CA1153355A - Solid titanium catalyst component for production of an olefin polymer or copolymer - Google Patents
Solid titanium catalyst component for production of an olefin polymer or copolymerInfo
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- CA1153355A CA1153355A CA000349576A CA349576A CA1153355A CA 1153355 A CA1153355 A CA 1153355A CA 000349576 A CA000349576 A CA 000349576A CA 349576 A CA349576 A CA 349576A CA 1153355 A CA1153355 A CA 1153355A
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- catalyst component
- titanium
- titanium catalyst
- component
- electron donor
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- G—PHYSICS
- G09—EDUCATION; CRYPTOGRAPHY; DISPLAY; ADVERTISING; SEALS
- G09G—ARRANGEMENTS OR CIRCUITS FOR CONTROL OF INDICATING DEVICES USING STATIC MEANS TO PRESENT VARIABLE INFORMATION
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- G09G5/02—Control arrangements or circuits for visual indicators common to cathode-ray tube indicators and other visual indicators characterised by the way in which colour is displayed
- G09G5/024—Control arrangements or circuits for visual indicators common to cathode-ray tube indicators and other visual indicators characterised by the way in which colour is displayed using colour registers, e.g. to control background, foreground, surface filling
Abstract
ABSTRACT OF THE DISCLOSURE
A solid titanium catalyst component for the pro-duction of olefin polymers or copolymers. comprising tita-nium, magnesium,halogen and an electron donor as essential ingredients, said component further comprising an inert liquid hydrocarbon in an amount of, based on the weight of said component. of about 1 to about 10% when said com-ponent has a uniformity coefficient of at least 4, and about 1 to about 25% when said component has a uniformi-ty coefficient of less than 4.
A solid titanium catalyst component for the pro-duction of olefin polymers or copolymers. comprising tita-nium, magnesium,halogen and an electron donor as essential ingredients, said component further comprising an inert liquid hydrocarbon in an amount of, based on the weight of said component. of about 1 to about 10% when said com-ponent has a uniformity coefficient of at least 4, and about 1 to about 25% when said component has a uniformi-ty coefficient of less than 4.
Description
" llS;~3S~
SOLID TITANIUM CATALYST COMPONENT FOR PRODUC-TION OF AN OLEFIN POLYMER OR COPOLYMER
This invention relates to an improved solid titanium catalyst compon-ent which exhibits superior performance with good reproducibility when used in producing an olefin polymer or copolymer ~sometimes generically referred to as an olefin polymer in this application~ having a high bulk density and high stereospecificity and a low content of an undesirable fine powdery polymer.
More specifically, this invention relates to a solid titanium catalyst component for the production of olefin polymers or copolymers, comprising titan-ium, magnesiumJ halogen and an electron donor as essential ingredients, said component further comprising about 1 to about 10%, based on the total weight of said component, of an inert liquid hydrocarbon.
It is well known, as disclosed in many publications to be exemplified hereinbelow, that a solid titanium catalyst component containing titanium, mag-nesium, halogen and an electron donor as essential ingredients, when combined ,,jl ~', with an organometallic compound of a metal of Groups I to III of the Mendeleejeff's periodic table, is useful in the homopolymerization or copolymer-ization of olefins, especially alpha-olefins having at least 3 carbon atoms; or : the copolymerization of alpha-olefins having at least 3 carbon atoms and ethyl-ene with or withol~t diolefins to provide highly stereospecifit ''';
-'.;' ' :
. ' , . .
, - llS33S5 polymers with high activity.
~ The bulk densities or stereospecificity indices of polymers obtained ; by polymerizing olefins with such catalysts by various polymerization methods such as solution polymerization, slurry polymerization or vapor-phase polymeriz-ation somewhat differ from each other, and the catalytic activities of such cat-' alysts also differ from each other slightly. In many cases, the solid titanium catalyst component of high performance can be obtained by treating the resulting solid carrier with a titanium compound in the liquid phase in the final stage of preparation of the catalyst component.
According to the conventional practice, the solid titanium catalyst component so obtained is well washed with, for example, an inert liquid hydro-carbon, and stored as a slurry in the inert hydrocarbon or as a dried product until it is used for polymeri~zation.
Noting that the performances of solid titanium catalyst components prepared from the same ingredients by the same means of preparation frequently differ considerably from batch to batch, the present inventors worked extensive-ly to find the cause of difference.
Consequently, the present inventors have found that by drying the sol-id titanium catalyst component so that a specified amount of the aforesaid liq-uid inert hydrocarbon remains therein, the final solid titanium catalyst compon-ent containing the specified amount of the inert liquid hydrocarbon can afford an olefin polymer having a high bulk density, high stereospecificity and a re-duced content of an undesirable fine powdery polymer, and that the reproducibil-ity of such a performance of the catalyst component is good, and marked indus-trial improvements can be achieved.
This fact was unexpected because it was not known previously that the inert liquid hydrocarbon which the solid titanium catalyst component may contain constitutes a factor which exerts a significant effect
SOLID TITANIUM CATALYST COMPONENT FOR PRODUC-TION OF AN OLEFIN POLYMER OR COPOLYMER
This invention relates to an improved solid titanium catalyst compon-ent which exhibits superior performance with good reproducibility when used in producing an olefin polymer or copolymer ~sometimes generically referred to as an olefin polymer in this application~ having a high bulk density and high stereospecificity and a low content of an undesirable fine powdery polymer.
More specifically, this invention relates to a solid titanium catalyst component for the production of olefin polymers or copolymers, comprising titan-ium, magnesiumJ halogen and an electron donor as essential ingredients, said component further comprising about 1 to about 10%, based on the total weight of said component, of an inert liquid hydrocarbon.
It is well known, as disclosed in many publications to be exemplified hereinbelow, that a solid titanium catalyst component containing titanium, mag-nesium, halogen and an electron donor as essential ingredients, when combined ,,jl ~', with an organometallic compound of a metal of Groups I to III of the Mendeleejeff's periodic table, is useful in the homopolymerization or copolymer-ization of olefins, especially alpha-olefins having at least 3 carbon atoms; or : the copolymerization of alpha-olefins having at least 3 carbon atoms and ethyl-ene with or withol~t diolefins to provide highly stereospecifit ''';
-'.;' ' :
. ' , . .
, - llS33S5 polymers with high activity.
~ The bulk densities or stereospecificity indices of polymers obtained ; by polymerizing olefins with such catalysts by various polymerization methods such as solution polymerization, slurry polymerization or vapor-phase polymeriz-ation somewhat differ from each other, and the catalytic activities of such cat-' alysts also differ from each other slightly. In many cases, the solid titanium catalyst component of high performance can be obtained by treating the resulting solid carrier with a titanium compound in the liquid phase in the final stage of preparation of the catalyst component.
According to the conventional practice, the solid titanium catalyst component so obtained is well washed with, for example, an inert liquid hydro-carbon, and stored as a slurry in the inert hydrocarbon or as a dried product until it is used for polymeri~zation.
Noting that the performances of solid titanium catalyst components prepared from the same ingredients by the same means of preparation frequently differ considerably from batch to batch, the present inventors worked extensive-ly to find the cause of difference.
Consequently, the present inventors have found that by drying the sol-id titanium catalyst component so that a specified amount of the aforesaid liq-uid inert hydrocarbon remains therein, the final solid titanium catalyst compon-ent containing the specified amount of the inert liquid hydrocarbon can afford an olefin polymer having a high bulk density, high stereospecificity and a re-duced content of an undesirable fine powdery polymer, and that the reproducibil-ity of such a performance of the catalyst component is good, and marked indus-trial improvements can be achieved.
This fact was unexpected because it was not known previously that the inert liquid hydrocarbon which the solid titanium catalyst component may contain constitutes a factor which exerts a significant effect
- 2 -. ~ . .
. .:
on the aforesaid properties of the catalyst component.
` It has also been found that the aforesaid improvements can be achieved by adjusting the amount of the inert liquid hydrocarbon to about 1 to about 10 based on the weight of the solid titanium catalyst component when the catalyst component has a uniformity coefficient of at least 4, and to about 1 to about 25% on the same basis when the catalyst component has a uniformity coefficient of less than 4; and that as shown in comparative tests given hereinbelow, if the titanium catalyst component is dried to an extent such that the amount of the - hydrocarbon retained exceeds the aforesaid lower limit, stereospecificity is re-duced, or when drying is omitted or is insufficient with the amount of the re-; tained hydrocarbon exceeding the upper limit, the resulting polymer has a low bulk density and a large content of a fine powdery polymer.
It was quite unexpected that in spite of the fact that the aforesaid inert liquid hydrocarbon may be the same as the liquid hydrocarbon used in poly-merization, the aforesaid improvements can be achieved by using the solid titan-ium catalyst component containing the hydrocarbon in the above-specified amount, ` and it is difficult to achieve these improvements when the amount of the hydro-- carbon falls outside the specified range.
It is an object of this invention therefore to provide a solid titan-ium catalyst component for olefin polymerization, which can achieve the aforesaidimprovements.
The above and other objects and advantages of this invention will be-come more apparent from the following description.
The solid titanium catalyst component of this invention for use in olefin polymerization contains titanium, magnesium, halogen and an electron do-nor as essential ingredients, and further comprises an inert liquid hydrocarbon in an amount, based on the weight of the titanium catalyst component, of about 1 to about 10% when the component has a ~niformity coefficient of at , . .
,'' :
.
