetravalent alkoxy titanium halides of the general formula Ti (OFU ^ X ^ with an organometallic compound of a metal of groups 35 I-III of the Periodic System, in which formula R atoms an alkyl, aryl or aralkyl group with 1-20 carbon , X is a halogen atom and m 0 <m Kk. Examples of the vanadium compound are tetravalent vanadium compounds • 1 8201252 ~. ~ -4-

* V

such as vanadium tetrachloride, vanadium tetrabromide, vanadium tetraiodide and tetraethoxyvanadium, pentavalent vanadium compounds, such as vanadium trichloride, ethoxydichloro vanadyl, triethoxy vanadyl and tributoxy vanadyl and trivalent vanadium compounds, such as vanadium trichloride and vanadium triad.

In order to practice the present invention even more effectively, both the titanium compound and vanadium compound are often used together, and in such a case, the V / Ti molar ratio is preferably in the range of 2/1 to 0.01 / 1.

. As a compound used in the invention represented by the general formula R "Si (OR ') X, wherein R' and R 'are each a hydrocarbon-n m 4-m-n · group such as an alkyl, aryl or aralkyl group with 1-24 carbon atoms, X is a halogen atom, n is 0 ^ n ^ 4, m is Q <m.4b, and n and m have the relationship 0 <m + m ^ 4, example be used mono- ^ methyltrimethoxys ilaan, monomethyltriëthoxysilaan, monomethyltri-n-outoxy-silane, monomethyltri-sec-butoxysilane, monomethyltrixsopropoxysilaan, monomethyltripentoxysilaan, monomethyltrioctoxysilaan, monomethyltristearo-xysilaan, monomethyltrifenoxysilaan, dimethyIdimethoxysilaan, dimethyldi-triethoxysilane, dimethyldixsopropoxysilaan, dimethyldifenoxysilaan, trimethyl-20 monomethoxysilane, trimethylmonoethoxysilane, trimethylmonoxsopropoxysilane, trimethylmonophenoxysilane, monomethyldimethoxymonochlorosilane, monomethyl diethoxymonochlorosilane, monomethylmonoethoxydichlorosomethyldiethylymethyl thoxymonobroomsilaan, monomethyldifenoxymonochloors ilaan, dimethylmonoëthoxymonochloorsilaan, 25 monoëthyltrimethoxysilaan, monoëthyltriëthoxysilaan, monoëthyltrixsopropoxy-silane, monoëthyltrifenoxysilaan, diethyldimethoxysilane, diëthyldiëthoxy-silane, diethyldiphenoxysilane, triëthylmonomethoxysilaan, triëthylmono-ethoxys ilaan, tri ëthylmono fenoxys ilaan, monoëthyldimethoxymonochloors ilaan, monoëthyldiëthoxymonochloorsilaan, monoëthyldifenoxymonochloorsilaan, mono-30 isopropyltrimethoxysilane, mono-n-butyltrimethoxysilane, mono-n-butyltri-silane, mono-sec-butyltriëthoxy silane, monofenyltriëthoxysilaan, diphenyldiethoxysilane, difenylmonoëthoxymonochloorsilaan, monomethoxytri-chlorosilane, monoëthoxytrichloorsilaan, monoxsopropoxytrichloorsilaan, mono-n-butoxytrichloorsilaan, monopentoxytrichloorsilaan, monoöctoxytri-35 chlorosilane, monostearoxytrichloorsilaan , monophenoxytrichlorosilane, mono-p-methylphenoxytrichlorosilane, dimethoxydichlorosilane, diethoxy dichlorosilane, dixsopropoxydichlorosilane, di-n-butoxydichlorosilane, di-actoxydichlorosilane, trimethoxymonochlorosilane, triethoxymonochlorosilane.

8201252 # · * -5-trilsopropoxymonochlorosilane, tri-n-butoxymonochlorosilane, tri-sec.-butoxymonochlorosilane, tetraethoxysilane and tetralsopropoxy silane.

Chain-like or cyclic polysiloxanes obtained by condensation of the aforementioned compounds, with repeating units represented by Y

5 —4- Si - 0 -4-, wherein Y and Z each represent R ", (OR") or halogen, \

Z.

can also be used in the present invention.

The compounds represented by the general formula Si (OR ') X, m 4-m are particularly preferred according to the invention.

The sequence and method for contacting the components (1) - (5) according to the invention are not particularly critical, but preferably the components (1), (2), (3) and (U) is reacted with each other and then component (5) is reacted with the product obtained, or component (U) is reacted with the reaction product of components (1), (2), (3) and (5) reacted.

