FR2553421A1 - CATALYTIC COMPONENT FOR THE POLYMERIZATION OF OLEFINS AND CATALYST FOR THIS POLYMERIZATION - Google Patents

Abstract

CATALYST FOR THE POLYMERIZATION OF OLEFINS CONSISTING OF: A. A CATALYTIC CONSTITUENT OBTAINED BY A PROCESS INCLUDING THE CONTACT OF: A. A SALT OF MAGNESIUM FATTY ACID AND OR B. A DIALCOXYMAGNESIUM, C. A MONO- OR DIESTER OF ' AN AROMATIC CARBOXYL DIACID, D. A HALOGENOUS HYDROCARBON AND E. A TITANIUM HALOGENIDE OF THE GENERAL FORMULA: TIX, IN WHICH X REPRESENTS A HALOGEN ATOM; B. A SILICON COMPOUND REPRESENTED BY THE GENERAL FORMULA: SIR (GOLD), IN WHICH R IS HYDROGEN, AN ALCOHYL GROUP OR AN ARYL GROUP, R IS AN ALCOHYL GROUP OR AN ARYL GROUP AND M IS SUCH AS O M 4; AND C. AN ORGANOALUMINUM COMPOUND. THE POLYMERIZATION OF OLEFINS BY USE OF THIS CATALYST OFFERS ADVANTAGES SUCH AS A HIGH POLYMERIZATION ACTIVITY PER UNIT OF WEIGHT OF CATALYTIC CONSTITUENT, A PROLONGED POLYMERIZATION ACTIVITY, A HIGH YIELD OF STEREOREGULAR POLYMER AND EXEMPTION OF POLYMER AND EXEMPTION OF POLYMERIZATION. ODOR OF ESTER SUCH AS THAT WE ARE ENCOUNTERED IN THE PRIOR ART.

Description

The present invention relates to an improved catalyst component for the

  olefin polymerization and a catalyst for this polymerization which are capable of providing a high polymerization activity per unit weight of the catalyst component and a high yield of stereoregular polymer when applied to the polymerization of olefins, and more In particular, a catalytic component obtained by contacting a fatty acid salt of magnesium and / or dialkoxy magnesium, a mono- or diester of an aromatic dicarboxylic acid, a halogenated hydrocarbon and a halide is particularly suitable. of titanium, and a catalyst for this polymerization comprising the catalytic component, a silicon compound

  and an organoaluminum compound, the term "polymerization" including homopolymerization and copolymerization.

  It is well known in practice a catalyst for the polymerization of olefins, formed by combining a solid titanium halide as a catalytic component with an organoaluminum compound. However, in the polymerization of olefins using the conventional catalyst, the yield of The polymer per unit weight of the catalyst component or the titanium portion of the catalyst component (hereinafter referred to for simplicity as polymerization activity per unit weight of catalytic component or titanium) is so low that the so-called ash removal operation for the Subsequent removal of the catalyst residues from the product polymer is essential if an industrially applicable polymer is to be obtained. In the centrifuge removal operation, alcohols or chelating agents are employed in large quantities, so that ash removal operation requires equipment for the recovery of these In addition to the ash removal apparatus itself, there are many problems with the supply of consumed materials, energy, etc. Thus, the operation of removing ash poses significant problems. which have to be urgently solved in practice A number of studies and suggestions have been made to increase the polymerization activity per unit weight of titanium in the catalytic component, so as to be able to dispense with the complicated operation. ash removal. In particular, according to a recent trend, numerous suggestions have been made to remarkably increase the weight-specific polymerization activity of titanium in the catalyst component in the polymerization of olefins with a catalytic component prepared with a transition metal compound. as an active ingredient, for example a titanium halide,

  on a support material such that the active ingredient can act effectively.

  However, the prior art employing magnesium chloride as a carrier as described above has the disadvantage that the chlorine portion contained in the magnesium chloride conventionally employed as a carrier has a deleterious effect on the polymer produced, the result being that there are still problems to be solved, for example the need for an activity

  sufficiently high that there is practically no deleterious effect due to the chlorine moiety, or the need to adjust the concentration of the magnesium chloride itself to a sufficiently low level.

  The present inventors have proposed a process for preparing a catalyst component for the polymerization of olefins in the application for

  Japanese Patent No 200454/1982 for the purpose of reducing

  In addition, the chlorine content of the polymer produced as well as the high polymerization activity and high yield of the stereoregular polymer is achieved. This process is also effective in the stated purpose. It is also essential for a catalyst formed by combining a catalytic component employing magnesium chloride as support with an organoaluminum compound, to carry out on an industrial scale the polymerization of olefins, in particular the stereoregular polymerization of propylene, 1-butene, and the like, in the presence of a donor compound However, the aromatic carboxylic acid ester mentioned above confers a similar amount of electron as aromatic carboxylic acid esters in the polymerization system.

  The particular ester odor of the polymer produced, which in practice poses a serious problem of deodorization.