.:
1~533S5 least 4, and about 1 to about 25% when the component has uniformity coefficient of less than 4~
The solid titanium component of the invention may be prepared by (a) intimately contacting (i) a magnesium compound or magnesium metal, (ii) a titanium compound wherein elther the titanium compound or the magnesium compound contains a halogen and (iii) an electron doner in such a manner that the resulting titanium catalyst component contains halogen, titanium, magnesium and the electron donor, (b) washing the thus obtained titanium catalyst component with an inert liquid hydrocarbon, and (c) drying the wet component so that the amount of the inert liquid hydrocarbon in the titanium catalyst component reaches, based on the weight of the compon-ent, about 1 to about 10% when the component has a uniformity coefficient of at least 4, or about 1 to about 25~ when the component has a uniformity coefficient of less than 4~
The amount of the inert liquid hydrocarbon in the titanium catalyst component of this invention is determined by gas chromatography after a predetermined amount of the titanium catalyst component is decomposed with a large amount of alcohol~
The uniformiLy coefficient of the titanium catalyst component in this invention is determined by the photo-extinction method~ Photo-extinction method is described in Fine Particle Measurement, published by The Macmillan Company, New York, P 75.
The titanium catalyst component is diluted with a liquid hydrocarbon to a concentration of about 0.3 9/1~ The resulting suspension is put into a measuring cell~ Light from a slit is applied to the cell, and the intensity of the light which has been transmitted throuah the suspension is continuously measured while particles of the catalyst component are precipitating in the suspension. From the results, the particle size distribution of the catalyst component is determined. An integral curve of the particle size distribution is drawn by plotting the weight proportions on the ordinate and the particle diameters on the abscissa on the basis of the partlcle size distribution so determined. The uniformity coe~ficient of the titanium catalyst component is defined as the ratio of the particle diameter corresponding to a weight of 10% to the particle diameter corresponding to a weight of 60% in the graph.
Uniformity coefficient is described in Chemical Engineering, October 13, 9 (1969).
The solid titanium catalyst component of this invention comprising titanium, magnesium halogen and an electron donor as essential ingredients can be obtained by selecting a magnesium compound with or withaut halogen, or magnesium metal, a titanium compound with or without halogen, and an electron donor such that the resulting titanium catalyst component contains halogen, and intimately contacting the selected ingredients by such a means as heating or co-pulverization. The halogen/titanium mole - ~a -' ratio of the resulting catalyst component preferably exceeds about 4, and the catalyst component does not substantially permit liberation of the titanium com-pound by such a simple means as washing with hexane. The exac~ chcmical struc-ture of the resulting catalyst component is not known, but it is presumed that the magnesium atom and the titanium atom are firmly bonded to each other having halogen in common. If desired, the solid titanium catalyst component may fur-ther comprise other metal atoms or elements such as aluminum, silicon, tin, boron, germanium, calcium, zinc and phosphorus, and functional groups. It may further include organic or inorganic inert solid diluents such as LiCl, CaCC3, 2 2 3' rC12' B203, Na2SC4, A1203, SiO2, TiC2, NaB407, Ca3(PC ) CaS04, A12(SC4)3, CaC12, ZnC12, polyethylene, polypropylene, and polystyrene.
Organic acid esters or ethers are preferred as the electron donor.
Advantageously, the solid titanium catalyst component of this inven-tion has a halogen/titanium mole ratio pf more than 4, preferably at least about 5, more preferably at least about 8, for example up to about 100, a magnesium/
titanium mole ratio of at least about 3, preferably about 5 to about 50, an electron donor/titanium mole ratio of from about 0.2 to about 6, preferably from about 0.4 to about 3, more preferably from about 0.3 to about 2, and a specific surface area of at least about 3 m2/g, preferably at least about 40 m2/g, more preferably at least about 100 m /g. Desirably, the X-ray spectrum of the com-plex shows it to be amorphous irrespective of the type of the starting magnesium compound, or to be much more amorphous than commercially available magnesium di-halides.
Various means are known to form the solid titanium catalyst component which contains titanium, magnesium, halogen and an electron donor before con-trolling its inert liquid hydrocarbon content to the specified range, and any of such means can be used in this invention. Some of such methods for the prep-1153;~55 aration of the solld titanium catalyst componont are disclosed, for exampl0, inJapanese Laid-Open Patent Publications Nos. 108385/75 (corresponding to west German DOS No. 2,504,036), 126590/75 (corresponding to United States Patent No.
4,069,169), 20297/76 (corresponding to west German DOS 2504036), 28189/76 (cor-responding to United States Patent No. 4,076,924), 64586/76, 92885/76, 127185/76, 136625/76, 87489/77 ~corresponding to west German DOS No. 2,701,647), 100596/77, 10459/77 ~corresponding to British Patent No. 1,540,323), 147688/77 ~correspond-ing to west German DOS No. 2,724,971), 151691/77 ~corresponding to west German DOS No. 2,643,143), 2580/78 ~corresponding to west German DOS No. 2,729,196), 21093/78 (corresponding to west German DOS No. 2,735,672), 30681/78 (correspond-ing to west German DOS No. 2,739,608), 39991/78 ~corresponding to west German DOS No. 2,743,415), and 40098/78 ~corresponding to west German DOS No. 2,743,366).
Some specific embodiments of these means are described below.
(1) A magnesium compound, preferably a magnesium compound expressed by the formula Mg(OR) X2 (in which R represents a hydrocarbon group, for example an alkyl group having 1 to 18 carbon atoms, a cycloalkyl group having 5 to 18 carbon atoms or an aryl group having 6 to 18 carbon atoms, n is a number repre-sented by O<n<2, and X represents a halogen atom, preferably chlorine, bromine or iodine), especially preferably magnesium chloride, is reacted with an elec-tron donor or an adduct of the electron donor with a halogen-containing alum-inum compound (the halogen-containing titanium compound and the electron donor may form an adduct in advance, or the electron donor may form a complex with such a halogen-containing aluminum compound as an aluminum trihalide); or these compounds are strongly pulverized mechanically in the absence or presence of a small amount of a hydrocarbon, a silicon compound, an aluminum compound, an ~j llS3355 alcohol, a phenol, etc. The resulting reactlon product or pulvcrizcd product, optionally treated further with a silicon compound, an organoaluminum compound, etc. with or without an alcohol, is then further reacted with a titanium halide, preferably titanium tetrachloride.
~ 2) A halogen-containing magnesium compound, preFcrably magncsium chloride, is reacted with an active hydrogen-containing electron donor such as alcohols or phenols and an electron donor free from active hydrogen such as an organic acid ester or an organic acid halide, then with an organoaluminum com-pound or a silicon halide, and further with a titanium compound, preferably titanium tetrachloride.
. .:
on the aforesaid properties of the catalyst component.
` It has also been found that the aforesaid improvements can be achieved by adjusting the amount of the inert liquid hydrocarbon to about 1 to about 10 based on the weight of the solid titanium catalyst component when the catalyst component has a uniformity coefficient of at least 4, and to about 1 to about 25% on the same basis when the catalyst component has a uniformity coefficient of less than 4; and that as shown in comparative tests given hereinbelow, if the titanium catalyst component is dried to an extent such that the amount of the - hydrocarbon retained exceeds the aforesaid lower limit, stereospecificity is re-duced, or when drying is omitted or is insufficient with the amount of the re-; tained hydrocarbon exceeding the upper limit, the resulting polymer has a low bulk density and a large content of a fine powdery polymer.
It was quite unexpected that in spite of the fact that the aforesaid inert liquid hydrocarbon may be the same as the liquid hydrocarbon used in poly-merization, the aforesaid improvements can be achieved by using the solid titan-ium catalyst component containing the hydrocarbon in the above-specified amount, ` and it is difficult to achieve these improvements when the amount of the hydro-- carbon falls outside the specified range.
It is an object of this invention therefore to provide a solid titan-ium catalyst component for olefin polymerization, which can achieve the aforesaidimprovements.
The above and other objects and advantages of this invention will be-come more apparent from the following description.
The solid titanium catalyst component of this invention for use in olefin polymerization contains titanium, magnesium, halogen and an electron do-nor as essential ingredients, and further comprises an inert liquid hydrocarbon in an amount, based on the weight of the titanium catalyst component, of about 1 to about 10% when the component has a ~niformity coefficient of at , . .
,'' :
.
.:
1~533S5 least 4, and about 1 to about 25% when the component has uniformity coefficient of less than 4~
The solid titanium component of the invention may be prepared by (a) intimately contacting (i) a magnesium compound or magnesium metal, (ii) a titanium compound wherein elther the titanium compound or the magnesium compound contains a halogen and (iii) an electron doner in such a manner that the resulting titanium catalyst component contains halogen, titanium, magnesium and the electron donor, (b) washing the thus obtained titanium catalyst component with an inert liquid hydrocarbon, and (c) drying the wet component so that the amount of the inert liquid hydrocarbon in the titanium catalyst component reaches, based on the weight of the compon-ent, about 1 to about 10% when the component has a uniformity coefficient of at least 4, or about 1 to about 25~ when the component has a uniformity coefficient of less than 4~
The amount of the inert liquid hydrocarbon in the titanium catalyst component of this invention is determined by gas chromatography after a predetermined amount of the titanium catalyst component is decomposed with a large amount of alcohol~
The uniformiLy coefficient of the titanium catalyst component in this invention is determined by the photo-extinction method~ Photo-extinction method is described in Fine Particle Measurement, published by The Macmillan Company, New York, P 75.
