GB2143834A - Polymerization catalyst - Google Patents

Abstract

A catalyst for the polymerization of olefins is formed from: (A) a catalyst component obtained by contacting (a) a fatty acid salt of magnesium and/or (b) dialkoxymagnesium, with (c) mono or diester of an aromatic dicarboxylic acid, (d) a halogenated hydrocarbon and (e) a titanium halide TiX4; (B) a silicon compound SiRm(OR')4-m, wherein R is hydrogen, alkyl group or aryl group, R' is alkyl group or aryl group, and 0</=m</=4; and (C) an organoaluminium compound. Polymerization of olefins by use of the catalyst provides such advantages as high polymerization activity per unit weight of the catalyst component, prolonged polymerization activity, high yield of stereoregular polymer, and a polymer product free of estereal odor.

Description

SPECIFICATION Polymerization catalyst and component thereof This invention relates to a catalystforthe polymerization of olefins, and a titanium-containing component thereof. (Polymerization includes homopolymerization and copolymerization.) Acatalystforthe polymerization of olefinsformed by combining a solid titanium halide as a catalyst component with an organoaluminium compound is well known in the art.However, in the polymerization of olefins by use ofthe conventional catalyst, the yield of polymer per unit weight of the catalyst component or titanium moiety in the catalyst component (hereinafter referred to simply as a polymerization activity per unitweight of the catalyst component or of titanium) is so low that a so-called deashing process for subsequently removing catalyst residues from the produced polymer is indispensable in order to obtain an industrially applicable polymer. In the deashing process, alcohols or chelating agents are used in large amounts, sothatthe deashing process needs an apparatus for recovery thereof as well as the deashing apparatus itself, and consequently has many problems accompanying therewith relative to resources, energy, and the like.Thus, the deashing process raises great problems to be solved urgently in the art. A number of studies and suggestions have been made for enhancing the polymerization activity per unit weight oftitanium in the catalyst component, so that the complicated deashing process may be dispensed with.

Especially as a recent tendency, a large number of suggestions have been made such that the polymerization activity per unitweight oftitanium in the catalyst component is remarkably enhanced in the polymerization of olefins with a catalyst component prepared by supporting a transition-metal compound as an active ingredient such as a titanium halide on a carrier material so that the active ingredient may act effectively.

However,the prior art employing magnesium chloride as the carrier as described above, has such a disadvantagethatthe chlorine moiety contained in the magnesium chloride conventionally used as the carrier has an adverse effect on the produced polymer, resulting in leaving problems to be solved such as requirements for such a high activity as to be substantially free from the adverse effect due to the chlorine moiety, or as requirements for controlling a concentration of the magnesium chloride itself at a sufficiently low level.

The present inventors proposed a process for preparing a catalyst componentforthe polymerization of olefins in Japanese Patent application No.

20045411982 (GB 2130226), to reduce chlorine content in the produced polymer with high polymerization activity and high yield ofstereoregular polymer, attaining the aforementioned object. Also required for a catalyst formed by combining a catalyst component using magnesium chloride as a carrier with an organoaluminium compound to carryouton an industrial scale the polymerization of olefins, especial lystereoregularpolymerizationofpropylene, 1butene, and the like, is the presence of an electron donor compound such as aromatic carboxylic acid esters in the polymerization system. However, the aforementioned aromatic carboxylic acid ester imparts a peculiar estereal odorto the produced polymer, raising a serious problem of deodorizing therefrom in the art.

It was substantially impossible for the so-called highly active supported catalyst formed by use of a catalyst component employing the aforementioned magnesium chloride as a carrier to be of practical use, because use of the supported catalyst results in abrupt deactivation thereof in spite of high activitythereofin the beginning of polymerization, and results in raising problems in process operations, particularly in the case where a prolonged polymerization time is required as in block copolymerization and the like.In orderto solve the aforementioned problems, Japanese patent laid-open publication No. 94590/ 1979 discloses a catalystforthe polymerization of olefinswhich comprises a catalyst component prepared by use of magnesium dihalide as one ofthe starting materials, an organoaluminium compound, an aromatic carboxylic acid ester, and a compound having a M-O-R group. However, the catalyst disclosed as above fails to solve the problem of deodorizing from the produced polymer in that organic carboxylic acid esters are used on polymerization, and requires complicated procedures for the preparation thereof with practically insufficient catalyst performance and polymerization activity with time.

Embodiments ofthe present invention may be a catalyst component for the polymerization of olefins and a catalystthereforwhich are capable of resulting in greatly reducing both the amount ofthe catalyst residues and halogen content in the produced polymerto such an extentthatthe deashing process may be completely dispensed with.