15 In the first method, i.e. in case component (5) is reacted with the reaction product of components (1), (2), (3) and (^), the sequence and reaction method between components (1), (2), (3) and (k) not particularly critical. For example, the reaction can be carried out in such a way that the components (1) and (2) are contacted, after which component (3) or component (U) is contacted with the product obtained and then the only remaining component . Preferably, the components (2) and (3) are reacted with each other in advance and the reaction product obtained thereby is used as components (2) and (3). More specifically, the silicon oxide and / or aluminum oxide (1), the reaction product (hereinafter referred to as component 2-3) of the magnesium halide (2) with the compound (3) of the general formula Me (0R) ^ X 2 wherein Me an element belonging to groups I-IV of the Periodic System is, z is the valence of the element Me, n is O ^ n ^ z, X is a halogen atom and R is a hydrocarbon group with 1-20 carbon atoms, and the titanium compound and / or vanadium compound (4), are contacted and reacted.

Regarding the order of contacting, the above-described touch procedure can be performed such that component (1) and component (2-3) are contacted and then component (^) is contacted with the product obtained or 8201252 * * -6- first the components (1) and (^) are brought into contact with each other 'and then the component (2-3) is brought into contact with the product obtained, or first component (2-3) and component (b) are contacted with each other and then component (1) is contacted with the product obtained.

Preferably, components (1) and (2-3) are contacted with each other, and then component {b) is contacted with the product obtained.

The method of contacting is not particularly critical, i.e. known methods can be used. In case components (1) and (2-3) are brought into contact with each other or in case component (2-3) is brought into contact with the contact product of components (1) and (1+), or in case component (1) is contacted with the contact product of components (2-3) and (k), an auxiliary pulverizing treatment can be carried out at a temperature of 0-200 ° C for a time period varying from 0.5 up to 50 hours, or it can be mixed at 50-300 ° C for 1 minute to 40 hours and heated in an organic solvent such as an inert hydrocarbon, an alcohol, an ether, a ketone or an ester followed by removal of the solvent. Furthermore, in case the components (1) and (b) can be contacted, or in case component (b) with the contact product of components (1) and (2-3). contacted, or in case components (2-3) and (! +) are contacted, an auxiliary pulverizing treatment is carried out at a temperature of 0-200 ° C for a time period ranging from 0.5 to 50 hours, or the product can be mixed for 5 minutes to 10 hours and heated at 50-300 ° C in the presence or absence of an inert solvent, followed by removal of unreacted titanium compound and / or vanadium compound by washing with an inert solvent.

The method of reacting the magnesium halide and the compound of the general formula MeQRQXXn is not particularly critical. Both can be reacted by mixing and heating for 5 minutes to 10 hours at a temperature in the range of 20-100C, preferably 50-300 ° C in an organic solvent, such as an inert hydrocarbon, an alcohol , an ether, a ketone or an ester.

Optionally, both can be reacted by an auxiliary pulverizing treatment.

8201252 *> -τ-

The use of an auxiliary pulverizing treatment is particularly preferred according to the present invention. The apparatus to be used for this pulverization treatment is not particularly critical, but one will usually use a ball mill, a vibration mill, a bar mill or an impact mill. "The conditions for the pulverization stage such as temperature and time can be easily determined by those skilled in the art.

Generally, the temperature is in the range of 0-200 ° C, preferably 200-100 ° C, and the time in the range of 0.5-50 hours, preferably 1-30 hours.

It goes without saying that the treatment is carried out in an inert gas-10 atmosphere and that moisture is avoided as much as possible.

The reaction ratio of the magnesium halide to the compound of the general formula Μβ (0Ε) χΧζ q is in the range 1: 0.01 to 1: .10, preferably 1: 0.1 to 1: 5, expressed in Mg : Me (molar ratio).

The amount of the component 15 (2-3) to be used in the invention is in the range of 0.01-5 g, preferably 0.1-2 g per g of component (1). Regarding the amount of component (U), it is desirable to adjust it so that the titanium and / or vanadium content of the obtained solid component is in the range of 0.5-20 wt%, the t range of 1- 10 wt.% Is particularly preferred to obtain a well-balanced activity per titanium and / or vanadium and that per solid component.

The most preferred sequence and method of contacting components (1) and (2-3) and (^) according to the invention are as follows: First, the component (2-3) which the reaction product is the magnesium chloride and the compound of the general formula Me (0R) QX 2 and the component (1) at 0-300 ° C, preferably 10-200 ° C and in particular 20-100 ° C for 1 minute up to 8 hours, preferably 2 minutes to 10 hours, in a solvent in which the component (2-3) is dissolved, reacted with each other. Examples of the solvent include alcohols, ether, ketones and amines. Preferred examples of such a solvent are methanol, ethano, isopropanol, butanol, pentanol, hexanol, octanol, benzyl alcohol, methyl cellosolve, ethyl cellosolve, methyl formate, ethyl formate, methyl acetate, ethyl acetate, butyl acetate, ethyl acrylate, methyl methyl acrylate, methyl methyl acrylate laurate, methyl benzoate, ethyl benzoate, octyl para-hydroxybenzoate, dibutyl phthalate, dioctyl phthalate, dimethyl malonate, dimethyl maleate, diethyl maleate, t 8201252 Μ -8-dimethyl ether, diethyl ether, diethyl ether, dibutyl ether, dibutyl ether -butyl ketone, ethyl butyl ketone, dihexyl ketone, acetophenone, diphenylic ketone, cyclohexanone, diethylamine, triethylamine, tetramethylenediamine, aniline, 5 I, N-dimethylaniline and pyridine. Most preferred are ethanol, tetrahydrofuran and ethyl acetate. In this case, the components (1) and (2-3) are contacted in a ratio of 0.01-5 g, preferably 0.1-2 g, of component (2-3) per gram of component (1). After the reaction, the solvent is removed to yield the reaction product of components (2) and (2-3).