The titanium catalyst component is diluted with a liquid hydrocarbon to a concentration of about 0.3 9/1~ The resulting suspension is put into a measuring cell~ Light from a slit is applied to the cell, and the intensity of the light which has been transmitted throuah the suspension is continuously measured while particles of the catalyst component are precipitating in the suspension. From the results, the particle size distribution of the catalyst component is determined. An integral curve of the particle size distribution is drawn by plotting the weight proportions on the ordinate and the particle diameters on the abscissa on the basis of the partlcle size distribution so determined. The uniformity coe~ficient of the titanium catalyst component is defined as the ratio of the particle diameter corresponding to a weight of 10% to the particle diameter corresponding to a weight of 60% in the graph.
Uniformity coefficient is described in Chemical Engineering, October 13, 9 (1969).
The solid titanium catalyst component of this invention comprising titanium, magnesium halogen and an electron donor as essential ingredients can be obtained by selecting a magnesium compound with or withaut halogen, or magnesium metal, a titanium compound with or without halogen, and an electron donor such that the resulting titanium catalyst component contains halogen, and intimately contacting the selected ingredients by such a means as heating or co-pulverization. The halogen/titanium mole - ~a -' ratio of the resulting catalyst component preferably exceeds about 4, and the catalyst component does not substantially permit liberation of the titanium com-pound by such a simple means as washing with hexane. The exac~ chcmical struc-ture of the resulting catalyst component is not known, but it is presumed that the magnesium atom and the titanium atom are firmly bonded to each other having halogen in common. If desired, the solid titanium catalyst component may fur-ther comprise other metal atoms or elements such as aluminum, silicon, tin, boron, germanium, calcium, zinc and phosphorus, and functional groups. It may further include organic or inorganic inert solid diluents such as LiCl, CaCC3, 2 2 3' rC12' B203, Na2SC4, A1203, SiO2, TiC2, NaB407, Ca3(PC ) CaS04, A12(SC4)3, CaC12, ZnC12, polyethylene, polypropylene, and polystyrene.
Organic acid esters or ethers are preferred as the electron donor.
Advantageously, the solid titanium catalyst component of this inven-tion has a halogen/titanium mole ratio pf more than 4, preferably at least about 5, more preferably at least about 8, for example up to about 100, a magnesium/
titanium mole ratio of at least about 3, preferably about 5 to about 50, an electron donor/titanium mole ratio of from about 0.2 to about 6, preferably from about 0.4 to about 3, more preferably from about 0.3 to about 2, and a specific surface area of at least about 3 m2/g, preferably at least about 40 m2/g, more preferably at least about 100 m /g. Desirably, the X-ray spectrum of the com-plex shows it to be amorphous irrespective of the type of the starting magnesium compound, or to be much more amorphous than commercially available magnesium di-halides.
Various means are known to form the solid titanium catalyst component which contains titanium, magnesium, halogen and an electron donor before con-trolling its inert liquid hydrocarbon content to the specified range, and any of such means can be used in this invention. Some of such methods for the prep-1153;~55 aration of the solld titanium catalyst componont are disclosed, for exampl0, inJapanese Laid-Open Patent Publications Nos. 108385/75 (corresponding to west German DOS No. 2,504,036), 126590/75 (corresponding to United States Patent No.
4,069,169), 20297/76 (corresponding to west German DOS 2504036), 28189/76 (cor-responding to United States Patent No. 4,076,924), 64586/76, 92885/76, 127185/76, 136625/76, 87489/77 ~corresponding to west German DOS No. 2,701,647), 100596/77, 10459/77 ~corresponding to British Patent No. 1,540,323), 147688/77 ~correspond-ing to west German DOS No. 2,724,971), 151691/77 ~corresponding to west German DOS No. 2,643,143), 2580/78 ~corresponding to west German DOS No. 2,729,196), 21093/78 (corresponding to west German DOS No. 2,735,672), 30681/78 (correspond-ing to west German DOS No. 2,739,608), 39991/78 ~corresponding to west German DOS No. 2,743,415), and 40098/78 ~corresponding to west German DOS No. 2,743,366).
Some specific embodiments of these means are described below.
(1) A magnesium compound, preferably a magnesium compound expressed by the formula Mg(OR) X2 (in which R represents a hydrocarbon group, for example an alkyl group having 1 to 18 carbon atoms, a cycloalkyl group having 5 to 18 carbon atoms or an aryl group having 6 to 18 carbon atoms, n is a number repre-sented by O<n<2, and X represents a halogen atom, preferably chlorine, bromine or iodine), especially preferably magnesium chloride, is reacted with an elec-tron donor or an adduct of the electron donor with a halogen-containing alum-inum compound (the halogen-containing titanium compound and the electron donor may form an adduct in advance, or the electron donor may form a complex with such a halogen-containing aluminum compound as an aluminum trihalide); or these compounds are strongly pulverized mechanically in the absence or presence of a small amount of a hydrocarbon, a silicon compound, an aluminum compound, an ~j llS3355 alcohol, a phenol, etc. The resulting reactlon product or pulvcrizcd product, optionally treated further with a silicon compound, an organoaluminum compound, etc. with or without an alcohol, is then further reacted with a titanium halide, preferably titanium tetrachloride.
~ 2) A halogen-containing magnesium compound, preFcrably magncsium chloride, is reacted with an active hydrogen-containing electron donor such as alcohols or phenols and an electron donor free from active hydrogen such as an organic acid ester or an organic acid halide, then with an organoaluminum com-pound or a silicon halide, and further with a titanium compound, preferably titanium tetrachloride.
(3) The product obtained in embodiment (1) or (2) is reacted further with an electron donor and a titanium compound, preferably titanium tetrachlor-ide.
(4) The product obtained in embodiment (1) or ~2) is reacted further with an electron donor, a titanium compound, preferably titanium tetrachloride, and an organoaluminum compound.
(5) A compound containing an organic magnesium compound is treated with a compound having a functional group such as a hydroxyl, ester or carboxyl group or a halogen containing compound, and then treated with a titanium com-pound, preferably titanium tetrachloride, in the presence of an electron donor.
The solid titanium catalyst component that can be formed by known meth-ods can be purified by washing it with an inert liquid hydrocarbon. The term "inert hydrocarbon", as used in this application denotes a hydrocarbon which does not markedly degrade the performance of catalyst. Examples of such a hydro-carbon include aliphatic hydrocarbons such as n-pentane, isopentane, n-hexane, isohexane, n-heptane, n-octane, iso-octane, n-decane, n-dodecane, kerosene, and liquid paraffin; alicyclic hydrocarbons such as cyclopentane, .. ; i llS3355 methylcyclopentane, cyclohexane and methylcyclohexane; and aromatic hydro-carbons such as benzene, toluene, xylene and cymene. These hydrocarbons may be used as a mixture of at least two.
In order to obtaln a titanium catalyst component having a degree of uniformity of less than 4, it is preferred to use a method which comprises narrowing the particle size disbribution of a magnesium compound, and then reacting such a magnesium compound with a titanium compound which is liquid under the reaction conditions, or a method which comprises reacting a liquid magnesium compound and a liguid titanium compound under conditions that particles having a narrow particle size distribution are precipitated. For example, such a solid titanium catalyst component can be prepared by the techniques disclosed in Japanese Laid-Open Patent Publications Nos. 38590/77, 146292/78 and 41985/79, and U.S. Patent No. 4,315,874 (corresponding to Japanese Patent Applications Nos. 43002/79, 43003/79) and U.S. Patent No.
4,330,649 (corresponding to Japanese Patent Application No. 75582/79).
Several examples of such techniques are described below briefly.
(1) An oxygen-containing magnesium compound, or a complex of a magnsium compound and an electron donor, having a particle diameter of about 1 to about 200 microns and a uniformity coefficient of less than about 4, optionally pre-treated with an electron donor and/or a reagent such as an organoaluminum compound or halogen-containing silicon compound, is reacted with a titanium halide which is liquid under the reaction conditions, prefer-ably titanium tetrachloride.
(2) A magnesium compound in the liquid state having no reducing ability is reacted with a liquid titanium compound in the absence or presence of an electron donor to precipitate a titanium catalyst component having a particle diameter of about 1 to about 200 microns and a uniformity coefficient .~
liS3~55 of less than about 4.
(3) The product obtained in (2) above is - 8a -~15335S
reacted with a titanium compound.
~ 4) The product obtained in (1) or (2) is reacted with an electron do-nor and a titanium compound.
(5~ The product obtaincd in (1) or t2) is reucted with an electron do-nor, a titanium compound and an organoaluminum compound.
Examples of the magnesium compound used in the preparation of the titanium catalyst component having a uniformity coefficient of less than 4 in-clude magnesium oxide, magnesium hydroxide, hydrotalcite, carboxylic acid salts of magnesium, alkoxymagnesiums, aryloxymagnesiums, alkoxymagnesium halides, aryloxymagnesium halides, magnesium dihalides, and the reaction products between organic magnesium compounds and silanols, siloxanes, halosilanes, etc.
The solid titanium catalyst component of this invention can be ob-tained, for example, by drying the wet component formed in the aforesaid manner by washing with an inert liquid hydrocarbon. When the aforesaid component has a uniformity coefficient of at least 4, the final product can be obtained by dry-ing it such that the content of the inert liquid hydrocarbon is about 1 to about 10%, preferably about 1 to about 6%, based on the weight of the component.