Embodiments ofthe present invention may be capable of resulting in high polymerization activity and in much smaller decrease of the polymerization activity with time, or a prolonged polymerization activity. Embodiments ofthe present invention may be capable of affording a high yield of polymer which is stereoregular and free of such an estereal odor as imparted in the case where aromatic carboxylic acid esters are used as the electron donor compound in the prior art.

Embodiments of the present invention may undergo little or no reduction in both the polymerization activity and yield of stereoregular polymer during polymerization of olefins in the presence of hydrogen; the thus produced polymer may have a very high melt index.

The present invention provides a catalyst component (A) forthe polymerization of olefins obtained by a process comprising contacting (a) a fatty acid salt of magnesium andlor (b) dialkoxymagnesium, with (c) a mono or diester of an aromatic dicarboxylic acid, (d) a halogenated hydrocarbon, and (e) a titanium halide of the general formula: TiS4, wherein X represents a halogen atom. This catalyst component is for use in combination with (B) a silicon compound represented bythegeneral formula: SiRm(OR')4 m, wherein R is hydrogen, alkyl group, or acryl group, R' is alkyl group or aryl group, and 0#m#R, and with (C) an organoaluminium compound.In anotheraspectthe invention provides such a catalystforthe polymerization of olefins comprising A, B and C. Polymerization of olefins using the catalyst component orthe catalyst og the present invention may show such a high catalyst activity to say nothing of an extremely high stereoregularity in the produced polymerthatthe amount of the catalyst residues in the produced polymer is reduced to a very low level, and chlorine content in the produced polymer is reduced to a trace amount, resulting in that influence chlorine on the produced polymer is reduced to such an extent that the deashing process may be completely dispensed with.

Since chlorine contained in the produced polymer causes corrosion of devices employed in such steps as pelletizing and molding, and further causes deterioration, yellowing, etc. of the produced polymer itself, reduction of chlorine content in the produced polymer as above has an extremely important meaning in the art.

Further advantages that may arise include: the problem ofthe estereal odor in the produced polymer may be solved by not using such problematic esters on polymerization, and the serious defect ofthe so-called highly active supported catalyst as mentioned above that catalyst activity per unittime is greatly reduced as polymerization proceeds can be overcome to provide a catalyst practically applicable to compolymerization of olefins as well as homopolymerization thereof.

It is of a common practice in the preparation of olefin polymer on an industrial scale that polymerization is carried out in the presence of hydrogen e.g. for controlling the melt index of polymer; the catalyst formed from the catalyst component prepared by use of magnesium chloride as a carrier in the prior art has such a disadvantage that both catalytic activity and stereoregularity of the polymer are greatly reduced.

However, polymerization of olefins in the presence of hydrogen using the catalyst ofthe present invention may be such that little or no decrease in catalytic activity and in stereoregularity of the polymer is observed in spite of a very high melt index ofthe polymer, providing extremely great advantages in the art.

Another possible advantage is that a catalyst ofthe present invention may lead to an excellent bulk density ofthe produced polymer, which is of great importance in the preparation of olefin polymers on an industrial scale.

Examples of the fatty acid salt of magnesium used in the present invention include saturated fatty acid salt of magnesium, preferably magnesium stearate, magnesium octanoate, magnesium decanoate, and magnesium laurate.

Examples of the dialkoxymagnesium used in the present invention include diethoxymagnesium, dibutoxymagnesium, diphenoxymagnesium, dipropoxymagnesium, di. sec-butoxymagnesium, di-tertbutoxymagnesium, diisopropoxymagnesium, and we prefer diethoxymagnesium and dipropoxymagne- sium.

The fatty acid salt of magnesium andlor dialkoxy magnesium are employed preferably in such a state that the moisture contained therein has been removed therefrom to be reduced to a minimum.

Examples of mono ordiesterofaromaticdicarboxy- lic acid include mono or diesters of phthalic acid or terephthalic acid, more specfflly, dimethylphthalate, dimethylterephthalate, diethylphthalate, diethylterephthalate, dipropylphthalate, dipropylterephthalate, dibutylphthalate, dibutylterephthalate.

diisobutylphthalate, diamylphtharate, dsisoamyl- phthalate, ethylbutylphthalate, ethylisabutyiphtha- late, ethylpropylphthalate.