Subsequently, component (b), ie, the titanium compound and / or vanadium compound, is heated with the above reaction product of components (1) and (2-3) at a temperature of 20-300 ° C, preferably 50-150 ° C »for 5 minutes to 10 hours in the presence or absence of an inert solvent, such as hexane, heptane, mixed together to support the titanium compound and / or the vanadium compound on the reaction product of components (1) and (2 -3). In the latter case, the amount of component (1) is adjusted such that the content of the titanium compound and / or the vanadium compound in the. solid component obtained is in the range of 0.5-20%, preferably 1-10% by weight. After the reaction, unreacted titanium compound and / or vanadium compound is removed by washing several times with a solvent inert to Ziegler catalysts, followed by evaporation under reduced pressure to obtain a solid powder.

2? The resulting reaction product (hereinafter simply referred to as component [1]) of components (1), (2-3) and (U) is then reacted with component (5) of the general formula R "Si (0R) X where n · m 4-m-n is obtained in the solid catalyst component of the invention.

The reaction method between component [i] and component (5) is not particularly critical. Both components can be reacted with each other by the pulverization treatment; in the presence or absence of an inert solvent, at a temperature of from 20 to 00, preferably from 50 to 300 ° C for 5 minutes to 20 hours.

The components [i] and (5) are reacted at a reaction ratio of 0.05-50 g, preferably 0.1-30 g, of component (5) per 100 g of component [I].

In case component (b) is reacted with the reaction product of components (1), (2), (3) and (5), the order and method 8201252 - -9- * of the reaction between the components are ( 1), (2), (3) and (5) are not particularly critical, but preferably components (2) and (3) or components (2) and (5) or components (2) and (3) and ( 5) reacted with each other beforehand.

More concretely, the reaction can be carried out by reacting the reaction product of components (2) and (3) with component (1) and then contacting component (5) with the product obtained or by reaction product of components (2) and (5) with component (1) and then contacting component (3) with the resulting product, or by component (1) with the reaction product of components (2 ), (3) and (5).

The contact between components (2) and (3), between components (2) and (5) s or between components (2), (3) and (5) »can be in an organic solvent, such as an inert hydrocarbon, a alcohol, an ether, a ketone or ester are carried out, preferably it is carried out by means of the pulverization treatment.

Contacting component (1) with the reaction product of components (2) and (3), with the reaction product of components (2) and (5) j or with the reaction product of components (2), (3) and ( 5) can be carried out by the auxiliary pulverizing treatment, but preferably in an organic solvent, such as an inert hydrocarbon, an alcohol, an ether, a ketone or an ester, at a temperature of 50-350 ° C for 1 minute to 1 *. O hours.

In case component (5) is contacted with the product by contacting the reaction product of components (2) and (3) with component (1) or in case component (3) is obtained with the product by contacting the reaction product of components (2) and (5) with component (1), the reaction can take place by means of the auxiliary pulverizing treatment, or in the presence or absence of an inert solvent.

As for the touch ratio (molar ratio) of components (1), (2), (3) and (5), component (1) is component (2) in the range of 1: 0.01 - 1: 5, preferably 1: 0.1 - 1: 2, component (2): component (3) in the range 1: 0.01 - 1:10, preferably 1: 0.1 - 1: 5, and component (2) : 35 component (5) in the range of 1: 0.01 - 1:10, preferably 1: 0.1 - 1: 5

The contacting of component (U) with the reaction product of components (1), (2), (3) and (5) can be carried out by the auxiliary * 8201252 -10 pulverizing treatment, but preferably component (ij ·) With bet. reaction product of components (1), (2), (3) and (5) mixed 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 20-300 ° C for 5 to 5 10 hours. The amount of component (4) is adjusted so that its content in the obtained solid component is in the range 0.5-20. preferably 1-10 wt.%.

As the organometallic compound used in the present invention, organometallic compounds of Group I-IV metals of the Periodic System, known as one component of Ziegler catalysts, may be used, with organoaluminum compounds and organo zinc compounds being particularly preferred, eg organoaluminum compounds having the general formulas R ^ Al, RgAlX, R ^ AlOR, RAi (0R) X and R ^ Al ^ X ^, wherein R is an alkyl or aralkyl group of 1-20 carbon atoms and may be the same or different and X is one. halogen, and organo-zinc compounds of the general formula R @ Zn, wherein R is an alkyl group of 1-20 carbon atoms, which may be the same or different, such as triethyl aluminum, triisopropyl aluminum, trixsobutyl aluminum, tri-sec-butyl aluminum, tri-tert- butyl aluminum, trihexyl aluminum, trioctyl aluminum-20,. diethyl aluminum chloride, diisopropyl aluminum chloride, ethyl aluminum sesauichloride, diethyl zinc and mixtures thereof. The amount of the organometallic compound is not particularly critical, but usually the organometallic compound can be used in an amount of 0.1-1000 moles per mole of the titanium compound and / or the vanadium compound.