If the aforesaid drying is omitted, or the drying resulted in a larger content of the inert liquid hydrocarbon than the specified upper limit, an ole-fin polymer obtained by, for example, slurry polymerization or vapor-phase poly-merization, does not have an increased bulk density, and the amount of a fine powdery polymer increases, and moreover, the reproducibility of the quality of the resulting polymer is poor. By drying the resulting titanium catalyst com-ponent such that its content of inert liquid hydrocarbon is within the specified range, there can be obtained a solid titanium catalyst component, which when used in the polymerization of olefins, can give a polymer having an increased bulk density with a reduced amount of a fine powdery polymer and a good reproduc-ibility of the quality of the resulting polymer. Eurthermore, the loss of the _ 9 _ , polymer decreases in block copolymerization in propylene polymerization, and a polymer of high quality can be produced. Moreover, the catalyst component is easier to transport or store. When the drying is carricd out such that the con~
tent of the inert liquid hydrocarbon decreases beyond the specified lower limit, the stereospecificity index of an olefin polymer obtained by the stereospecific polymerization of olefin using the resulting titanium catalyst component is re-duced.
The solid titanium catalyst component of this invention may be stored as such, preferably in an inert atmosphere, such as a nitrogen atmosphere, until it is used for polymerization. If desired, it may be again suspended in an inert liquid hydrocarbon and stored in this state. When it is stored for an excessive-ly long period of time, the effect of drying may be lost. Accordingly, it should be used for polymerization as early as possible, even when it is stored as sus-pended in an inert liquid hydrocarbon. For example, when the titanium catalyst component has been dried to such an extent that its content of the hydrocarbon is about 1 to about 6%, its performance does not change for about 10 days at room temperature. When the drying is done to such an extent that the content of the hydrocarbon is about 6 to about 10%, the performance of the resulting cata-lyst component begins to decrease when it is maintained at room temperature for about 2 days. In such a case, the catalyst component may be again suspended in the inert liquid hydrocarbon and again dried to adjust its content to the speci-fied range, before it is used for polymerization.
When the uniformity coefficient of the aforesaid catalyst component is less than 4, it is dried until the amount of the liquid hydrocarbon reaches about 1 to about 25%, preferably about 1 to about 20%, based on the weight of the component. When no drying is done, or the drying is insufficient so that the amount of the liquid hydrocarbon exceeds the specified upper limit, the cat-alyst particles are liable to undergo agglomeration during transportation or .
llS33SS
storage, and are difficult to discharge rom a catalyst reservoir. By drying the catalyst component to the specified extent, it can be more easily trans-ported or stored.
The drying treatment is carried out preferably under relatively mild temperature conditions. For exampleJ it is carried out at a temperature of not more than about 80C, preferably about OC to about 60C, in an a~mosphere of aninert gas. Temperatures in excess of about 80C tend to cause a reduction in polymerization activity in contrast to the case of performing the drying treat-ment at temperatures lower than about 80C. Accordingly, drying at temperatures lower than about 80 is preferred. On the other hand, too low a drying temper-ature, for example temperatures below about 0 C, is not practical because it will prolong the treating time to no advantage.
The drying time depends upon various operating conditions such as tem-perature. Drying is carried out until the content of the inert liquid hydro-carbon in the solid titanium catalyst component reaches the values within the specified range. Generally, the drying time is from about 15 minutes to about 100 hours, preferably from about 30 minutes to about 48 hours. The pressure maintained during the drying of the solid titanium catalyst component is not critical so long as it is lower than the saturated pressure of the liquid held in the catalyst component. For example, the drying can be carried out at atmos-s pheTic pressure or reduced pressure. If the drying temperature is as low as room temperature, it is advantageous to perform the drying under reduced pres-sure so as to promote removal of the inert liquid medium.
; Drying of the solid titanium catalyst component may be carried out in an atmosphere of an inert gas. The use of nitrogen is preferred for this pur-pose.
Drying of the solid titanium catalyst component in this invention may be carried out in an apparatus having a specification suitable for the opera-. .
.
1~5335S
tion, for example a moving bed dryer such as a horizontal stirred dryer, a rotary drum-type dryer or a vertical stirred dryer. A fixed bed dryer through which an inert gas flows may also be used, but the moving bed-type is advan-tageous because the drying time is shorter. Advantageously, the solid titanium catalyst component to be subjected to the drying step is moderately deprived of the inert liquid hydrocarbon before the drying treatment. Filtration, centri-fugation, precipitating separation using a siphon, etc. may be used to remove the hydrocarbon prior to the drying treatment.
The halogen which constitutes the solid titanium catalyst component ~, 10 of this invention is fluorine, chlorine, bromine, iodine or mixtures thereof.
Chlorine is preferred.
The electron donor used in the production of the solid titanium cat-alyst component includes, for example, oxygen-containing electron donors such as alcohols,-phenols, ketones, aldehydes, carboxylic acids, organic or inorganic acid esters, ethers, acid amides and acid anhydrides, and nitrogen-containing electron donors such as ammonia, amines, nitriles and isocyanates.
Specific examples of these electron donors are alcohols having 1 to 18 carbon atoms such as methanol, ethanol, propanol, pentanol, hexanol, octanol, dodecanol, octadecyl alcohol, benzyl alcohol, phenethyl alcohol, cumyl alcohol and isopropyl benzyl alcohol; phenols having 6 to 15 carbon atoms and optionally containing a lower alkyl group, such as phenol, cresol, xylenol, ethylphenol, propylphenol cumylphenol and naphthol; ketones having 3 to 15 carbon atoms such as acetone, methyl ethyl ketone, methyl isobutyl ketone, acetophenone and benzo-phenone; aldehydes having 2 to 15 carbon atoms such as acetaldehyde, benzalde-` hyd~, tolualdehyde and naphthoaldehyde; organic acid esters having 2 to 18 car-bon atoms such as methyl formate, methyl acetate, ethyl acetate, vinyl acetate, propyl acetate, octyl acetate, cyclohexyl acetate, ethyl propionate, methyl butyrate, ethyl valerate, methyl chloroacetate, ethyl dichloroacetate, methyl - 12 _ .
~ .. .
.
.' ' ~153355 methacrylate, ethyl crotonate, ethyl cyclohexanecarboxylate, methyl benzoate, ethyl benzoate, propyl benzoate, butyl benzoate, octyl benzoate, cyclohexyl benzoate, phenyl benzoate, benzyl benzoate, methyl toluate, ethyl toluate, amyl toluate, ethyl ethylbenzoate, methyl anisate, ethyl anisate, ethyl ethoxybenzo-ate, y-butyrolactone, ~-valerolactone, coumarine, phthalide and ethylene carbon-ate; inorganic acid esters such as ethyl silicate and ethylethoxysilane; acid halides such as acetyl chloride, benzyl chloride, toluoyl chloride and anisoyl chloride; ethers having 2 to 20 carbon atoms such as methyl ether, ethyl ether, isopropyl ether, butyl ether, amyl ether, tetrahydrofuran, anisole and diphenyl ether; acid amides such as acetamide, benzamide and toluamide; amines such as methylamine, ethylamine, diethylamine, tributylamine, piperidine, tribenzyl-amine, aniline, pyridine, picoline and tetramethyl ethylene diamine; and nit-riles such as acetonitrile, benzonitrile and tolunitrile. Two or more of these electron donors may be used in combination.
Preferred electron donors to be included in the titanium catalyst com-ponent as an essential ingredient are those not having active hydrogen, such as organic or inorganic acid esters, ethers, ketones, tertiary amines, acid halides "
and acid anhydrides. The organic acid esters and ethers are especially pre-ferred. Of these, aromatic carboxylic acid esters, and alkyl-containing ethers are most preferred. Typical examples of the preferred aromatic carboxylic acid esters include aromatic carboxylic acid esters having 8 to 18 carbon atoms, espe-cially lower alkyl or alkoxy esters of benzoic acid, lower alkyl benzoic acids - and lower alkoxybenzoic acids. Preferably, these lower alkyl or alkoxy esters ~ have l to 4 carbon atoms, especially 1 or 2 carbon atoms. Suitable alkyl-con-;~ taining ethers are those having 4 to 20 carbon atoms such as diisoamyl ether and dibutyl ether.
The solid titanium catalyst component for olefin polymerization in ac-cordance with this invention can be advantageously utilized for polymerization of .;
',, , ,-,,, , , ,,~ ~ . .
, , ... . . . . .
. .
. ~ ' . .
olefins when combined with organometallic compounds oE m0tals of Groups I to III
of the periodic table, especially organoaluminum compounds.
Organoaluminum compounds containing one Al-carbon bond at least in the molecule. Examples are ~i) organoaluminum compounds of the general formula RlmAl(OR2)nH Xq (wherein each of Rl and R2 represents a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms, for example, an alkyl, cycloalkyl or aryl group and may be identical or different, X represents halogen, m is a number represented by O<mc3, n is a number represented by Ocn<3, p is a number represented by Ocpc3, and q is a number represented by Ocp<3, with the proviso that m + n + p + q = 3); and (ii) complex alkylated products of metals of Group I and aluminum, as represented by the general formula MlAlR14 (wherein M represents Li, Na or K, and R is as defined above).
Examples of the organoaluminum compounds that fall within the category (i) include those of the general formula Rl Al~OR2)3 m wherein Rl and R are as defined above, and m is preferably a number represented by 1.5cm<3; those of the general formula R mAlX3 m wherein Rl is as defined above and X is halogen9 and m is preferably O<m<3; those of the general formula RlmAlH3 m wherein Rl is as de-fined above, and m is a number preferably a number represented by 2<m<3; and those of the general formula R mAl(OR )nXq wherein Rl and R are as defined above, X is halogen, O<mc3~ Ocn<3, Ocq<3, and m + n + q = 3.