The halogenated hydrocarbon used in the present invention preferably includes liquid chlofi;desaf aromatic or aliphatic hydrocarbons, preferredexa plebs thereof include propyl chloride, butyl chloride; butyl bromide, propyl iodide, chlorobenzene, benzyl chloride, dichloroethane, trichloroethylene, dichior- opropane, dichlorobenzene, trichloroethane, carbon tetrachloride, chloroform, methylene dichloride Parti- cularly preferred are propyl chloride, dichlornethane, chloroform, and methylene dichloride.

Examples ofthetitanium halide represented by the general formula TiX4wherein Xis a halogen atom, include titanium tetrachloride, titanium tetrabromide, and titanium tetraiodide; titanium tetrachloride being preferred.

The silicon compound used in the present invention may be a phenylalkoxysilaneoralkylakoxysilane.

Examples of phenylalkoxysilane include pheny Itrimethoxysilane, phenyltriethoxysilane, phenyltripropoxysilane, phenyltriisopropoxysilane, dipheny Idimethoxysilane, diphenyldiethoxysilane. Examples of aliphatic compounds include tetramethoxysilane, tetraethoxysilane, trimethoxyethylsilane, trimethoxymethylsilane, triethoxymethylsilane, ethyltriethoxysilane, ethyltriisopropoxysilane.

Examples ofthe organoaluminium compound used in the present invention include trialkoxyaluminium dialkylaluminium halide, alkylaluminium dihalide, and mixtures thereof, preferably trialkylaluminium, more preferablytriethylaluminium and triisobutylaluminium.

The amountto be used ofthe ingredients for the preparation ofthe catalyst component is not specific cally limited unless it has adverse effects on the performance of the catalyst componentformed therefrom, but mono or diester of aromatic dicarboxylic acid is used normally in an amount or from 0.01 to 2 g, preferably from 0.1 to 1 g,andthetitanitim halide used normally in an amount morethan g, preferably more than 1 g per 1 g of thefutty a'sattcf magnesium and/or dialkoxymagnesium respectively.

The halogenated hydrocarbon may be used in an arbitrary amount, preferably in such an amount as to form a suspension.

The contacting order and manner ofthe starting materials used for the formation Of the catalyst component are not specifically limited, but the following processes are preferred: (1 ) a process which comprises suspending the ingredients (a) and (b) into the ingredient (d), and adding a resulting suspension to the ingredient (e) for reaction, the ingredient (c) being present in at least one ofthe stages in the course of the process as well as other ingredients (a), (b), (d) and (e); (2) a process which comprises suspending the ingredient (a) into the ingredient (d), and adding a resulting suspension tothe ingredient (e) containing the ingredient (b) for reaction, the ingredient (c) being present in at least one ofthe stages in the course of the process as well as other ingredients (a), (b), (d) and (e);; (3) a process which comprises suspending the ingredient (b) into the ingredient (d), and adding a resulting suspension to the ingredient (e) containing the ingredient (a) for reaction, the ingredient (c) being present in at least one ofthe stages in the course ofthe process as well as other ingredients (a), (b), (d) and (e); (4) a process which comprises suspending the ingredient (a) into the ingredient (d), and adding a resulting suspension to the ingredient (e) for reaction, the ingredient (c) being present in at least one of the stages in the course ofthe process as well as other ingredients (a), (d) and (e); and (5) a process which comprises suspending the ingredient (b) into the ingredient (d), and adding a resulting suspension to the ingredient (e) for reaction, the ingredient (c) being present in at least one of the stages in the course of the process as well as other ingredients (b), (d) and (e).

The starting materials used for the formation ofthe catalyst component of the present invention are brought into contact under such conditions that fatty acid salt of magnesium and/or dialkoxymagnesium is suspended into halogenated hydrocarbon preferably in such a manner as to keep under suspension ata temperature offrom generaliy O"C to boiling point of the halogenated hydrocarbon used for less than 100 hours, preferablyfor less than 10 hours in the presence of or in the absence of mono or diester of aromatic dicarboxylic acid.

The resulting suspensions as above are preferably brought into contactwith titanium halide orwith titanium halide containing fatty acid salt of magnesium or dialkoxymagnesium respectively at a temperaturegenerallyoffrom -10 Cto boiling point of titanium halide used for a period of time from 10 minutesto 100 hours in the presence of or in the absence of mono or diester of aromatic dicarboxylic acid.

The compositions obtained according to the aforementioned processes in the preparation ofthe catalyst component may be further brought into contact once or more times with the titanium halide, and also may be washed with an organic solvent such as n-heptane.

All the procedures described above in the present invention should be preferably conducted in the absence of oxygen, water, or other unwanted reactants.