  It was virtually impossible for the so-called high activity support catalyst formed by the use of a catalytic component using the above-mentioned magnesium chloride to be used in a practical manner since the use of the supported catalyst results in a sudden deactivation of the latter despite its high activity at the beginning of the polymerization, which causes problems in the manufacturing operations, in particular in cases where a prolonged polymerization time is required, as in block copolymerization and analogs In order to solve the above-mentioned problems, Japanese Patent Publication No. 94590/1979 discloses a catalyst for olefin polymerization which comprises a catalytic component prepared by use of a magnesium dihalide as one of the raw materials, an organoaluminum compound, an aromatic carboxylic acid ester and a However, the catalyst described above fails to solve the problem of the deodorization of the polymer produced because

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  aromatic carboxylic acid esters are used for the polymerization, and this requires complicated operations for the preparation, performance of the catalyst and

  the polymerization activity becoming practically insuf fi cient with time.

  An object of the present invention is to provide a catalyst component for the polymerization of olefins and a catalyst for this polymerization which are capable of greatly reducing both the amount of catalyst residue and the halogen content of the polymer.

  produced to the point that we can completely eliminate the ash removal operation.

  Another object of the present invention is to provide a catalyst component for the polymerization of olefins and a catalyst for this polymerization which have a high polymerization activity, whose polymerization activity decreases much less with time (or which exhibit a polymerization activity during

an extended period).

  Still another object of the present invention is to provide a catalyst component for the polymerization of olefins and a catalyst for this polymerization which can give a high yield of a stereoregular polymer and produce a polymer free of ester odor such that the one he acquires in cases where

  employing aromatic carboxylic acid esters as the electron donor compound in the prior art.

  Still another object of the present invention is to provide a catalyst component for the polymerization of olefins and a catalyst for this polymerization which allows a low or zero decrease in both the polymerization activity and the yield of

  Stereoregular polymer in the case where the polymerization of olefins is carried out in the presence of hydrogen and the produced polymer has a very high melt index.

  The present invention also provides a catalyst component (A) for the polymerization of olefins, obtained by a process comprising contacting (a) a magnesium fatty acid salt and / or (b) a dialkoxy magnesium salt, ( c) a mono- or diester of an aromatic dicarboxylic acid, (d) a halogenated hydrocarbon and (e) a titanium halide of the general formula: Ti X 4, wherein X represents a halogen atom wherein said catalytic component is employed in combination with, (B) a silicon compound represented by the general formula: Si Rm (OR ') 4 m, wherein R is hydrogen, an alkyl group or an aryl group, R is an alkyl group or an aryl group and m is such that O <m-4, and with (C) an organoaluminum compound; and a catalyst for olefin polymerization comprising: (A) a catalytic component obtained by a process comprising contacting (a) a magnesium fatty acid salt and / or (b) dialkoxymagnesium salt, (c) of a mono- or diester of an aromatic dicarboxylic acid, (d) a halogenated hydrocarbon, and (e) a titanium halide of the general formula: Ti X 4, wherein X represents a halogen atom (B) a silicon compound represented by the general formula: wherein R m (OR ') m wherein R is hydrogen, an alkyl group or an aryl group, R' is an alkyl group or an aryl group, and m is such that

  O m <4, and (C) an organoaluminum compound.

  The polymerization of the olefins by use of the catalyst component or catalyst of the present invention exhibits such high catalytic activity, not to mention the extremely high stereoregularity of the polymer produced, that the amount of catalyst residue in the polymer produced is reduced to a minimum. very low level and the chlorine content of the produced polymer is reduced to a trace level, the result being that the influence of chlorine on the polymer produced is

  so much so that the ash removal process can be completely dispensed with.

  As the chlorine contained in the produced polymer causes the corrosion of the devices used in operations such as granulation and molding, and further causes the deterioration, yellowing, etc., of the polymer produced itself, the decrease in the chlorine content of the polymer produced as stated above is of a

extreme importance in practice.

  Other features of the present invention are that the problem of the ester odor of the produced polymer has been solved without the use of aromatic carboxylic acid ester during the polymerization and that the important defect has been removed. of the so-called high activity supported catalyst mentioned above,

  which is that the catalytic activity per unit of time decreases sharply as the polymerization proceeds, so as to provide a catalyst practically applicable to the copolymerization of olefins as well as to their homopolymerization.

  It is common practice, in the preparation of olefin polymers on an industrial scale, to polymerize in the presence of hydrogen for the purpose of controlling the melt index of the polymer, and the catalyst. The catalyst formed from the catalytic component prepared using magnesium chloride as a support in the prior art has the disadvantage that both the catalytic activity and the stereoregularity of the polymer are greatly reduced. However, the polymerization of olefins in the presence of With the use of the catalyst of the present invention, the result is that little or no decrease in the catalytic activity and stereoregularity of the polymer is observed.

  despite a very high fluidity index of the polymer, which is a very important advantage in practice.

  Another effect of the present invention is that the catalyst of the present invention has an excellent influence on the apparent density of the polymer produced,

  bulk density being of great importance in the preparation of olefin polymers on an industrial scale.