Specific examples of the aluminum compounds (i) include trialkyl alum-inums such as triethyl aluminum and tributyl aluminum; trialkenyl aluminums such as triisoprenyl aluminum; dialkyl aluminum alkoxides such as diethyl aluminum ; ethoxide and dibutyl aluminum butoxide; alkyl aluminum sesquiethoxide and butyl aluminum sesquibutoxide; partially alkoxylated alkyl aluminums having an average - composition R 2 5Al(OR )O 5; partially halogenated alkyl aluminums, for example, ; dialkyl aluminum halogenides such as diethyl aluminum chloride, dibutyl aluminum chloride and diethyl aluminum bromide, alkyl aluminum sesquihalogenides such as . ~ l ., .
i'`
..
, .. . .
~lS3355 ethyl aluminum sesquichloride, butyl aluminum sesquichloride and ethyl aluminum sesquibromide, and alkyl aluminum dihalogenides such as ethyl aluminum dichlor-ide, propyl aluminum dichloride and butyl aluminum bromide; partially hydrogen-ated alkyl aluminums, for example dialkyl aluminum hydrides such as diethyl aluminum hydride and butyl aluminum hydride, and alkyl aluminum dihydrides such as ethyl aluminum dihydride and propyl aluminum dihydride; and partially alkoxyl-ated and halogenated alkyl aluminums such as ethyl aluminum ethoxy chloride, butyl aluminum butoxy chloride and ethyl aluminum ethoxybromide. Organoaluminum compounds in which two or more aluminum atoms are bonded through an oxygen or ~ 10 nitrogen atom, which are similar to the compounds ~i), may also be used. Ex-; ample of these compounds are (C2H5)gAlOAl~C2H5)2, ( 4 9)2 4 9 2 (C2H5)2AlNAl(C2H5)2
The solid titanium catalyst component that can be formed by known meth-ods can be purified by washing it with an inert liquid hydrocarbon. The term "inert hydrocarbon", as used in this application denotes a hydrocarbon which does not markedly degrade the performance of catalyst. Examples of such a hydro-carbon include aliphatic hydrocarbons such as n-pentane, isopentane, n-hexane, isohexane, n-heptane, n-octane, iso-octane, n-decane, n-dodecane, kerosene, and liquid paraffin; alicyclic hydrocarbons such as cyclopentane, .. ; i llS3355 methylcyclopentane, cyclohexane and methylcyclohexane; and aromatic hydro-carbons such as benzene, toluene, xylene and cymene. These hydrocarbons may be used as a mixture of at least two.
In order to obtaln a titanium catalyst component having a degree of uniformity of less than 4, it is preferred to use a method which comprises narrowing the particle size disbribution of a magnesium compound, and then reacting such a magnesium compound with a titanium compound which is liquid under the reaction conditions, or a method which comprises reacting a liquid magnesium compound and a liguid titanium compound under conditions that particles having a narrow particle size distribution are precipitated. For example, such a solid titanium catalyst component can be prepared by the techniques disclosed in Japanese Laid-Open Patent Publications Nos. 38590/77, 146292/78 and 41985/79, and U.S. Patent No. 4,315,874 (corresponding to Japanese Patent Applications Nos. 43002/79, 43003/79) and U.S. Patent No.
4,330,649 (corresponding to Japanese Patent Application No. 75582/79).
Several examples of such techniques are described below briefly.
(1) An oxygen-containing magnesium compound, or a complex of a magnsium compound and an electron donor, having a particle diameter of about 1 to about 200 microns and a uniformity coefficient of less than about 4, optionally pre-treated with an electron donor and/or a reagent such as an organoaluminum compound or halogen-containing silicon compound, is reacted with a titanium halide which is liquid under the reaction conditions, prefer-ably titanium tetrachloride.
(2) A magnesium compound in the liquid state having no reducing ability is reacted with a liquid titanium compound in the absence or presence of an electron donor to precipitate a titanium catalyst component having a particle diameter of about 1 to about 200 microns and a uniformity coefficient .~
liS3~55 of less than about 4.
(3) The product obtained in (2) above is - 8a -~15335S
reacted with a titanium compound.
~ 4) The product obtained in (1) or (2) is reacted with an electron do-nor and a titanium compound.
(5~ The product obtaincd in (1) or t2) is reucted with an electron do-nor, a titanium compound and an organoaluminum compound.
Examples of the magnesium compound used in the preparation of the titanium catalyst component having a uniformity coefficient of less than 4 in-clude magnesium oxide, magnesium hydroxide, hydrotalcite, carboxylic acid salts of magnesium, alkoxymagnesiums, aryloxymagnesiums, alkoxymagnesium halides, aryloxymagnesium halides, magnesium dihalides, and the reaction products between organic magnesium compounds and silanols, siloxanes, halosilanes, etc.
The solid titanium catalyst component of this invention can be ob-tained, for example, by drying the wet component formed in the aforesaid manner by washing with an inert liquid hydrocarbon. When the aforesaid component has a uniformity coefficient of at least 4, the final product can be obtained by dry-ing it such that the content of the inert liquid hydrocarbon is about 1 to about 10%, preferably about 1 to about 6%, based on the weight of the component.
If the aforesaid drying is omitted, or the drying resulted in a larger content of the inert liquid hydrocarbon than the specified upper limit, an ole-fin polymer obtained by, for example, slurry polymerization or vapor-phase poly-merization, does not have an increased bulk density, and the amount of a fine powdery polymer increases, and moreover, the reproducibility of the quality of the resulting polymer is poor. By drying the resulting titanium catalyst com-ponent such that its content of inert liquid hydrocarbon is within the specified range, there can be obtained a solid titanium catalyst component, which when used in the polymerization of olefins, can give a polymer having an increased bulk density with a reduced amount of a fine powdery polymer and a good reproduc-ibility of the quality of the resulting polymer. Eurthermore, the loss of the _ 9 _ , polymer decreases in block copolymerization in propylene polymerization, and a polymer of high quality can be produced. Moreover, the catalyst component is easier to transport or store. When the drying is carricd out such that the con~
tent of the inert liquid hydrocarbon decreases beyond the specified lower limit, the stereospecificity index of an olefin polymer obtained by the stereospecific polymerization of olefin using the resulting titanium catalyst component is re-duced.
The solid titanium catalyst component of this invention may be stored as such, preferably in an inert atmosphere, such as a nitrogen atmosphere, until it is used for polymerization. If desired, it may be again suspended in an inert liquid hydrocarbon and stored in this state. When it is stored for an excessive-ly long period of time, the effect of drying may be lost. Accordingly, it should be used for polymerization as early as possible, even when it is stored as sus-pended in an inert liquid hydrocarbon. For example, when the titanium catalyst component has been dried to such an extent that its content of the hydrocarbon is about 1 to about 6%, its performance does not change for about 10 days at room temperature. When the drying is done to such an extent that the content of the hydrocarbon is about 6 to about 10%, the performance of the resulting cata-lyst component begins to decrease when it is maintained at room temperature for about 2 days. In such a case, the catalyst component may be again suspended in the inert liquid hydrocarbon and again dried to adjust its content to the speci-fied range, before it is used for polymerization.
When the uniformity coefficient of the aforesaid catalyst component is less than 4, it is dried until the amount of the liquid hydrocarbon reaches about 1 to about 25%, preferably about 1 to about 20%, based on the weight of the component. When no drying is done, or the drying is insufficient so that the amount of the liquid hydrocarbon exceeds the specified upper limit, the cat-alyst particles are liable to undergo agglomeration during transportation or .
llS33SS
storage, and are difficult to discharge rom a catalyst reservoir. By drying the catalyst component to the specified extent, it can be more easily trans-ported or stored.
The drying treatment is carried out preferably under relatively mild temperature conditions. For exampleJ it is carried out at a temperature of not more than about 80C, preferably about OC to about 60C, in an a~mosphere of aninert gas. Temperatures in excess of about 80C tend to cause a reduction in polymerization activity in contrast to the case of performing the drying treat-ment at temperatures lower than about 80C. Accordingly, drying at temperatures lower than about 80 is preferred. On the other hand, too low a drying temper-ature, for example temperatures below about 0 C, is not practical because it will prolong the treating time to no advantage.
The drying time depends upon various operating conditions such as tem-perature. Drying is carried out until the content of the inert liquid hydro-carbon in the solid titanium catalyst component reaches the values within the specified range. Generally, the drying time is from about 15 minutes to about 100 hours, preferably from about 30 minutes to about 48 hours. The pressure maintained during the drying of the solid titanium catalyst component is not critical so long as it is lower than the saturated pressure of the liquid held in the catalyst component. For example, the drying can be carried out at atmos-s pheTic pressure or reduced pressure. If the drying temperature is as low as room temperature, it is advantageous to perform the drying under reduced pres-sure so as to promote removal of the inert liquid medium.
; Drying of the solid titanium catalyst component may be carried out in an atmosphere of an inert gas. The use of nitrogen is preferred for this pur-pose.
Drying of the solid titanium catalyst component in this invention may be carried out in an apparatus having a specification suitable for the opera-. .
.
1~5335S
tion, for example a moving bed dryer such as a horizontal stirred dryer, a rotary drum-type dryer or a vertical stirred dryer. A fixed bed dryer through which an inert gas flows may also be used, but the moving bed-type is advan-tageous because the drying time is shorter. Advantageously, the solid titanium catalyst component to be subjected to the drying step is moderately deprived of the inert liquid hydrocarbon before the drying treatment. Filtration, centri-fugation, precipitating separation using a siphon, etc. may be used to remove the hydrocarbon prior to the drying treatment.
The halogen which constitutes the solid titanium catalyst component ~, 10 of this invention is fluorine, chlorine, bromine, iodine or mixtures thereof.
Chlorine is preferred.