The catalyst component thus obtained may be combined with the aforementioned silicon compound and an organo-aluminium compound to form a catalyst for the polymerization of olefins. The organoaluminium compound may be in a molar ratio of from 1 to 1000 per atom oftitanium inthecatalyst component, and the silicon compound may be in a molar ratio of less than 1, preferably from 0.005 to 0.5 per more ofthe organoaluminium compound.

The polymerization of olefines may be performed in the presence of, or in the absence of an organic solvent, and olefin monomers may be used in the gaseous or liquid state.

The polymerization temperature is below 200"C, preferably below 1 OO"C, and the polymerization pressure is below 100 kg/cm2 gauge, preferably below 50 kg/cm2 gauge.

Examples of olefins homopolymerized or copolymerized by use of the catalyst component and the catalyst of the present invention include ethylene, propylene, and 1-butene.

The following Examples and Comparative Examples illustrate the present invention more in detail.

Examples (Preparation of catalyst component) To a 200 ml round flaskfitted with a stirrer and thoroughly purged with nitrogen are charged 5 g of magnesium stearate, 5 g of diethoxymagnesium, 1.5 g of dipropyl phthalate, and 50 ml of methylene dichloride to form a suspension followed by stirring for 1 hour under reflux. The suspension isthen injected into 200 ml of TiC14 at room temperature in a 500 ml round flaskfitted with a stirrerfollowed by heating up to 90"C for reacting with agitation at that temperature for 2 hours. After the completion of the reaction, a reaction product is washed 10 times with 200 ml of dehydrated n-heptane at 40"C, and 200 ml of fresh titanium tetrachloride is added thereto for reacting with agitation at 900C for 2 hours.Afterthe completion ofthe reaction, the reaction mixture is cooled down to 40"C. Awashing procedure with 200 ml of dehydrated n-heptane is repeated until no chlorine is detected in the n-heptane afterwashing to complete the washing procedure and to obtain a catalyst component. The catalyst component thus obtained is subjected to solid-liquid separation procedure with the resultthatthe titanium content in the solids thus separated is measured to be 3.86% by weight.

Polymerization of propylene: To a 2.0 liter autoclave fitted with a stirrer, the air in which is thoroughly replaced by nitrogen, 700 ml of n-heptane,301 mg of triethylaluminium,32 mg of phenyltriethoxysilane and 0.3 mg as titanium atom of the catalyst component obtained as above are charged in an atmosphere of nitrogen. Thereafter 300 ml of hydrogen gas is charged thereinto and the resulting mixture is heated to 70"C and subjected to propylene polymerization under a pressure of 6 kglcm2 gaugefor4 hours introducing thereinto propylene gas. Afterthe completion of polymerization reaction, solid polymer thus obtained is collected by filtration and dried by heating at 800C under reduced pressure.On the other hand, the filtrate is thickened to obtain polymer soluble in a solvent used in polymerization.

The amount ofthe polymer soluble in the solvent used in polymerization is represented by (A), and the amount ofthe solid polymer obtained as above is represented by (B). The solid polymer is subjected to extraction with boiling n-heptane for 6 hours to obtain polymer insoluble in boiling n-heptane,the amountofwhich is represented by (C).The polymerization activity (D) per unitweightofthe catalyst component is represented by the formula [(A) + (B)1 (g) (D) = amount of catalyst component (g) and the yield (E) of crystalline polymer is represented bytheformula (C) (E)= x 100% x100% (B) Further, the overall yield (F) of crystalline polymer is represented by the formula (C) (F) x100% (A) + (B) The chlorine content and meltindexofthe produced polymer are represented by (G) and (H) respectively.

Resultsthus obtained are shown inTable-1.

Example2 The procedures of Example 1 are repeated except that polymerization reaction is effected for 6 hours.

Results thus obtained are shown in Table-1.

Example 3 The procedures of Example 1 are repeated except that 1.2 g of dipropylphthalate is used to prepare a catalyst component. Thetitanium content in the solids separated is 3.54% byweight In the polymerization of propylene, the procedures of Example 1 are also repeated except that 64 mg of phenyltriethoxysilane is used. Results thus obtained are shown inTable-1.

Example 4 The procedures of Example 1 are repeated except thatthesuspension is injected under pressure into titanium tetrachloride at O"C to prepare a catalyst component. The titanium content in the solids separated is 3.62% by weight In the polymerization of propylene, the procedures of Example 1 are repeated. Results thus obtained are shown in Table-l .

Example 5 The procedures of Example 1 are repeated except that reaction with titanium tetrachloride is effected at 1 OO"C to prepare a catalyst component. The titanium content in the solids seperated is 3.12% by weight. In the polymerization of propylene, the procedures of Example 1 are repeated. Results thus obtained are shown inTable-1.