  Detailed Description of the Preferred Embodiments

  Examples of magnesium fatty acid salts employed in the present invention preferably include a magnesium salt of a saturated fatty acid, more preferably

  especially magnesium stearate, magnesium octanoate, magnesium decanoate and magnesium laurate.

  Examples of dialkoxymagnesium employed in the present invention include diethoxymagnesium,

  dibutoxymagnesium, diphenoxymagnesium, dipropoxymagnesium, disec-butoxymagnesium, di-tert-butoxymagnesium, diisopropoxymagnesium, and the like, in particular diethoxymagnesium and dipropoxymagnesium.

  The magnesium salt of fatty acid and the dialkoxymagnesium are preferably used in a state such that the moisture contained therein has been removed to be

reduced to a minimum.

  Examples of aromatic carboxylic acid diisocyanate mono or diester preferably include a phthalic acid mono or diester or terephthalic acid, more particularly dimethyl phthalate, dimethyl terephthalate, diethyl phthalate, terephthalic acid terephthalate and the like. diethyl, dipropyl phthalate, dipropyl terephthalate, dibutyl phthalate, dibutyl tetraphthalate, diisobutyl phthalate, diamyl phthalate, diisoamyl phthalate, ethylbutyl phthalate, ethylisobutyl phthalate, the

  ethylpropyl phthalate, and the like.

  The halogenated hydrocarbons employed in the present invention preferably include chlorinated derivatives of aromatic or aliphatic liquid hydrocarbons, more particularly these examples include propyl chloride, butyl chloride, butyl bromide, propyl iodide, chlorobenzene, benzyl chloride, dichloroethane, trichlorethylene, dichloropropane, dichlorobenzene, trichloroethane,

  carbon tetrachloride, chloroform, methylene dichloride, and the like, and more preferably propyl chloride, dichloroethane, chloroform, and methylene dichloride.

  Examples of the titanium halide represented by the general formula Ti X 4, wherein X is a halogen atom, include titanium tetrachloride,

  titanium tetrabromide, titanium tetraiodide, and the like, with titanium tetrachloride being preferred.

  The silicon compounds employed in the present invention include a phenylalkoxysilane, an alkylalkoxysilane, and the like. Examples of phenylaloxysilane include phenyltrimethoxysilane, phenyltriethoxysilane, phenyltripropoxysilane, phenyltriisopropoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, and the like. Examples of the alkylalkoxysilane include tetramethoxysilane, tetraethyloxysilane, trimethoxyethylsilane, trimethoxymethylsilane, triethoxymethylsilane, ethyltriethoxysilane, ethyltriisopropoxysilane, and the like.

  Examples of organoaluminum compounds employed in the present invention include a trialkoxy aluminum, a dialkyl aluminum halide, an alkyl aluminum dihalide, and mixtures thereof,

  preferably trialkyl aluminum, more preferably triethylaluminum and triisobutylaluminum.

  The amount of ingredient to be used for the preparation of the catalyst component is not specifically limited, unless it has adverse effects on the performance of the catalytic component prepared therefrom, but the mono or The aromatic dicarboxylic acid diester is normally employed in amounts of 0.01 to 2 g, preferably 0.1 to 1 g, and the titanium halide is normally employed in amounts greater than 0.1 g, preferably more than 1 g per gram of magnesium salt of fatty acid and / or dialkoxymagnesium respectively The halogenated hydrocarbon may be employed in arbitrary amount, preferably in amount

as it forms a suspension.

  The order and method of contacting the raw materials employed for the preparation of the catalyst component are not specifically limited, but preferably include the following operations: (1) an operation which comprises suspending the ingredients (a ) and (b) in the ingredient (d), and adding the resulting suspension to the ingredient (e) for the reaction, the ingredient (c) being present during at least one of the steps during operations and the other ingredients (a), (b), (d) and (e); (2) an operation which comprises suspending the ingredient (a) in the ingredient (d) and adding the resulting suspension to the ingredient (e) containing the ingredient (b) in order to of the reaction, ingredient (c) being present in at least one of the steps during the operations, and the other ingredients (a), (b), (d) and (e); (3) an operation which comprises suspending the ingredient (b) in the ingredient (d), and adding the resulting suspension to the ingredient (e) containing the ingredient (a) in in view of the reaction, ingredient (c) being present in at least one of the steps during the operations as well as the other ingredients (a), (b), (d) and (e);

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  (4) an operation which comprises suspending the ingredient (a) in the ingredient (d), and adding the resulting suspension to the ingredient (e) for reaction, the ingredient (c) being present during at least one of the steps during the operations, as well as the other ingredients (a), (d) and (e); and (5) an operation which comprises suspending the ingredient (b) in the ingredient (d), and adding the resulting suspension to the ingredient (e) for reaction, the ingredient (c) being present during at least one of the steps during the operations, as well as

  other ingredients (b), (d) and (e).