It is also preferred in the invention to use the organometallic compound component as a mixture or compound of the organometallic compound, as mentioned above, with an organic acid ester, If the organometallic compound and the organic acid ester are used as a mixture, the organic acid ester usually becomes. an amount of 0.1-1, preferably 0.2-0.5 mol, per mol of the organometallic compound is used. When the organometallic compound and the organic acid ester are used as the addition compound, the ratio of the organometallic compound to the acid ester is preferably in the range of 2: 1 - 1: 2, expressed in molar ratio.

The organic acid ester is an ester of a saturated or unsaturated * 8201252-11 mono- or dibasic organic carboxylic acid with 1 to 2 carbon atoms with an alcohol of 1 to 30 carbon atoms. Examples of such organic acid esters are methyl formate, ethyl acetate, amyl acetate, phenyl acetate, octyl acetate, methyl methacrylate, ethyl stearate, methyl benzoate, ethyl 5 benzoate, n-propyl benzoate, isopropyl benzoate, butyl benzoate, hexyl benzoalate, cyclopentyl benzoate, methyl benzylate, phenyl benzoate, phenyl benzylate -hydroxybenzoate, ethyl p-hydroxybenzoate, phenyl salicylate, cyclohexyl p-hydroxybenzoate, benzyl salicylate, ethyl α-resorcinate, methyl anisate, ethyl anisate, phenyl anisate, 10-benzyl anisate, ethyl-O-methoxybenzoate, methyl-p-ethoxybenzo toluylate, ethyl p-toluylate, phenyl p-toluylate, ethyl o-toluylate, ethyl m-toluylate, methyl p-aminobenzoate, ethyl p-aminobenzoate, vinyl benzoate, allyl benzoate, benzyl benzoate , methyl naphthoate, and ethyl naphthoate. Particular preference is given to alkyl esters, in particular methyl and ethyl esters of benzoic acid, 2- or U-with hyb1 and zoeic acid and methoxybenzoic acid.

The olefin polymerization using the catalyst of the invention can be conducted as a slurry polymerization, a solvent polymerization, or a vapor phase polymerization. The catalyst of the invention is particularly suitable for vapor phase polymerization. The polymerization reaction is carried out in the same manner as in a conventional olefin polymerization reaction using a Ziegler type catalyst; i.e., the reaction is carried out under substantially oxygen and water-free conditions and in the presence or absence of an inert hydrocarbon. The olefin polymerization conditions include temperatures ranging from 20 to 120, preferably from 50 to 100 ° G, and pressures ranging from atmospheric pressure to 70 kg / cm 2, preferably 2 to 60 kg / cm. The molecular weight can be adjusted to some extent by changing the polymerization conditions, such as the polymerization temperature and the catalyst molar ratio, but the addition of hydrogen to the polymerization system is more effective for this purpose. Of course, two or multi-stage polymerization reactions at different polymerization conditions, such as different hydrogen concentrations and different polymerization temperatures, can be performed without any problems using the catalyst of the invention.

The present invention applies to the polymerization of olefins polymerizable with Ziegler catalysts, preferably q-olefins having 2-12 carbon atoms. For example, the present invention is 8201252 * -12- \ i.

suitable for the hamopolymerization of such ct-olefins as ethylene, propylene, 1-butene, hexene-1 and U-methylpentene-1, the copolymerization of ethylene and propylene, ethylene and 1-hutene, ethylene and hexene- 1, propylene and 1-hutene, and the copolymerization of ethylene with two or more other 5 alpha olefins.

Copolymerization with polyolefins modification is also preferred. Examples of diene compounds used in this copolymerization are butadiene, 1,1-hexadiene, ethylidene norbornene and dicyclopentadiene.

By using the catalyst according to the invention, a high-active polyolefin with a large average particle size, a narrow particle size distribution and a reduced amount of fine particles is obtained, the mass density of the polyolefin being high, which is very favorable for the polymerization. The polyolefin 15 thus obtained can not only be pressed into balls, but also directly into a powder, with few problems encountered during the shaping steps. Polyolefins can thus be prepared very advantageously.

The polymer obtained by using the catalyst according to the invention is further characteristic in that the molecular weight distribution is very narrow and the smaller the hexane extraction, the poorer polymer by-product production. is lower. Therefore, when the narrow molecular weight distribution polyolefin obtained by using the catalyst of the invention is used to form a film, the film obtained will have many good properties, such as high strength, high degree of transparency, no tendency to contact adhesion and with good heat sealability.

The invention provides a narrow catalyst system which has such characteristic properties and obviates the drawbacks mentioned in the prior art. It is very surprising that the above-mentioned advantages can be easily achieved when using the catalyst according to the invention.