Exampte6 The procedures of Example 1 are repeated except that 2.0 g of dibutylphth alate instead of dipropylphthalate is usedto prepare a catalyst component.

The titanium content in the solids seperated is 2.91% by weight. In the polymerization of propylene, the procedures of Example 1 are repeated. Results thus obtained are shown in Table-1.

Example 7 The procedures of Example 1 are repeated except that 2.0 g ofdiamylphthalate instead of dipropylphthalate is used to prepare a catalyst component.

The titanium content in the solids seperated is 3.70% by weight In the polymerization of propylene, the procedures of Example 1 are repeated. Resultsthus obtained are shown in Table-l.

Example8 The procedures of Example 1 are repeated except that magnesium laurate instead of magnesium stearate is used to prepare a catalyst component. The titanium content in the solids separated is 3.52% by weight. In the polymerization of propylene, the procedures of Example 1 are repeated. Results thus obtained are shown in Table-1.

Example 9 The procedures of Example 1 are repeated except that carbon tetrachloride instead of methylene dich chloride is used to prepare a catalyst component. The titanium content in the solids separated is 3.48% by weight In the polymerization of propylene, the procedures of Example 1 are repeated. Results thus obtained are shown inTable-l.

Example 10 The procedures of Example 1 are repeated except that chloroform instead of methylene dichloride is used to prepare a catalyst component. The titanium content in the solids seperated is 3.61% by weight. In the polymerization of propylene, the procedures of Example 1 are repeated. Results thus obtained are shown in Table-1.

Example 11 To a 100 ml round flask fitted with a stirrer and thoroughly purged with nitrogen are charged 5 g of diethoxymagnesium and 50 ml of methylene dichlor ide to form a suspension followed bystirring for 1 hour under reflux. Separatelytherefrom, to a 500 ml round flask fitted with a stirrer and thoroughly purged with nitrogen are charged 5 g of magnesium stearate, 1.5 g of dipropylphthalate and 200 ml of TiCl4 to be reacted with agitation at room temperature for one hour. Thereafter, the former suspension is injected into the latter reaction mixturefollowed by heating to 90 Cfor allowing to reactwith agitation atthe elevated temperature for 2 hours. Thereafter the procedures of Example 1 are repeated to prepare a catalyst component. Thetitanium content in the solids separated is 3.50% weight In the polymerization of propylene, procedures of Example 1 are repeated. Results thus obtained are shown in Table-1.

Example 12 (Preparation of catalyst component) To a 200 ml round flaskfitted with a stirrer and thoroughly purged with nitrogen are charged 10g of magnesium stearate, 1.2 g of dibutylphthalate, and 50 ml of methylene chloride to form a suspension followed by stirring for 1 hour under reflux.The suspension is then injected into 200 ml of TiC4 at room temperature in a 500 ml round flaskfitted with a stirrerfollowed by heating up to 80 C for reacting with agitation at thattemperature for 2 hours. After the completion of the reaction, a reaction product is washed 10 times with 200 ml of dehydrated nheptane at 40"C, and 200 ml offresh titanium tetrachloride is added thereto for reacting with agitation at800Cfor2 hours.

The procedures of Example 1 are repeated to prepare a catalyst component The titanium content in the solids seperated is 2.77% by weight.

In the polymerization of propylene, the procedures of Example 1 are repeated except that 0.2 mg as titanium atom ofthe catalyst component is added thereto. Results thus obtained are shown in Table-1.

Example 13 The procedures of Example 12 are repeated except thatpolymerization reaction is effected for 6 hours.

Results thus obtained are shown in Table-l .

Example 14 The procedures of Example 12 are repeated except that 25ml of methylene dichtoride is used to prepare a catalystcomponent. The titanium content in the solids separated is 2.62% by weight.

In the polymerization of propylene, the procedures of Example 1Zare repeated. Resultsthusobtained are shown in Table-i.

Example 75 The procedures of Example 12 are repeated except that carbon tetrachloride in place of methylene dichloride is used to prepare a catalystcomponent The titanium content in the solids separated is 2.86% by weight.

In the polymerization of propylene, the procedures of Example 12 are repeated. Results thus obtained are shown in Table-1.

Example 16 The procedures of Example 12 are repeated except that reaction with titanium tetrachloride is effected at 650CSo prepare a catalyst component. The titanium content in the solids seperated is 3.01% by weight.

Irsthe polymerization of propylene, the procedures of Example 12 are repeated. Results thus obtained are shawn in Table-i.