  The raw materials used for the preparation of the catalyst component of the present invention are contacted under conditions such that the magnesium salt of the fatty acid and / or the dialkoxymagnesium is suspended in the halogenated hydrocarbon, preferably to remain in suspension at a temperature between generally OC and the boiling point of the halogenated hydrocarbon used for less than 100

  hours, preferably for less than 10 hours, in the presence or absence of the mono- or diester of the aromatic dicarboxylic acid.

  The suspensions obtained as above are preferably brought into contact with the titanium halide or with the titanium halide containing the magnesium salts of the fatty acid or dialkoxymagnesium respectively, a temperature generally between -10 ° C. and the

  boiling point of the titanium halide employed, for a period ranging from 10 minutes to 100 hours, in the presence or absence of the mono- or diester of the aromatic dicarboxylic acid.

  The compositions obtained by the above-mentioned operations in the preparation of the catalyst component can be further contacted at one or

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  repeatedly with titanium halide and can

  also be washed with an organic solvent such as nheptane.

  All the operations described above in the present invention should preferably be carried out in the absence of oxygen, water, etc. The catalytic component thus obtained is combined with the above-mentioned silicon compound and an organoaluminum compound to form a catalyst for the polymerization of olefins. The organoaluminum compound is employed in a molar ratio of 1 to 1000 per atom. of titanium in the catalytic component, and the silicon compound is employed in a

  molar ratio of less than 1, preferably from 0.005 to 0.5 per mole of organoaluminum compound.

  The polymerization of the olefins can be carried out in the presence or absence of organic solvent and the monomeric olefins can be used in the state

gaseous or in the liquid state.

  The polymerization temperature is less than 200 ° C., preferably less than 100 ° C., and the polymerization pressure is less than 9.8 M Pa, preferably

  less than 49 M Pa (gauge).

  Examples of homopolymerized or copolymerized olefins by use of the catalytic component and

  catalyst of the present invention include ethylene, propylene, 1-butene, and the like.

  The following Examples and Comparative Examples further illustrate the present invention.

Example 1

  (Preparation of the catalytic component)

  In a 200 ml round bottom flask equipped with a stirrer and thoroughly purged with nitrogen, are introduced 5 g of magnesium stearate, 5 g of diethoxymagnesium, 1.5 g

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  of dipropyl phthalate and 50 ml of methylene dichloride to form a suspension and then added for 1 hour under reflux. The suspension is then added to 200 ml of Ti C 14 at room temperature in a bottom flask. 500 ml round equipped with a stirrer, then heated up to 90 ° C. to carry out the reaction with stirring at this temperature for 2 hours After completion of the reaction, the reaction product is washed once with 200 ml of n-heptane dehydrated at 40 ° C. and 200 ml of fresh titanium tetrachloride are added thereto to react with stirring at 90 ° C. for 2 hours. After completion of the reaction, the reaction mixture is cooled to 40 ° C. The washing operation is repeated with 200 ml of dehydrated n-heptane until no more chlorine is detected in the n-heptane after washing, in order to complete the washing operation and obtain a catalytic component. if obtained is subjected to a liquid-solid separation operation, the result being that the titanium content of the thus separated solids was found to be 3.86 X

in weight.

  Polymerization of nropylene: In a 2.0-liter autoclave equipped with a stirrer, the air of which was completely replaced by nitrogen, 700 ml of n-heptane, 301 mg, were introduced under a nitrogen atmosphere. triethylaluminum, 32 mg of phenyltriethoxysilane and 0.3 mg of titanium in the form of the catalytic component obtained above. 300 ml of hydrogen gas are then introduced and the mixture obtained is heated to 70 ° C. and the reaction mixture is heated therein. polymerization of propylene under a pressure of 0.6 M Pa (manometer) for 4 hours, introducing gaseous propylene After completion of the polymerization reaction, the solid polymer thus obtained is collected by filtration and is dry by heating at 80 ° C. under reduced pressure

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  on the other hand, the filtrate is thickened to obtain soluble polymer in a solvent used in polymerization.

  The amount of polymer soluble in the solvent employed in the polymerization is represented by (A), and the amount of solid polymer obtained above is represented by (B). The solid polymer is extracted with boiling n-heptane for 6 hours. to obtain polymer insoluble in boiling n-heptane, the amount of this polymer being represented by (C)> The polymerization activity (D) per unit weight of the catalyst component is represented by the formula I (A) + ( B) l (g)

(D) = (I)

  amount of catalyst component (g) and the yield (E) of crystalline polymer is represented by the formula: (c) (E) = x 100 (II) (B) Further, the overall yield (F) of crystalline polymer is represented by the formula (c) (F) = x 100% (III)

(A) + (B)

  The chlorine content and the melt index of the

  produced polymer are represented by (G) and (H) respectively.

  The results thus obtained are presented in

Table 1.

Example 2

  The procedures of Example 1 are repeated, except that the polymerization reaction is carried out in 6 hours. The results thus obtained are presented in

Table 1.