The electron donor used in the production of the solid titanium cat-alyst component includes, for example, oxygen-containing electron donors such as alcohols,-phenols, ketones, aldehydes, carboxylic acids, organic or inorganic acid esters, ethers, acid amides and acid anhydrides, and nitrogen-containing electron donors such as ammonia, amines, nitriles and isocyanates.
Specific examples of these electron donors are alcohols having 1 to 18 carbon atoms such as methanol, ethanol, propanol, pentanol, hexanol, octanol, dodecanol, octadecyl alcohol, benzyl alcohol, phenethyl alcohol, cumyl alcohol and isopropyl benzyl alcohol; phenols having 6 to 15 carbon atoms and optionally containing a lower alkyl group, such as phenol, cresol, xylenol, ethylphenol, propylphenol cumylphenol and naphthol; ketones having 3 to 15 carbon atoms such as acetone, methyl ethyl ketone, methyl isobutyl ketone, acetophenone and benzo-phenone; aldehydes having 2 to 15 carbon atoms such as acetaldehyde, benzalde-` hyd~, tolualdehyde and naphthoaldehyde; organic acid esters having 2 to 18 car-bon atoms such as methyl formate, methyl acetate, ethyl acetate, vinyl acetate, propyl acetate, octyl acetate, cyclohexyl acetate, ethyl propionate, methyl butyrate, ethyl valerate, methyl chloroacetate, ethyl dichloroacetate, methyl - 12 _ .
~ .. .
.
.' ' ~153355 methacrylate, ethyl crotonate, ethyl cyclohexanecarboxylate, methyl benzoate, ethyl benzoate, propyl benzoate, butyl benzoate, octyl benzoate, cyclohexyl benzoate, phenyl benzoate, benzyl benzoate, methyl toluate, ethyl toluate, amyl toluate, ethyl ethylbenzoate, methyl anisate, ethyl anisate, ethyl ethoxybenzo-ate, y-butyrolactone, ~-valerolactone, coumarine, phthalide and ethylene carbon-ate; inorganic acid esters such as ethyl silicate and ethylethoxysilane; acid halides such as acetyl chloride, benzyl chloride, toluoyl chloride and anisoyl chloride; ethers having 2 to 20 carbon atoms such as methyl ether, ethyl ether, isopropyl ether, butyl ether, amyl ether, tetrahydrofuran, anisole and diphenyl ether; acid amides such as acetamide, benzamide and toluamide; amines such as methylamine, ethylamine, diethylamine, tributylamine, piperidine, tribenzyl-amine, aniline, pyridine, picoline and tetramethyl ethylene diamine; and nit-riles such as acetonitrile, benzonitrile and tolunitrile. Two or more of these electron donors may be used in combination.
Preferred electron donors to be included in the titanium catalyst com-ponent as an essential ingredient are those not having active hydrogen, such as organic or inorganic acid esters, ethers, ketones, tertiary amines, acid halides "
and acid anhydrides. The organic acid esters and ethers are especially pre-ferred. Of these, aromatic carboxylic acid esters, and alkyl-containing ethers are most preferred. Typical examples of the preferred aromatic carboxylic acid esters include aromatic carboxylic acid esters having 8 to 18 carbon atoms, espe-cially lower alkyl or alkoxy esters of benzoic acid, lower alkyl benzoic acids - and lower alkoxybenzoic acids. Preferably, these lower alkyl or alkoxy esters ~ have l to 4 carbon atoms, especially 1 or 2 carbon atoms. Suitable alkyl-con-;~ taining ethers are those having 4 to 20 carbon atoms such as diisoamyl ether and dibutyl ether.
The solid titanium catalyst component for olefin polymerization in ac-cordance with this invention can be advantageously utilized for polymerization of .;
',, , ,-,,, , , ,,~ ~ . .
, , ... . . . . .
. .
. ~ ' . .
olefins when combined with organometallic compounds oE m0tals of Groups I to III
of the periodic table, especially organoaluminum compounds.
Organoaluminum compounds containing one Al-carbon bond at least in the molecule. Examples are ~i) organoaluminum compounds of the general formula RlmAl(OR2)nH Xq (wherein each of Rl and R2 represents a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms, for example, an alkyl, cycloalkyl or aryl group and may be identical or different, X represents halogen, m is a number represented by O<mc3, n is a number represented by Ocn<3, p is a number represented by Ocpc3, and q is a number represented by Ocp<3, with the proviso that m + n + p + q = 3); and (ii) complex alkylated products of metals of Group I and aluminum, as represented by the general formula MlAlR14 (wherein M represents Li, Na or K, and R is as defined above).
Examples of the organoaluminum compounds that fall within the category (i) include those of the general formula Rl Al~OR2)3 m wherein Rl and R are as defined above, and m is preferably a number represented by 1.5cm<3; those of the general formula R mAlX3 m wherein Rl is as defined above and X is halogen9 and m is preferably O<m<3; those of the general formula RlmAlH3 m wherein Rl is as de-fined above, and m is a number preferably a number represented by 2<m<3; and those of the general formula R mAl(OR )nXq wherein Rl and R are as defined above, X is halogen, O<mc3~ Ocn<3, Ocq<3, and m + n + q = 3.
Specific examples of the aluminum compounds (i) include trialkyl alum-inums such as triethyl aluminum and tributyl aluminum; trialkenyl aluminums such as triisoprenyl aluminum; dialkyl aluminum alkoxides such as diethyl aluminum ; ethoxide and dibutyl aluminum butoxide; alkyl aluminum sesquiethoxide and butyl aluminum sesquibutoxide; partially alkoxylated alkyl aluminums having an average - composition R 2 5Al(OR )O 5; partially halogenated alkyl aluminums, for example, ; dialkyl aluminum halogenides such as diethyl aluminum chloride, dibutyl aluminum chloride and diethyl aluminum bromide, alkyl aluminum sesquihalogenides such as . ~ l ., .
i'`
..
, .. . .
~lS3355 ethyl aluminum sesquichloride, butyl aluminum sesquichloride and ethyl aluminum sesquibromide, and alkyl aluminum dihalogenides such as ethyl aluminum dichlor-ide, propyl aluminum dichloride and butyl aluminum bromide; partially hydrogen-ated alkyl aluminums, for example dialkyl aluminum hydrides such as diethyl aluminum hydride and butyl aluminum hydride, and alkyl aluminum dihydrides such as ethyl aluminum dihydride and propyl aluminum dihydride; and partially alkoxyl-ated and halogenated alkyl aluminums such as ethyl aluminum ethoxy chloride, butyl aluminum butoxy chloride and ethyl aluminum ethoxybromide. Organoaluminum compounds in which two or more aluminum atoms are bonded through an oxygen or ~ 10 nitrogen atom, which are similar to the compounds ~i), may also be used. Ex-; ample of these compounds are (C2H5)gAlOAl~C2H5)2, ( 4 9)2 4 9 2 (C2H5)2AlNAl(C2H5)2
6 5 Examples of the compounds that fall within the category ~ii) are LiAl-(C2H5)4 and LiAl(C7H15)4 Among the above compounds, trialkyl aluminums and mixtures of trialkyl aluminums and alkyl aluminum halides are preferred.
The solid titanium catalyst component containing an inert liquid hydro-carbon in accordance with this invention can be used advantageously in the poly-merization or copolymerization of olefins. For example, the olefins are thosehaving 2 to 8 carbon atoms such as ethylene, propylene, l-butene, 4-methyl-1-pentene and l-octene. These olefins may be subjected not only to homopolymeriz-ation, but also to random copolymerization or block copolymerization. In the co-polymerization, polyunsaturated compounds such as conjugated or non-conjugated dienes may be selected as comonomers. Particularly, by utilizing the catalyst component of this invention in the polymerization or copolymerization of alpha-olefins having at least 3 carbon atoms, the copolymerization of these with di-; enes, or copolymerization of these with not more than 10 mole~ of ethylene, ',~
.~ ~
,~ ;
llS33S5 polymers IIAving high stereospec:i.flc:ity can be obtained in high yields with good reproducibility.
The polymerization can be performed either in the liquid phase or in the vapor phase. When it is carried out in the liquid phasel an inert liquid hydrocarbon solvent such as hexane, heptane and kerosene may bc used as a reac-tion medium, but the olefin itself may be used as a reaction mcdium. In the liquid-phase polymerization it is preferred to use the solid titanium catalyst component of this invention in an amount of about 0.0001 to about 1 millimole, calculated as titanium atom, and an organoaluminum compound in an amount of about 0.1 to about 50 millimoles, calculated as aluminum atom, both per liter of liquid phase, and to adjust the aluminum/titanium atomic ratio to about 1:1 to about 1000:1. A molecular weight controlling agent such as hydrogen may be used in the polymerization process. To control the stereospecificity of alpha-ole-fins having at least 3 carbon atoms, the polymerization may also be carried out in the co-presence of an ethylene glycol derivative (e.g., ethylene glycol mono-methyl ether), an ether, an amine, a sulfur-containing compound, a nitrile, an organic or inorganic ester, an acid anhydride, analcohol, etc. The presence of an aromatic carboxylic acid ester such as a benzoate, p-toluate or anisate as exemplified hereinabove with regard to the preparation of the titanium catalyst component is preferred. These compounds may be used in the form of an adduct with the organoaluminum compound. The effective amount of the aforesaid addi-tional compound is usually about 0.01 to about 2 moles, preferably about 0.1 to about 1 mole, per mole of the organoaluminum compound.