Example 17 The procedures of Example 12 are repeated except that 1.2 g of dipropylphthalate is used to prepare a catalyst component. The titanium content in the solids separated is 2.97% byweight.

In the polymerization of propylene, the procedures of Example 12 are repeated. Results thus obtained are shown in Table-1.

Example 18 The procedures of Example 1 are repeated except that magnesium stearate is not used to prepare a catalyst component. The titanium content in the solidssepernted is 4.01% by weight.

In the polymerization of propylene, the procedures of Example 1 are repeated. The bulk density of the produced polymer is 0.38. Results thus obtained are shown in Table-l.

Example 19 The procedures of Example 18 are repeated except that polymerization reaction is effectedfor 6 hours.

The bulk density ofthe produced polymer is 0.39.

Resultsthus obtained are shown in Table-l .

Example 20 The procedures of Example 18 are repeated except that 25 ml of methylene dichloride is used to prepare a catalyst component. The titanium content in the solids separated is 3.92% byweight.

In the polymerization of propylene, the procedures of Example 18 are repeated. The bulk density of the produced polymer is 0.39. Results thus obtained are shown in Table-l.

Example 21 The procedures of Example 18 are repeated except that carbon tetrachloride in place of methylene dich loride is used to prepare a catalyst component.

The titanium content in the solids separated is 3.71% by weight.

In the polymerization of propylene, the procedures of Example 18 are repeated. The bulk density of the produced polymer is 0.38. Results thus obtained are shown in Table-l.

Example 22 The procedures of Example 18 are repeated except that chloroform in place of methylene dichloride is used to prepare a catalyst component. The titanium content in the solids separated is 3.86% by weight.

In the polymerization of propylene, the procedures of Example 18 are repeated. The bulk density of the produced polymer is 0.37. Results thus obtained are shown in Table-l.

Example 23 The procedures of Example 18 are repeated except that reaction with titanium tetrachloride is effected at 100 C to prepare a catalyst component. The titanium content in the solids separated is 3.36% by weight.

In the polymerization of propylene, the procedures of Example 18 are repeated. The bulk density of the produced polymer is 0.37. Results thus obtained are shown in Table-l.

Example 24 The procedures of Example 18 are repeated except that the suspension is injected into titanium tetrach chloride at 00C to prepare a catalyst component. The titanium content in the solids separated is 4.11 % by weight.

In the polymerization of propylene, the procedures of Example 18 are repeated. The bulk density of the produced polymer is 0.39. Results thus obtained are shown in Table-l.

Example 25 The procedures of Example 18 are repeated except that 1.2 g of dipropylphthalate is used to prepare a catalyst component. The titanium content in the solids separated is 3.64% by weight.

In the polymerization of propylene, the procedures of Example 18 are repeated except that 64 mg of phenyltriethoxysilane is used. The bulk density of the produced polymer is 0.37. Results thus obtained are shown in Table-l.

Example 26 The procedures of Example 18 are repeated except that 2.0 9 ofdibutylphthalatein place of dipropy lphthafate is usedto prepare a catalyst component.

The titanium content in the solids seperated is 3.66% by weight.

In the polymerization of propylene, the procedures of Example 18 are repeated. The bulk density of the produced polymer is 0.37. Results thus obtained are shown inTable-1.

Example 27 The procedures of Example 18 are repeated except that2.0 g ofdiamylphthalate in place of dipropylphthalate is used to prepare a catalyst component.

The titanium content in the solids seperated is 4.19% by weight.

In the polmerization of propylene, the procedures of Example 18 are repeated. The bulk density ofthe produced polymer is 0.37. Results thus obtained are shown in Table-1.

Comparative Example 1 (Preparation of catalyst component) 100 g of MgCl2 and 31.5 g of ethyl benzoate are copulverized under an atmosphere of nitrogen for 18 hours. 100 g of the copulverized product is charged into a 2000 ml glass flask under an atmosphere of nitrogen, and 500 ml of TiCI4is is added thereto to be reacted with agitation at 650C for 2 hours. After the completion ofthe reaction, the reaction mixture is cooled down to 40 C and left at rest for removing the resulting supernatant liquid by decanting.

Awashing procedure with 1000 ml of n-heptane is repeated until no chlorine is detected in the n-heptane afterwashingto completethewashing procedure and to obtain a catalyst component. The catalyst component thus obtained is subjected to solid-liquid separation procedure with the result that the titanium content in the solids thus separated is measured to be 1.28% weight In the polymerization of propylene, the procedures of Example 1 are repeated except that 1.0 mg as titanium atom ofthe catalyst component is added thereto. The bulk density of the produced polymer is 0.30. Results thus obtained are shown in Table-1.