Example 3

  The procedures of Example 1 are repeated except that 1.2 g of dipropyl phthalate are used to prepare a catalyst component. The titanium content of the separated solids is 3.54% by weight. In the polymerization of propylene, the procedures of Example 1 are repeated, except that 64 mg of phenyltriethoxysilane are used.

  thus obtained are shown in Table 1. Example 4

  The procedures of Example 1 are repeated except that the suspension under pressure is injected into OOC titanium tetrachloride to prepare a

  catalytic component The titanium content of the separated solids is 3.62% by weight.

  In the polymerization of propylene, the procedures of Example 1 are repeated.

  obtained are shown in Table 1.

Example 5

  The procedures of Example 1 are repeated except that the reaction is carried out with titanium tetrachloride at 100 ° C. to prepare a catalytic component. The titanium content of the separated solids is

of 3.12% by weight.

  In the polymerization of propylene, the procedures of Example 1 are repeated.

  obtained are shown in Table 1.

Example 6

  The procedures of Example 1 were repeated except that 2.0 g of dibutyl phthalate was used instead of dipropyl phthalate to prepare a catalyst component. The titanium content of the separated solids

  is 2.91% by weight. In the polymerization of propylene, the procedures of Example 1 are repeated. The results thus obtained are shown in Table 1.

Example 7

  The procedures of Example 1 are repeated except that 2.0 g of phthalate diamine is used instead of dipropyl phthalate to prepare a catalyst component. The titanium content of the separated solids is 3.70% by weight. weight In the polymerization of propylene,

  the procedures of Example 1 are repeated. The results thus obtained are presented in Table 1.

Example 8.

  The procedures of Example 1 are repeated except that magnesium laurate is used in place of magnesium stearate to prepare a catalytic component. The titanium content of the separated solids is 3.52% by weight. polymerization of propylene,

  the procedures of Example 1 are repeated. The results thus obtained are presented in Table 1.

Example 9.

  The procedures of Example 1 are repeated except that carbon tetrachloride is used in place of methylene dichloride to prepare a catalyst component. The titanium content of the separated solids is 3.48% by weight. polymerization of the

  propylene, the procedures of Example 1 are repeated.

  The results thus obtained are presented in Table 1.

Example 10

  The procedures of Example 1 are repeated except that chloroform is used instead of methylene dichloride to prepare a cationic lycate component. The titanium content of the separated solids is 3.61% by weight in the polymerization. propylene, the procedures of Example 1 are repeated. The results thus obtained are presented in Table 1.

Example 11

  In a 100 ml round bottom flask equipped with a stirrer and totally purged with nitrogen, 5 μl of diethoxymagnesium and 50 ml of methylene dichloride are introduced to form a suspension and then the mixture is stirred for 1 hour under reflux. a 500 ml round-bottomed flask equipped with a stirrer and completely purged with nitrogen, 5 g of magnesium stearate, 1.5 g of dipropyl phthalate and 200 ml of Ti Cl 4 are introduced to make them react.

  with stirring at room temperature for 1 hour.

  Then, the first suspension is injected into the last reaction mixture and then heated to 900 ° C to react with stirring at this elevated temperature for 2 hours. Thereafter, the procedures are repeated.

  of Example 1 to prepare a catalyst component.

  The titanium content of the separated solids is 3.50% by weight.

  In the polymerization of propylene, the procedures of Example 1 are repeated.

  obtained are shown in Table 1.

Example 12.

  (Preparation of the catalytic component)

  200 g of magnesium stearate, 1.2 g of dibutyl phthalate and 50 ml of methylene dichloride are introduced into a 200 ml round bottom flask equipped with a stirrer and completely purged with nitrogen. The suspension is then stirred for 1 hour at reflux. The suspension is then injected into 200 ml of Ti C 14 at room temperature in a 500 ml round-bottomed flask equipped with a stirrer and heated to 80.degree. C to react with stirring at this temperature for 2 hours After completion of the reaction, the reaction product is washed 10 times with 200 ml of dehydrated r-heptane at 40 ° C., and 200 ml of titanium tetrachloride are added thereto. fresh to react with stirring at 80 C

during 2 hours.

  The procedures of Example 1 are repeated to prepare a catalyst component.

  Titanium solids separated is 2.77% by weight.

  In the polymerization of propylene, the procedures of Example 1 are repeated except that 0.2 mg of titanium is added in the form of the catalyst component. The results thus obtained are presented in FIG.

table 1.

Example 13

  The procedures of Example 12 are repeated except that the polymerization reaction is carried out.

  for 6 hours The results thus obtained are presented in Table 1.

Example 14.

  The procedures of Example 12 are repeated except that 25 ml of methylene dichloride are used to prepare a catalyst component.

  in titanium separated solids is 2.62% by weight.

  In the polymerization of propylene, we repeat

  Procedures of Example 12 The results thus obtained are shown in Table 1.

Example 15

  The procedures of Example 12 are repeated except that carbon tetrachloride is employed.

  instead of methylene dichloride to prepare a catalyst component The titanium content of the separated solids is 2.86% by weight.