The polymerization temperature for olefins is preferably about 20 C to about 200 C, more preferably about 50C to about 180C. The reaction pressure is from atmospheric pressure to about 50 kg/cm , preferably an elevated pressure of from about 2 to about 20 kg/cm2. The polymerization can be carried out in any of batchwise, semi-continuous and continuous modes. The polymerization may, if de-- : -`
1~53355 :' sirod, be carried out in two or more stages in which the reaction conditions and/or the reaction zones are different.
The solid titanium catalyst component of this invention is especially suitable for the production of highly steTeospecific polymers of high bulk den-sities in high yields from alpha-olefins having at least 3 carbon atoms. Since the amount of a fine powdery polymer formed is small, the solid catalyst compon-ent can be used with commercial advantage.
r' The following examples illustrate the present invention in more detail.
Example 1 Preparation of a Ti-containing catalyst component:-Under a nitrogen atmosphere, 20 g of MgC12, 5.25 g of ethyl benzoate and 3 ml of dimethylpolysiloxane (viscosity 20 c.s.) were fed into a stainless steel (SUS-32) ball mill vessel having an inside diameter of 100 mm and contain-ing 2.8 kg of stainless steel (SUS-32) balls each having a diameter of 15 mm, and were contacted under mechanically pulverizing conditions for 24 hours at an acceleration of impact of 7G. Fifteen ~15) grams of the resulting pulverized product was suspended in 150 ml of titanium tetrachloride, and contacted at 80 for 2 hours with stirring. The solid portion was collected by filtration. Fur-thermore, 150 ml of titanium tetrachloride was added to the solid portion on the filter, and they were stirred at 80 C for 1 hour. The mixture was filtered, and thoroughly washed with fresh hexane. The resulting Ti-containing catalyst com-;~ ponent had an average particle diameter of 14 microns, and a uniformity coeffi-cient of 4.55.
i Drying of the Ti-containing catalyst component:-A suspension of 10 g of the resulting Ti-containing catalyst component in 30 ml of hexane as an inert liquid hydrocarbon was taken into a 300 ml flask ` which had been purged fully with nitrogen. The flask was dipped in an oil bath ;-~ maintained at 80C, and a stream of N2 was passed through it for 5 hours to dry :. ~', .
~. ' ` 1153;~55 the titanium catalyst con~onent. Thc rosulting solid titanium catalyst compon-ent containod 1.7% by weight of Ti; 64.5% by weight of Cl, 20.6% by weight of Mg, 7.1% by weight of ethyl benzoate, and 4.8% by weight of hexane.
Polymerization:-A 2-litor autoclave was charged with 0.75 liter of hexane, and the in-side of the autoclave was fully purged with propylene. The inside of the auto-clave was heated to 55C, and then 3.75 millimoles of triethyl aluminum, 1.25 millimoles of methyl toluate and 0.0225 mg-atom, calculated as Ti atom, of the resulting Ti catalyst component were added. H2 was added in an amount of 300 N
10 ml, and immediately then, the temperature of the polymerization system was raised. Propylene was polymerized therein at 70C for 4 hours while maintaining the pressure at 7 kg/cm .C. After the polymerization, the solid portion was collected by filtration. There was obtained 237.8 g of white powdery polypropyl-ene having a boiling n-heptane extraction residue of 96.2%, a melt flow index (MI) of 4.6 g/10 min. and an apparent density of 0.33 g/ml. There was obtained 14.4% by weight of a fine powdery polymer having a particle diameter of less , than 105 microns. Concentrating the liquid phase afforded 8.6 g of a solvent-soluble polymer.
Comparative Example Propylene was polymerized under the same conditions as in Example 1 except that the titanium catalyst component obtained in Example 1 was used as a ; hexane suspension without subjecting it to the drying step. There was obtained ~ 173.7 g of a white powdery polymer having a boiling n-heptane extraction residue : of 97.0%, a melt flow index of 3.0 and an apparent density of O.Z0 g/ml. There : .:
was obtained 25.5% by weight of a fine powdery polymer having a particle diameter of less than 105 microns. Concentrating the liquid phase afforded 5.5 g of a ' solvenc-soluble polymer.
~., ;l - lg --` : , .
.~, . . i ` ` ` `
. ~
, .
Comparative ~xample 2 Propylene was polymerized under the same conditions as in example 1 except that the titanium catalyst component obtained in Example 1 was dried . under a stream of nitrogen gas at 40C for 2 hours to a hexane content of 12.5%
by weight prior to use in the polymerization. There was obtained 266.2 g of a white powdery polymer having a boiling n-heptane extraction residue of 95 2% by weight, a melt flow index of 6.2 and an apparent density of 0.27 g/ml. There was obtained 19.5% by weight of a fine powdery polymer having a particle diam-eter of less than 105 microns. Concentrating the liquid phase afforded 9.8 g of a solvent-soluble polymer.
Comparative Example 3 .
The titanium catalyst component obtained in Example 1 was washed with hexane, and then dried at 2 mmHg for 3 hours. The hexane content of the dried product was 0.1% by weight.
Polymerization:-Propylene was polymerized under the polymerization conditions shown inExample 1 using the resulting titanium catalyst component. There was obtained ~; 225.8 g of a white powdery polymer having a boiling n-heptane extraction residue o 94.1%, an apparent density of 0.36 g/ml and a melt flow index of 5.3. There was obtained 10.6% by weight of a fine powdery polymer having a particle diam-eter of less than 105 microns. Concentrating the solvent layer afforded 12.5 g of a solvent-soluble polymer.
Example 2 The same titanium catalyst component as obtained in Example 1 was dried first at 70C for 30 minutes until it became a mud, and then the mud was ..
maintained at 50C for 1.5 hours. The resulting catalyst component was found to, contain 4.2% of hexane.
. Propylene was polymerized under the same conditions as in Example 1 ' - 19 -'~`'' ~,i ~ .
,..
' ,, ` ` 1153355 using the resulting catalyst component.
The results are shown in Table 1.
Example 3 A titanium catalyst component was prepared in the same way as in ex-ample 1 except that 8.6 g of ethyl o-toluate was used instead of 5.25 g of ethyl ~ benzoate, and dimethylpolysiloxane was not used. The resulting titanium cat-`~ alyst component had an average particle diameter of 13.5 microns and a uniform-ity coefficient of 4.6.
Drying:-A mixture of 7 g of hexane and 11 g of the resulting solid titanium catalyst component was dried at 25C for 30 minutes ~mder a pressure of 10 mmHg.
The resulting solid contained 1.9% by weight of Ti, 18.0% by weight of Mg, 60.0%
;; , ~. by weight of Cl, 8.5% by weight of ethyl benzoate and 3.1% by weight of hexane.
,~ Polymerization:-Propylene was polymerized under the same conditions as in Example 1.
The results are shown in Table 1.
Table 1 .~ Example Amount of Boiling Appar- MI Amount of Amount a white n-hept- ent (g/10 a fine pow- of a powdery ane density min.) dery polymer solvent-,~ polymer residue (g/ml) with a size soluble ~'~ (g) (%) of less than polymer .- 105 microns(g) - _ (wt. %) 2 215.7 95.2 0.35 6.9 14.3 8.2 3 279.2 94.1 0.36 4.4 11.5 12.8 Example 4 ; Preparation of a titanium catalyst component:-; 20 Anhydrous magnesium chloride (4.79 g), 25 ml of n-decane and 18.3 ml of 2-ethyl hexanol were heat-treated a* 130C for 2 hours to form a uniform so-lution. Then, 0.84 ml of ethyl benzoate was added. The solution was added . .~
,:
dropwise with stirring over 20 minutes in 200 ml of titanium tetrachloride cooled at 0C. The temperature was gradually raised, and then 1.39 ml of ethyl benzoate was added at 80C. The mixture was stirred at 80C for 2 hours. The solid portion was collected by filtration, and again suspended in 100 ml of titanium tetrachloride. The suspension was heated at 90C for 2 hours, and then the solid was collected by filtration. The solid was thoroughly washed with purified hexane until no free titanium compound was detected in the weighing.
The resulting titanium catalyst component contained 3.4% by weight of Ti, 20.0% by weight of Mg, 59.0% by weight of Cl and 16.6% by weight of ethyl benzoate, and had a spherical particle shape, an average particle diameter of 5 microns, and a uniformity coefficient of 1.34.
; Drying of the titanium catalyst component:-~ A suspension of 3 g of the titanium catalyst component in 30 ml of i~ hexane was fed into a 300 ml flask fully purged with nitrogen, and then main-tained at 25C. The flask was dipped in a bath, and nitrogen was passed through ;" it for 50 minutes. The resulting dry titanium catalyst component was a solid .,.
. powder having good flowability. By analysis, the solid was found to contain ,.~
16.6% by weight of hexane.
Polymerization:-n 20 A 2-liter autoclave was charged with 0.75 liter of hexane, and the in-side of the autoclave was purged fully with propylene. The polymerization sys-tem was heated to 68C, and 0.50 millimole of triethyl aluminum, 0.25 millimole of ethyl aluminum sesquichloride, 0.15 millimole of methyl toluate, and 0.015 mg-atom, calculated as Ti atom, of the resulting titanium catalyst component were fed into the autoclave. H2 was introduced in an amount of 400 ml, and propylene was charged into it continuously. Propylene was polymerized at 70C
for 2 hours while maintaining the pressure at 7 kg/cm .G. After the polymeriz-ation, the solid component was collected by filtration. There was obtained ~ ` ~
:' ,'~.~,''1 . -' llS335S
197.0 g of white powdery polypropylene having a boiling n-heptane extraction residue of 97.4%, a melt flow index of 4.1 and an apparent density of 0.38 g/ml.
j The polymer was in the form of spherical particles having an average particle diameter of 120 microns and a uniformity coefficient of 1.4. Concentrating the liquid phase afforded 1.7 g of a solvent-soluble polymer.