Comparative Example 2 The procedures of Example 1 are repeated except that 2.0 ml of ethyl benzoate in place of dipropylphthalate is used to prepare a catalyst component.

Thetitanium content in the solids separated is 3.83% by weight.

In the polymerization of propylene, the procedures of Example 1 are repeatedexceptthat 137 mg of ethyl p-toluate and 0.5 mg as titanium atom of the catalyst component are used. The bulk density ofthe produced polymer is 0.32. Results thus obtained are shown in Table-1.

Table-l

Examples 1 2 3 4 5 6 7 8 9 lss Amount of polymer soluble in the solvent used in polymerization 6.1 8.4 6.8 6.4 6.2 6.9 6.2 7.2 6.0 7.0 Amount of solid polymer 226 314 248 241 253 276 220 240 227 239 (B) g Amount of polymer insoluble in boiling 223 310 244 238 250 272 216 236 223 236 n-heptane Polymerization activity per unit weight of 29900 41500 30100 29800 27000 27500 27900 29000 27000 29600 catalyst component 0 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 95.7 95.9 (F) (%) Chlorine content in the produced polymer 18 13 18 18 21 20 20 19 20 18 (G) ppm Melt index of the produced polymer 26.5 29.3 22.1 23.0 15.1 17.2 12.6 26.1 27.3 21.6 (H) Table-l (continued)

Examples 11 12 13 14 15 16 17 18 | 19 20 Amount of polymer soluble in the solvent 6.8 5.9 8.2 6.0 4.8 4.3 4.8 5.8 8.1 6.0 used in polymerization A Amount of solid polymer 243 210 294 220 196 190 192 219 307 211 (B) g Amount of polymer insoluble in boiling 240 207 290 217 193 187 189 216 303 208 n-heptane (C) g Polymerization aetivity ~ . ~~ ~ per unit weight of 29100 29900 41860 29620 28730 29260 29240 30050 42130 28370 catalyst component Yield of crystalline polymer 98.8 98.6 98.6 98.6 98.5 98.4 98.4 98.6 98.7 98.6 (E) (X) Overall yield of crystallne polymer 96.1 95.9 96.0 96.1 96.2 96.0 96.1 96.2 95.9 (F) (%) Chlorine content in the produced polymer 19 18 13 | 19 | 19 19 19 18 13 20 (E) ppm Melt index of the produced polymer 26.0 21.6 23.6 31.3 25.9 31.9 31.2 33.6 30.3 (H) Table-l (continued)

Comparative Examples Examples 21 | 22 | 23 | 24 1 25 1 26 | 27 1 1 2 Amount of polymer soluble in the solvent used in polymerization (A) g Amount of solid polymer 228 229 255 220 250 235 195 372 336 (B) g Amount of polymer insoluble in boiling 224 226 252 217 246 232 192 352 325 n-heptane (C) g Polymerization activity per unit weight of 28920 30350 29270 30960 31200 29460 28040 4860 26400 catalyst component 0 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 95,8 96,4 96,0 95,7 96,0 95,6 92,8 94,6 (F) (%) Chlorine content in the produced polymer 19 18 19 18 17 19 20 138 22 (G) ppm Melt index of the produced polymer 31.6 29.2 22.3 40.1 29.1 28.6 22.6 3.1 6.9 (H)

Claims (26)

1. A catalyst component (A) for use in polymeriza tion of olefins obtained by a process comprising contacting (a) a fatty acid salt of magnesium and/or (b) dialkoxymagnesium, (c) mono or diester of an aromatic dicarboxylic acid, (d) a halogenated hydro carbon, and (e) a titanium halide of the general formula: TiX4, wherein X represents a halogen atom, said catalyst component being for use in combination with (B) a silicon compound represented by the general formula: SiRrn(OR')4.rn, wherein R is hydrogen, alkyl group, oraryl group, R' is alkyl group or aryl group, and m is represented as O # m S 4, and with (C) an organoaluminium compound.

2. Acatalystcomponent according to claim 1, wherein said catalyst component is obtained by a process which comprises suspending the ingredients (a) and (b) into the ingredient (d), and adding a resulting suspension to the ingredient (e)for reaction, the ingredient (c) being present in at least one of the stages in the course of the process.

3. Acatalystcomponent according to claim 1, wherein said catalyst component is obtained by a process which comprises suspending the ingredient (a) into the ingredient (d), and adding a resulting suspension to the ingredient (e) containing the ingredient (b) for reaction, the ingredient (c) being present in at least one ofthe stages in the course of the process.