  In the polymerization of propylene, the procedures of Example 12 are repeated.

  The results are shown in Table 1. Example 16

  The procedures of Example 12 are repeated except that the reaction is carried out with titanium tetrachloride at 650 ° C. to prepare a constituent

  The titanium content of the separated solids is 3.01% by weight.

  In the polymerization of propylene, the procedures of Example 12 are repeated.

  obtained are shown in Table 1.

Example 17

  The procedures of Example 12 are repeated except that 1.2 g of dipropyl phthalate are used to prepare a catalyst component.

  Titanium solids separated is 2.97% by weight.

  In the polymerization of propylene, the procedures of Example 12 are repeated.

  obtained are shown in Table 1.

Example 18.

  The procedures of Example 1 are repeated except that no magnesium stearate is used to prepare the catalyst component.

  Titanium solids separated was 4.01% by weight.

  In the polymerization of propylene, the procedures of Example 1 are repeated. The apparent density

  of the polymer produced is 0.38. The results thus obtained are shown in Table 1.

Example 19

  The procedures of Example 18 are repeated except that the polymerization reaction is carried out in 6 hours. The apparent density of the polymer produced is 0.39. The results thus obtained are presented in US Pat.

Table 1.

Example 20.

  The procedures of Example 18 are repeated except that 25 ml of methylene dichloride are used to prepare a catalyst component.

  in titanium separated solids is 3.92% by weight.

  In the polymerization of propylene, we repeat

  EXAMPLES OF EXAMPLE 18 The apparent density of the polymer produced is 0.39. The results thus obtained are shown in Table 1.

Example 21.

  The procedures of Example 18 are repeated except that carbon tetrachloride is employed.

  instead of methylene dichloride to prepare a catalytic component The titanium content of the separated solids is 3.71% by weight.

  In the polymerization of propylene, we repeat

  EXAMPLES OF EXAMPLE 18 The apparent density of the polymer produced is 0.38. The results thus obtained are shown in Table 1.

Example 22.

  The procedures of Example 18 are repeated except that chloroform is used in place of methylene dichloride to prepare a catalytic component. The titanium content of the separated solids is

3.86% by weight.

  In the polymerization of propylene, we repeat

  the procedures of Example 18 The apparent density of the polymer produced is 0.37. The results thus obtained are shown in Table 1.

Example 23.

  The procedures of Example 18 are repeated except that the reaction is carried out with titanium tetrachloride at 100 ° C. to prepare the catalyst component. The titanium content of the separated solids is

3.36% by weight.

  In the polymerization of propylene, we repeat

  the procedures of Example 18 The apparent density of the polymer produced is 0.37. The results thus obtained are shown in Table 1.

Example 24.

  The procedures of Example 18 are repeated except that the slurry is injected into titanium tetrachloride at 0 ° C. to prepare a catalyst component. The titanium content of the separated solids is

of 4.11% by weight.

  In the polymerization of propylene, the procedures of Example 18 are repeated. The apparent density of the polymer produced is 0.39. The results thus obtained are presented in Table 1.

Example 25

  The procedures of Example 18 are repeated except that -1.2 g of dipropyl phthalate are used.

  The titanium content of the separated solids is 3.64% by weight.

  In the polymerization of propylene, the procedures of Example 18 are repeated, except that

  The apparent density of the product polymer is 0.37. The results thus obtained are shown in Table 1.

Example 26.

  The procedures of Example 18 were repeated except that 2.0 g of dibutyl phthalate was used instead of dipropyl phthalate to prepare a catalytic component. The titanium content of the separated solids

is 3.66% by weight.

  In the polymerization of propylene, we repeat

  EXAMPLES OF EXAMPLE 18 The apparent density of the polymer produced is 0.37. The results thus obtained are shown in Table 1.

Example 27.

  The procedures of Example 18 are repeated

  except that 2.0 g of diammonium phthalate is used in place of dipropyl phthalate to prepare a catalytic component. The titanium content of the separated solids is 4.19% by weight.

  In the polymerization of propylene, we repeat

  EXAMPLES OF EXAMPLE 18 The apparent density of the product polymer is 0.37. The results thus obtained are shown in Table 1.

Comparative Example 1

  (Catalyst component preparation).

  100 g of Mg C 12 and 31.5 g of ethyl benzoate are sprayed together in a nitrogen atmosphere for 18 hours. 100 g of the copulverized product are introduced into a 2000 ml glass flask under a nitrogen atmosphere, and 500 ml of Ti C 14 are added thereto and the mixture is reacted with stirring at 65 ° C. for 2 hours. After completion of the reaction, the reaction mixture is cooled to 40 ° C. and left to settle to settle by settling.

the supernatant liquid obtained.

  The washing operation is repeated with 1000 ml of n-heptane until no more chlorine is detected in the n-heptane after washing in order to carry out a complete washing and to obtain a catalytic component. The catalytic component thus obtained is subjected to a solid-liquid separation operation, the result being that the titanium content of the solids thus separated has been found

equal to 1.28% by weight.