The invention is illustrated by the following examples which are not intended to limit the invention.

Example I

(A) Preparation of a solid catalyst component 10 g of a commercially available anhydrous magnesium chloride and kt2 g of aluminum trioxide were placed in a stainless steel crucible 8201252 -13- \ l Λ \ containing 25 ml stainless steel balls each with a diameter of 1.3 cm, and the mixture was ground to a reaction product under nitrogen at room temperature for 16 hours. Then, a three-necked flask, equipped with a stirrer and reflux condenser, was purged with nitrogen and charged with 5 g of the aforementioned reaction product and 5 g of SiOg (Fuji-Davison # 952), which had been calcined at 600 ° C; after which 100 ml of tetrahydrofuran were added and the reaction was carried out at 60 ° C for 2 hours, followed by drying at 120 ° C under reduced pressure to remove tetrabydrofuran. Then, after addition of 50 cc of hexane and subsequent stirring, 1.1 ml of titanium tetrachloride was added and the reaction was carried out under reflux of hexane for 2 hours to obtain a solid powder (A) containing 10 mg of titanium per g thereof.

The solid powder (A) was added to 50 ml of hexane, then 1 ml of tetraethoxysilane was added and. The reaction was allowed to proceed under reflux of hexane for 2 hours to obtain a solid catalyst component.

(b) Vapor phase polymerization.

A stainless steel autoclave was used as a vapor phase polymerization device, and a cycle was formed by a fan, a blower, and a dry cyclone. The autoclave temperature was adjusted by passing warm water through a jacket.

Into the autoclave held at 80 ° C, the aforementioned solid catalyst component and triethyl aluminum were introduced at rates of 25 and 10, respectively. 250 mg / h and 50 mmol / h, and but 1-1, ethylene and hydrogen were fed under adjustment such that the butene-1 / ethylene ratio (molar ratio) in the vapor phase within the autoclave was 0.27 and the hydrogen concentration was 17 $ of the total pressure, the polymerization being carried out with recirculation of the intrasystem gases through the fan.

The resulting ethylene copolymer was a powder with an average particle size of 750 µm that contained no particles below 150 mu and with a mass strength of 0.22, a melt index (Mi) of 1.0 and a density of 0 , 9208. The catalyst activity was 100,000 g copolymer / g Ti.

The PR value (FR ^ MI ^^ / MI ^) represented in the ratio of a melt index (MI) of the copolymer of 2.16 determined at a load of 2.16 kg to a melt index (MI) thereof of 10 at a load of 10 kg, both at 190 ° C according to the method of ASTM-D 1238-65T, was 7.2 and thus 8201252-1 ^ 4- the molecular weight distribution was very narrow.

A film was formed from this copolymer and extracted in boiling hexane for 10 hours; it was found that the extraction was 0.8 wt% and thus the amount of the extract was very small.

5 Comparative example 1

The following vapor phase polymerization was carried out using the device described in Example I.

The autoclave held at 80 ° C was charged with the solid powder (A) obtained in Example I and triethyl aluminum in amounts of resp.

250 mg / h and 5 mmol / h, and to which butene-1, ethylene and hydrogen gas were fed under such a setting that the butene-1 / ethylene (molar ratio) in the vapor phase within the autoclave was 0.25 and the hydrogen concentration was 15% of the total pressure, while the polymerization was carried out at a total pressure of 10 kg / cm with recirculation of the intrasystem gases through the fan. The ethylene polymer obtained was a powder with an average particle size of TOO mu containing no particles smaller than 150 mu and having a mass density of 0.11, a melt index (M1) of 1.2 and a density of 0.9210. The catalyst activity was 112,000 g copolymer / g TI.

20 The F.R. value of this copolymer was 7.6 and thus the molecular weight distribution was broader than in Example I.

A film was formed from this copolymer and extracted in boiling hexane for 10 hours; hexane extraction was found to be 1.1% by weight.

Example II

(a) Preparation of a solid catalyst component.

10 g of anhydrous magnesium chloride and k, 2 g of tetraethoxysilane were placed in the ball mill described in Example 1 and the mixture was ground under nitrogen for 16 hours to a reaction product. Then, 5 g of the reaction product and 5 g of SiO 2, which had been calcined at 600 ° C, were placed in the three-necked flask described in Example 1, after which 100 ml of tetrahydrofuran were added and the reaction was allowed to proceed for 2 hours at 60 ° C, followed by drying at 120 ° C under reduced pressure to remove tetrahydrofuran. Then, after addition of 50 cc of hexane and subsequent stirring, 0.1 ml of titanium tetrachloride was added and the reaction was allowed to proceed under reflux of hexane for 2 hours to obtain a solid powder (B) containing Uo mg 8201252 -15- titanium contained per g of the solid powder (B).

The solid powder (B) was added to 50 ml of hexane, then 1 ml of tetraethoxysilane was added, and the reaction was carried out under reflux of hexane for 2 hours to obtain a solid catalyst component 5.