4. Acatalystcomponent according to claim 1,said catalyst component is obtained by a process which comprises suspending the ingredient (b) into the ingredient (d), and adding a resulting suspension to the ingredient (e) containing the ingredient (a) for reaction,the ingredient (c) being present in at least one ofthe stages in the course of the process.

5. Acatalystcomponent according to claim 1, wherein said catalyst component is obtained by a process which comprises suspending the ingredient (a) into the ingredient (d), and adding a resulting suspension to the ingredient (e) for reaction, the ingredient (c) being present in at least one of the stages in the course of the process.

6. Acatalystcomponent according to claim 1, wherein said catalyst component is obtained by a process which comprises suspending the ingredient (b) into the ingredient (d), and adding a resulting suspension to the ingredient (e) for reaction,the ingredient (c) being present in at least one ofthe stages in the course ofthe process.

7. A catalyst component according to claim 1,2,3, 4 or 5, wherein said fatty acid salt of magnesium is saturated fatty acid salt of magnesium.

8. Acatalystcomponentaccording to claim 7, wherein said saturated fatty acid salt of magnesium is selected from magnesium stearate, magnesium octanoate, magnesium decanoate and magnesium laurate.

9. A catalyst component according to claim 1,2,3, 4or6,wherein dialkoxymagnesium is selected from diethoxymagnesium and dipropoxymagnesium.

10. A catalyst component according to any pre ceding claim wherein mono ordiesterofaromatic dicarboxylic acid is selected from mono or diester of phthalic acid orterephthalic acid.

11. A catalyst component according to claim 10, wherein mono or diester of phthalic acid ortereph thalic acid is selected from dimethylphthalate, dimth- ylterephthalate, diethylphthalate, diethylterephtha late, dipropylphthalate, dipropylterephthalate, dibutylphthalate, dibutylterephthalate, diisobuty Iphthalate, diamylphthalate, diisoamylphthalate, ethylbutylphthalate, ethylisobutylphthalate and ethylprnpylphthalate.

12. A catalyst component according to any preceding claim wherein said halogenated hydrocarbon is selected from chlorides of aromatic or aliphatic hydrocarbon in the liquid state at room temperature.

13. A catalyst component according to any of claims 1 to 11, wherein said halogenated hydrocarbons is selected from chlorobenzene, benzylchloride, propylchloride, butylchloride, dichloroethane,trich- loroethane, carbon tetrachloride, chloroform and methylene dichloride.

14. A catalyst component according to any preceding claim wherein said titanium halide is titaniumtetrachloride.

15. Acatalystcomponent according to any preceding claim for use with a said silicon compound selected from phenyl- and alkyl-alkoxysilane.

16. A catalyst component according to any preceding claim for use with a said organoaluminium compound selected from triethylaluminium and triisobutylaluminium.

17. Acatalyst component according to any preceding claim for homopolymerization orcopolymerization of ethylene, propylene or l-butene.

18. A catalyst for the polymerization of olefins comprising: (A) a catalyst component obtained by a process comprising contacting (a) a fattyy acid salt of magnesium and/or (b) dialkoxymagnesium, (c) mono ordiesterofan aromatic dicarboxylic acid, (d) a halogenated hydrocarbon, and (e) a titanium halide ofthe general formula: TiX4, wherein X represents a halogen atom, (B) a silicon compound represented by the general formula: SIR,(OR')d,, wherein R is hydrogen,alkyl group or aryl group, R' isalkyl grouporaryl group, and m is represented as O S m 4, and (C) an organoaluminium compound.

19. A catalyst according to claim 18, wherein said catalyst component (A) is selected from the catalyst components claimed in claims 2to 14.

20. Acatalystaccordingto claim 18 or 19 wherein said silicon compound is selected from phenyl- and alkyl-alkoxysilane.

21. Acatalystaccordingto any of claims 18to20 wherein said organoaluminium compound is selected from triethylaluminium and triisobutylaluminium.

22. Acatalyst according to any of claims 18 to 21 for use in homopolymerization or compolymerization of olefins selected from ethylene, propylene and l-butene.

23. A catalyst ortitanium-containing catalyst component substantially as any herein described and exemplified in any of examples 1 to 27.

24. A process for polymerization of an olefin employing a catalyst or titanium-containing catalyst component according to any preceding claim.

25. A process for polymerization of an olefin substantially as any herein described and exemplified in any of examples 1 to 27.

26. A polymer produced by a process according to claim 24 or 25.