  In the polymerization of propylene, the procedures of Example 1 are repeated except that 1.0 mg of titanium is added in the form of the catalytic component. The apparent density of the polymer produced is

  0.30 The results thus obtained are presented in Table 1.

Comparative Example 2

  The procedures of Example 1 were repeated except that 2.0 g of ethyl benzoate was used instead of dipropyl phthalate to prepare a catalytic mixture. The titanium content of the separated solids

is 3.83% by weight.

  In the polymerization of propylene, the procedures of Example 1 are repeated, except that

  employs 137 mg of ethyl p-toluate and 0.5 mg of titanium as catalyst component.

  The resulting polymer is 0.32. The results thus obtained are shown in Table 1.

TABL'E A IJ 1

Examples

1 2 3 4 5 6 7 8 9 10

  Quantity of soluble polymer in the solvent used in 6.1 8.4 6.4 6.4 6.2 6.9 6.2 7.2 6.0 7.0 Polymerization (A) g Quantity of solid polymer Quantity of solid polymer 226 (B) g Quantity of polymer insoluble in boiling n-heptane 223 310 244 238 250 272 216 236 223 236 (C) g Polymerization activity per unit weight 29900 41500 30100 29800 27000 27500 27900 29000 27000 29600 catalytic component (D) Yield of crystalline polymer 98.7 98.7 98.4 98.7 98.8 98.6 98.2 98.3 98.2 98.7 (E) % Overall yield of crystalline polymer 96.1 96.2 95.8 96.2 96.5 96.1 95.5 95.5 95.7 95.9 (F) Z Chlorine content of the polymer produced 18 13 18 18 (G) ppm Melt flow rate of the product polymer 26.5 29.3 22.1 23.0 15.1 17.2 12.6 26.1 27.3 21.6 (H) w ru Ln t> 'P TABLE 1 (continued)

Examples

11 12 13 14 15 16 17 18 19 20

  Quantity of polymer soluble in the solvent used in 6.8 5.9 8.2 6.0 4.8 4.3 4.8 5.8 8.1 6.0 Polymerization (A) g Quantity of solid polymer 243 210 294 220 196 190 192 219 307 211 (B) g Quantity of polymer insoluble in boiling n-heptane 240 207 290 217 193 187 189 216 303 208 (C) g Polymerisation activity per unit weight of 29100 29900 41860 29620 28730 29260 29240 30050 42130 28370 Catalyst Component (D) Yield in Crystalline Polymer 98.8 98.6 98.6 98.6 98.5 98.4 98.4 98.6 98.7 98.6 (E)% Overall Yield crystalline polymer 96, 1 95.9 96.0 96.0 96.1 96.2 96.0 96.1 96.2 95.9 (F)% Chlorine content of the polymer produced 19 18 13 19 19 19 19 18 13 20 (G) ppm Flow rate of polymer produced 26.0 21.6 23.6 31.3 29.5 29.3 31.9 31.2 33.6 30.3 (H) N n Ln 4 - TABLE 1 (continued) Eepe Comparative Examples

21 22 23 24 25 26 27 1 2

  Quantity of soluble polymer in the solvent used in vantutili lepsol 6.0 6.8 6.4 6.0 7.1 6.6 7.5 7.3 7.4 Polymerization (A) g Amount of solid polymer 228 229 255 220 250 235 195 372 336 (B) g Quantity of polymer insoluble in boiling n-heptane 224 226 223 246 232 192 352 325 (C) Polymerization activity per unit weight of 28920 30350 29270 30960 31200 29460 28040 4860 Catalyst component (D) Yield of crystalline polymer 98.2 98.7 98.8 98.6 98.4 98.7 98.5 94.6 96.7 (E)% Overall yield of crystalline polymer 95.7 95 , 96.4 96.0 95.7 96.0 95.6 92.8 94.6 (F)% Chlorine content of the product polymer 19 18 19 18 17 19 20 138 22 (G) ppm Melt flow rate polymer produced 31.6 29.2 22.3 40.1 29.1 28.6 22.6 3.1 6.9 (H), O 1 j Ln Ln -ul Ol N

Claims (19)