(b) Vapor phase polymerization.

The following vapor phase polymerization was performed with the device described in Example I.

The autoclave held at 80 ° C was charged with the above solid catalyst component and triethyl aluminum in amounts of resp.

250 mg and 50 mmol per hour, and to which were added butene-1, ethylene and hydrogen gases under such a setting that the butene-1 / ethylene ratio (mol ratio) in the vapor phase within the autoclave was 0.28 and the hydrogen concentration was $ 17 of the total pressure, while polymerization was carried out with recirculation of the intrasystem gases through the fan. The resulting ethylene copolymer was a powder with an average particle size of 750 mu containing no particles smaller than 150 mu and having a mass density of 0.38, a melt index (MI) of 1.1 and a density of 0.9250. The catalyst activity was 100,000 g copolymer / g 20 Ti;

The F.R. value of the copolymer was 7.2. When a film is formed from this copolymer it is placed in boiling hexane for 10 hours. was extracted, the hexane extraction was found to be 0.8 wt%.

Comparative Example 2 The following vapor phase polymerization was carried out with the device described in Example I.

The autoclave held at 80 ° C was charged with a solid powder (B) obtained in Example II and triethyl aluminum in an amount of resp. 250 mg / h and 50 mmol / h, to which butene-1, ethylene and hydrogen gases were fed under such a setting that the butene-1 / ethylene ratio (mol ratio) in the vapor phase within the autoclave was 0.28 and the hydrogen concentration was 15% of the total pressure while the polymerization was carried out at a total pressure of 10 kg / cm with recirculation of the intrasystem gases by the fan. The ethylene copolymer obtained was a powder with an average particle size of 750 mu · h and containing no particles smaller than 150 m ^u and with a mass density of 0.38, a melt index (MI) of 1.0 and a density from 8201252 \ \ 1 \ '\ -16- 0.9100. The catalyst activity was 120,000 g copolymer / g Ti.

The F.R. value of the copolymer was 8.0 and thus the molecular weight distribution was broader than that in Example II.

A film was formed from this copolymer and placed in boiling hexane for 5 hours. extracted. As a result, the hexane extraction was 2.0 wt%.

Example III

(a) Preparation of a solid catalyst component.

10 g of anhydrous magnesium chloride and k, 2 g of aluminum trioxide were placed in the ball mill jar described in Example 1 and the mixture was ground at room temperature under nitrogen atmosphere for 16 hours to obtain a reaction product. 5 g of the reaction product and.

5 g of SiO 2 previously calcined at 600 ° C were placed in the three-necked flask described in Example I, after which 100 ml of ethyl acetate was added and the reaction was carried out at 60 ° C for 2 hours, followed by drying at 120 ° C under reduced pressure to remove ethyl acetate.

Then, after addition of 50 cc of hexane and subsequent stirring, 1.1 ml of titanium tetrachloride was added and the reaction was carried out for 2 hours, whereby a. solid powder (C) was obtained, containing ^0 mg of titanium per g of 20 thereof.

j

The solid powder (C) was added to 50 ml of hexane, then 0.5 ml of tetraethoxysilane was added and the reaction was allowed to proceed under reflux of hexane for 3 hours to obtain a solid catalyst component.

(B) Vapor phase polymerization.

The following vapor phase polymerization was performed with the device described in Example I.

The autoclave held at 80 ° C was charged with the aforementioned solid catalyst component and triethyl aluminum in an amount of resp.

250 mg / h and 50 mmol / h and to which butene-1, ethylene and hydrogen gases were fed under such a setting that a butene-1 / ethylene ratio (mol ratio) in the vapor phase within the autoclave of 0.27 and a hydrogen concentration of M% of the total pressure was obtained, while the polymerization was carried out with recirculation of the intrasystem gases from the fan. The ethylene copolymer obtained was a powder with an average particle size of 600 mu containing no particles smaller than 150 mu and having a mass density of 0.39, a melt index (MI) of% 8201252-17.

♦ \ 1.5 and a density of 0.9200. The catalyst activity was 90,000 g copolymer / g Ti.

The F.R. value of the copolymer was 7.5. A film was formed from this copolymer and extracted in boiling hexane for 10 hours; as a result, the hexane extraction was 0.9 wt%.

Example IV

(a) Preparation of a solid catalyst component.

10 g of anhydrous magnesium chloride and 4.1 g of triethoxyboron were placed in the ball mill crucible described in Example I and the mixture was ground for 16 hours at room temperature under a nitrogen atmosphere to obtain the reaction product. 5 g of the reaction product and 5 g of SiO4, previously calcined at 600 ° C, were placed in the three-necked flask described in Example I, after which 100 ml of tetrahydrofuraa were added and the reaction was allowed to proceed for 2 hours at 60 ° C followed by drying 15 at 120 ° C under reduced pressure to remove tetrahydrofuraa. Then, after addition of 50 cc of hexane and subsequent stirring, 1.1 ml of titanium tetrachloride was added and the reaction was carried out under reflux of hexane for 2 hours to obtain a solid powder (D), which was found to contain 40 mg of titanium per g thereof.

The solid powder (D) was added to 50 ml of hexane, then 1 ml of tetrasilane was added and the reaction was allowed to proceed under reflux of hexane for 2 hours to obtain a solid catalyst component.

(b) Vapor phase polymerization.

The following vapor phase polymerization was performed using the device described in Example I.

The aforementioned solid catalyst component and triethyl aluminum were fed to the autoclave maintained at 80 ° C in an amount of resp. 250 mg / h and 50 mmol / h, to which butene-1,> 30 ethylene and hydrogen gases were fed, such that a butene-1 ethylene ratio (mol ratio) in the vapor phase was obtained within the autoclave of 0.27 and a hydrogen concentration of 17% of the total pressure, while the polymerization was carried out with recirculation of the intrasystem gases by the fan. The ethylene-35 copolymer obtained was a powder with an average particle size of 500 mu containing no particles smaller than 44 mu and with a mass density of 0.42, a melt index (Ml) of 1.3 and a density of 0.925- De kata Lysator activity was JO,000 g copolymer / g Ti.

The F.R. value of the copolymer was 7 Π. A film was formed from this copolymer and extracted in boiling hexane for 10 hours. As a result, the hexane extraction was 0.9 wt.%.

5 Example V

(a) Preparation of a solid catalyst component.

. 10 g of anhydrous magnesium chloride and. 1.2 g of diethoxymagnesium were placed in the ball mill described in Example 1 and the mixture was ground under a nitrogen atmosphere at room temperature for 16 hours to obtain a reaction product. 5 g of the reaction product and 5 g of SiOg. previously calcined at 600 ° C were placed in the three-necked flask described in Example 1, 100 ml of tetrahydrofuran were added and the reaction was completed. run at 60 ° C for 2 hours, followed by drying at 120 ° C under reduced pressure to remove tetrahydrofuran. Then, after addition of 50 cc of hexane and subsequent stirring, 1.1 ml of titanium tetrachloride was added and the reaction was carried out under reflux of hexane for 2 hours to obtain a solid powder (e) which was found to contain HO ml of titanium per g thereof.

The solid powder (E) was added to 50 ml of hexane, then 1 ml of tetraethoxysilane was added and the reaction was carried out under reflux of hexane for 2 hours to obtain a solid catalyst component.

(b) Vapor phase polymerization.

The following vapor phase polymerization was performed with the device described in Example I.

The aforementioned solid catalyst component and the triethyl aluminum were fed into the autoclave maintained at 180 ° C at a rate of resp. 250 mg / h and 50 mmol / h and to which butene-1, ethylene and hydrogen gas were added under such a setting that a butene-1 / ethylene ratio (mol ratio) in the vapor phase within the autoclave of 0.27 and a hydrogen concentration of 17% of the total pressure was obtained while the polymerization was carried out with recirculation of the intrasystem gases by the fan. The ethylene copolymer obtained was a powder 35 with an average particle size of 600 mu containing no particles smaller than 100 mu and with a mass density of 0.05, a melt index (M1) of 0.5 and a density of 0.9250. The catalyst activity was 100,000 g / copolymer / g Ti.

8201252 ^ c- -19-

The F.B. value of the copolymer was 7.5. A film was formed from this copolymer and extracted in boiling hexane for 10 hours; as a result, the hexane extraction was 0.1% by weight.

Example VI

(A) Preparation of a solid catalyst component.

10 g of a commercially available anhydrous magnesium chloride and 2 g of aluminum triethoxide were placed in a stainless steel crucible with a volume of 400 ml containing 25 stainless steel balls with a diameter of 1.3 cm each and the mixture was ground under nitrogen at room temperature for 16 hours to obtain a reaction product. Then a three-necked flask equipped with stirrer and reflux condenser was purged with nitrogen into which 5 g of the aforementioned reaction product and 5 g of SiO 2 (Fuji-Davison 952), previously calcined at 600 ° C, were added, and 100 ml of tetrahydrofuran was added and the reaction was carried out at 60 ° C for 2 hours followed by drying at 120 ° C under reduced pressure to remove tetrahydrofuran. Then, 50 cc of hexane and 2 ml of tetraethoxysilane were added, and the reaction was carried out at 50 ° C for 2 hours, after which 1.1 ml of titanium tetrachloride was added and the reaction was allowed to proceed under reflux of hexane for 2 hours, whereby a solid catalyst component was obtained which was found to contain 38 mg of titanium per g of it.

(b) Vapor phase polymerization.

A vapor phase polymerization was carried out in the device described in Example 1 as follows.