  A catalytic component (A) for the polymerization of olefins obtained by a process comprising contacting (a) a magnesium salt of a fatty acid and / or (b) a dialkoxymagnesium, (c) a mono- or diester of an aromatic dicarboxylic acid, (d) a halogenated hydrocarbon, and (e) a titanium halide of the general formula: Ti X 4, wherein X represents a halogen atom, this catalytic component being used in combination with (B) a silicon compound represented by the general formula: wherein R m (OR ') 4 m, wherein R is hydrogen, an alkyl group or an aryl group, R' is an alkyl group or an aryl group, and m is such that O <m 4, and with (C) an organoaluminum compound. Catalyst component according to claim 1, characterized in that said catalytic component is obtained by a process which comprises suspending the ingredients (a) and (b) in the ingredient (d), and adding the the suspension obtained with the ingredient (e) for the reaction, wherein ingredient (c) is present in at least one of the steps in the process as well as the   other ingredients (a), (b), (d) and (e).   Catalyst component according to claim 1, characterized in that said catalytic component is obtained by a process which comprises suspending the ingredient (a) in the ingredient (d), and adding the suspension obtained with ingredient (e) containing ingredient (b) for the reaction, wherein ingredient (c) is present in at least one of the steps in the process as well as the other ingredients (a), ( b), (d) summer).   Catalytic component according to Claim 1, characterized in that this catalytic constituent   is obtained by a process which comprises suspending the ingredient (b) in the ingredient (d), and adding the   the suspension obtained to ingredient (e) containing ingredient (a) for the reaction, wherein ingredient (c) is present in at least one of the steps in the process as well as the other ingredients (a). ), (b), (d) and (e). Catalyst component according to claim 1, characterized in that said catalytic component is obtained by a process which comprises suspending the ingredient (a) in the ingredient (d), and adding the resulting suspension to ingredient (e) for the reaction, ingredient (c) being present in at least one of the steps in the process and the other ingredients (a), (d) and (e).   Catalyst component according to Claim 1, characterized in that this catalyst component is obtained by a process which comprises suspending the ingredient (b) in the ingredient (d), and adding the resulting suspension. to ingredient (e) for the reaction, ingredient (c) being present in at least one of the steps in the process as well as the other ingredients (b), (d) and (e).   Catalyst component according to any one of claims 1 to 5, characterized in that the magnesium salt of the fatty acid is a magnesium salt of a saturated fatty acid.   Catalyst component according to claim 7, characterized in that the magnesium salt of a   Saturated fatty acid is selected from magnesium stearate, magnesium octanoate, magnesium decanoate and magnesium laurate.   Catalyst component according to one of Claims 1, 2, 3, 4 or 6, characterized in that   that the dialkoxymagnesium is selected from diethoxymagnesium and dipropoxymagnesium.   10 Catalytic constituent according to any one   claims 1 to 6, characterized in that the   mono or diester of the aromatic dicarboxylic acid is chosen from the mono and diesters of phthalic acid or terephthalic acid.   Catalyst component according to Claim 10, characterized in that the mono- or di-ester of phthalic acid or terephthalic acid is chosen from dimethyl phthalate, dimethyl terephthalate, diethyl phthalate and diethyl terephthalate. , dipropyl phthalate, dipropyl terephthalate, dibutyl phthalate, dibutyl terephthalate, diisobutyl phthalate, diamyl phthalate, diisoamyl phthalate, ethylbutyl phthalate, phthalate   of ethylisobutyl and ethylpropyl phthalate.   Catalytic component according to any one of Claims 1 to 6, characterized in that the said   halogenated hydrocarbon is selected from chlorinated derivatives   aromatic or aliphatic hydrocarbons in the liquid state at room temperature.   Catalyst component according to one of Claims 1 to 6, characterized in that the said   Halogenated hydrocarbon is selected from chlorobenzene, benzyl chloride, propyl chloride, butyl chloride, dichloroethane, trichloroethane, carbon tetrachloride, chloroform and dichloride. methylene.   Catalyst component according to one of Claims 1 to 6, characterized in that the said   Titanium halide is titanium tetrachloride.   Catalyst component according to one of Claims 1 to 6, characterized in that the said   The silicon compound is selected from phenyl and alkylalkoxysilane.   Catalyst component according to one of Claims 1 to 6, characterized in that the said   organoaluminum compound is selected from triethylaluminum and triisobutylaluminum.   Catalyst component according to Claim 1, characterized in that the said olefins are selected from ethylene, propylene and 1-butene, this catalytic component being used in the homopolymerization or copolymerization thereof.   A catalyst for the polymerization of olefins comprising: (A) a catalytic component obtained by a process comprising contacting (a) a magnesium salt of a fatty acid and / or (b) a dialkoxymagnesium, ( c) a mono- or diester of an aromatic dicarboxylic acid, (d) a halogenated hydrocarbon and (e) a titanium halide of the general formula: Ti X 4, wherein X represents a halogen atom, (B) a compound silicon compound represented by the general formula: wherein R m (OR ') 4 m, wherein R is hydrogen, an alkyl group or an aryl group, R' is an alkyl group or an aryl group, and m is such that O <m <4, and (C) an organoaluminum compound.   Catalyst according to Claim 18, characterized in that the said catalytic component (A) is chosen from the catalytic constituents claimed in any one of Claims 2 to 14.   Catalyst according to Claim 18, characterized in that the said silicon compound is chosen from phenyl and alkylalkoxysilane.   Catalyst according to claim 18, characterized in that said organoaluminum compound is selected from triethylaluminum and triisobutylaluminum.   Catalyst according to Claim 18, characterized in that the said olefins are chosen from ethylene, propylene and 1-butene, the catalyst   being used for homopolymerization or copolymerization thereof.