The aforementioned solid catalyst component and triethyl aluminum were fed to the autoclave, which was kept at 80 ° C, at a rate of resp. 250 mg / h and 50 mmol / h and to which butene-1, ethylene and hydrogen gases were fed under such a setting that a butene-1 / ethylene ratio (mol ratio) in the vapor phase within the auto-30 claaf of 0.28 and a hydrogen concentration of the total pressure was obtained, while the polymerization was carried out with recirculation of the intrasystem gases by the fan. The ethylene copolymer obtained was a powder with an average particle size of 730 mu containing no particles smaller than 150 mu and with a mass density of 0.35, a melt index (Ml) of 1.0 and a density of 0.9221 . The catalyst activity was 135,000 g copolymer / g Ti.

The F.R. value of the copolymer was 7.2. A film was formed from this copolymer 8201252 -20- and extracted in boiling hexane for 10 hours; as a result, the hexane extraction was 0.9 wt.%.

Example VII

(a) Preparation of a solid catalyst component.

10 g of a commercially available anhydrous magnesium chloride ij, 2 g of aluminum triethoxide and 3 g of monoethyl triethoxysilane were contained in a stainless steel balls with a diameter of 1.3 cm each and the mixture was ground under nitrogen at room temperature for 16 hours to give a reaction product. was obtained. Then, a three-necked flask was provided with stirrer and reflux condenser purged with nitrogen, and 5 g of the aforementioned reaction product and 5 g of SiO4 (Fuji Davison 952), previously calcined at 600 ° C, were charged therein, followed by 100 ml of tetrahydrofuran was added and the reaction was allowed to proceed at 10 ° C for 2 hours, followed by drying at 120 ° C under reduced pressure to remove 15 tetrahydrofuran. Then, after addition of 50 cc of hexane and subsequent stirring, 1.1 ml of titanium tetrachloride was added and the reaction was carried out under reflux of hexane for 2 hours, whereby a solid powder (A) was found to contain 10 mg of titanium per g thereof.

(b) Vapor phase polymerization.

A stainless steel autoclave was used as a vapor phase polymerizer, and a fan cycle, a flow controller and a dry cyclone. The autoclave temperature was adjusted by passing warm water through a jacket.

The aforementioned solid catalyst component and the triethylaluminum 25 were fed into the autoclave maintained at 80 ° G at a rate of resp. 250 mg / h and 50 mmol / h, to which butene-1, ethylene and hydrogen gases were fed under such a setting that a butene-1 / ethylene ratio (molar ratio) in the vapor phase within the autoclave of 0.27 and a hydrogen concentrations of 17% of the total pressure were obtained, while the polymerization was carried out with recirculation of the intra-system gases by the fan. The ethylene copolymer obtained was a powder with an average particle size of 710 mu containing no particles smaller than 150 mu and with a mass density of 0.000, melt index (Ml) of 0.8 and a density of 0.9210. The catalyst activity was 130,000 g copolymer / g Ti.

The F.R. value of 7.1 · A film was formed from this copolymer and extracted in boiling hexane for 10 hours; as a result, the hexane extraction was 0.8 wt.%.

8201252

Claims (8)

1. Olefin polymerisat alysator comprising a solid cat alysor component and an organometallic compound, characterized in that the solid catalyst component is a material obtained by contacting and reacting the following compounds: 1) at least one compound selected from silica and an alumina (2) a magnesia halide, (3) a compound represented by the general formula Me (OR) X, where H Z- * 0, in Me is an element belonging to groups Ι-Γ7 of the Periodic Table 10, z is the valency of the element Me, n is 0 <n4z, X is a halogen atom and R is a hydrocarbon group with 1-20 carbon atoms, (it ·) At least one compound selected from a titanium compound and a vanadium compound, and (5) at least one compound selected from the compounds represented by the general formula R "Si (OR ') X", wherein R' and R, r each a hydrocarbon nm 4-m-n material group with 1 -2 U · carbon atoms, X a is halogen, n is O ^ h ^ it-, and -m is 0 with the limitation that 0 is Am + η, and a polysiloxane. Catalyst according to claim 1, characterized in that the silicon oxide is silica. Catalyst according to claim 1, characterized in that the aluminum oxide is alumina. The catalyst according to claim 1, characterized in that the magnesium halide is magnesium chloride. Catalyst according to claim 1, characterized in that Me, Ha, Mg, Ca, Zn, Cd, B or Al. Catalyst according to claim 1, characterized in that the titanium compound is a tetravalent titanium compound represented by the general formula TiCOR ^ X ^, wherein R is an alkyl, aryl or aralkyl group with 1-20 carbon atoms, X is a halogen atom and n is 0 in ^ or a tri-valent titanium compound is obtained by reducing said titanium compound. Catalyst according to claim 1, characterized in that the solid catalyst component is obtained by previously reacting components (2) and (3) with each other and components (1) and (U) and (5) in reacting a 8201252 m% -22 desired sequence with the reaction product obtained. Catalyst according to claim 1, characterized in that the ratio of component (1) to component (2) is in the range from 1: 0.01 to 1: 5. Catalyst according to claim 1, characterized in that the ratio of component (2) to component (3) is in the range from 1: 0.01 to 1:10. _ Catalyst according to claim 1, characterized in that the ratio of component (2) to component (5) 'is in the range from 1: 0.01 to 1:10. 8201252