Example 5 In the preparation of the titanium catalyst component in Example 4, the drying was perfoTmed at 50C for 15 minutes to afford a solid titanium cat-alyst component having a hexane content of 11.6% by weight.
Polymerization:-Propylene was polymerized under the same conditions as in Example 4.
The results are shown in Table 2.
"~ Examp e 6 In the preparation of the titanium catalyst component in Example 4, heptane was used instead of the hexane, and drying was performed at 30C for 4 ' hours under a stream of N2. By analysis, the solid catalyst component was found to have a heptane content of 18.6% by weight.
' Polymerization:-
The solid titanium catalyst component containing an inert liquid hydro-carbon in accordance with this invention can be used advantageously in the poly-merization or copolymerization of olefins. For example, the olefins are thosehaving 2 to 8 carbon atoms such as ethylene, propylene, l-butene, 4-methyl-1-pentene and l-octene. These olefins may be subjected not only to homopolymeriz-ation, but also to random copolymerization or block copolymerization. In the co-polymerization, polyunsaturated compounds such as conjugated or non-conjugated dienes may be selected as comonomers. Particularly, by utilizing the catalyst component of this invention in the polymerization or copolymerization of alpha-olefins having at least 3 carbon atoms, the copolymerization of these with di-; enes, or copolymerization of these with not more than 10 mole~ of ethylene, ',~
.~ ~
,~ ;
llS33S5 polymers IIAving high stereospec:i.flc:ity can be obtained in high yields with good reproducibility.
The polymerization can be performed either in the liquid phase or in the vapor phase. When it is carried out in the liquid phasel an inert liquid hydrocarbon solvent such as hexane, heptane and kerosene may bc used as a reac-tion medium, but the olefin itself may be used as a reaction mcdium. In the liquid-phase polymerization it is preferred to use the solid titanium catalyst component of this invention in an amount of about 0.0001 to about 1 millimole, calculated as titanium atom, and an organoaluminum compound in an amount of about 0.1 to about 50 millimoles, calculated as aluminum atom, both per liter of liquid phase, and to adjust the aluminum/titanium atomic ratio to about 1:1 to about 1000:1. A molecular weight controlling agent such as hydrogen may be used in the polymerization process. To control the stereospecificity of alpha-ole-fins having at least 3 carbon atoms, the polymerization may also be carried out in the co-presence of an ethylene glycol derivative (e.g., ethylene glycol mono-methyl ether), an ether, an amine, a sulfur-containing compound, a nitrile, an organic or inorganic ester, an acid anhydride, analcohol, etc. The presence of an aromatic carboxylic acid ester such as a benzoate, p-toluate or anisate as exemplified hereinabove with regard to the preparation of the titanium catalyst component is preferred. These compounds may be used in the form of an adduct with the organoaluminum compound. The effective amount of the aforesaid addi-tional compound is usually about 0.01 to about 2 moles, preferably about 0.1 to about 1 mole, per mole of the organoaluminum compound.
The polymerization temperature for olefins is preferably about 20 C to about 200 C, more preferably about 50C to about 180C. The reaction pressure is from atmospheric pressure to about 50 kg/cm , preferably an elevated pressure of from about 2 to about 20 kg/cm2. The polymerization can be carried out in any of batchwise, semi-continuous and continuous modes. The polymerization may, if de-- : -`
1~53355 :' sirod, be carried out in two or more stages in which the reaction conditions and/or the reaction zones are different.
The solid titanium catalyst component of this invention is especially suitable for the production of highly steTeospecific polymers of high bulk den-sities in high yields from alpha-olefins having at least 3 carbon atoms. Since the amount of a fine powdery polymer formed is small, the solid catalyst compon-ent can be used with commercial advantage.
r' The following examples illustrate the present invention in more detail.
Example 1 Preparation of a Ti-containing catalyst component:-Under a nitrogen atmosphere, 20 g of MgC12, 5.25 g of ethyl benzoate and 3 ml of dimethylpolysiloxane (viscosity 20 c.s.) were fed into a stainless steel (SUS-32) ball mill vessel having an inside diameter of 100 mm and contain-ing 2.8 kg of stainless steel (SUS-32) balls each having a diameter of 15 mm, and were contacted under mechanically pulverizing conditions for 24 hours at an acceleration of impact of 7G. Fifteen ~15) grams of the resulting pulverized product was suspended in 150 ml of titanium tetrachloride, and contacted at 80 for 2 hours with stirring. The solid portion was collected by filtration. Fur-thermore, 150 ml of titanium tetrachloride was added to the solid portion on the filter, and they were stirred at 80 C for 1 hour. The mixture was filtered, and thoroughly washed with fresh hexane. The resulting Ti-containing catalyst com-;~ ponent had an average particle diameter of 14 microns, and a uniformity coeffi-cient of 4.55.
i Drying of the Ti-containing catalyst component:-A suspension of 10 g of the resulting Ti-containing catalyst component in 30 ml of hexane as an inert liquid hydrocarbon was taken into a 300 ml flask ` which had been purged fully with nitrogen. The flask was dipped in an oil bath ;-~ maintained at 80C, and a stream of N2 was passed through it for 5 hours to dry :. ~', .
~. ' ` 1153;~55 the titanium catalyst con~onent. Thc rosulting solid titanium catalyst compon-ent containod 1.7% by weight of Ti; 64.5% by weight of Cl, 20.6% by weight of Mg, 7.1% by weight of ethyl benzoate, and 4.8% by weight of hexane.
Polymerization:-A 2-litor autoclave was charged with 0.75 liter of hexane, and the in-side of the autoclave was fully purged with propylene. The inside of the auto-clave was heated to 55C, and then 3.75 millimoles of triethyl aluminum, 1.25 millimoles of methyl toluate and 0.0225 mg-atom, calculated as Ti atom, of the resulting Ti catalyst component were added. H2 was added in an amount of 300 N
10 ml, and immediately then, the temperature of the polymerization system was raised. Propylene was polymerized therein at 70C for 4 hours while maintaining the pressure at 7 kg/cm .C. After the polymerization, the solid portion was collected by filtration. There was obtained 237.8 g of white powdery polypropyl-ene having a boiling n-heptane extraction residue of 96.2%, a melt flow index (MI) of 4.6 g/10 min. and an apparent density of 0.33 g/ml. There was obtained 14.4% by weight of a fine powdery polymer having a particle diameter of less , than 105 microns. Concentrating the liquid phase afforded 8.6 g of a solvent-soluble polymer.
Comparative Example Propylene was polymerized under the same conditions as in Example 1 except that the titanium catalyst component obtained in Example 1 was used as a ; hexane suspension without subjecting it to the drying step. There was obtained ~ 173.7 g of a white powdery polymer having a boiling n-heptane extraction residue : of 97.0%, a melt flow index of 3.0 and an apparent density of O.Z0 g/ml. There : .:
was obtained 25.5% by weight of a fine powdery polymer having a particle diameter of less than 105 microns. Concentrating the liquid phase afforded 5.5 g of a ' solvenc-soluble polymer.
~., ;l - lg --` : , .
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, .
Comparative ~xample 2 Propylene was polymerized under the same conditions as in example 1 except that the titanium catalyst component obtained in Example 1 was dried . under a stream of nitrogen gas at 40C for 2 hours to a hexane content of 12.5%
by weight prior to use in the polymerization. There was obtained 266.2 g of a white powdery polymer having a boiling n-heptane extraction residue of 95 2% by weight, a melt flow index of 6.2 and an apparent density of 0.27 g/ml. There was obtained 19.5% by weight of a fine powdery polymer having a particle diam-eter of less than 105 microns. Concentrating the liquid phase afforded 9.8 g of a solvent-soluble polymer.
Comparative Example 3 .
The titanium catalyst component obtained in Example 1 was washed with hexane, and then dried at 2 mmHg for 3 hours. The hexane content of the dried product was 0.1% by weight.
Polymerization:-Propylene was polymerized under the polymerization conditions shown inExample 1 using the resulting titanium catalyst component. There was obtained ~; 225.8 g of a white powdery polymer having a boiling n-heptane extraction residue o 94.1%, an apparent density of 0.36 g/ml and a melt flow index of 5.3. There was obtained 10.6% by weight of a fine powdery polymer having a particle diam-eter of less than 105 microns. Concentrating the solvent layer afforded 12.5 g of a solvent-soluble polymer.
Example 2 The same titanium catalyst component as obtained in Example 1 was dried first at 70C for 30 minutes until it became a mud, and then the mud was ..
maintained at 50C for 1.5 hours. The resulting catalyst component was found to, contain 4.2% of hexane.
. Propylene was polymerized under the same conditions as in Example 1 ' - 19 -'~`'' ~,i ~ .
,..
' ,, ` ` 1153355 using the resulting catalyst component.
The results are shown in Table 1.
Example 3 A titanium catalyst component was prepared in the same way as in ex-ample 1 except that 8.6 g of ethyl o-toluate was used instead of 5.25 g of ethyl ~ benzoate, and dimethylpolysiloxane was not used. The resulting titanium cat-`~ alyst component had an average particle diameter of 13.5 microns and a uniform-ity coefficient of 4.6.
Drying:-A mixture of 7 g of hexane and 11 g of the resulting solid titanium catalyst component was dried at 25C for 30 minutes ~mder a pressure of 10 mmHg.
The resulting solid contained 1.9% by weight of Ti, 18.0% by weight of Mg, 60.0%
;; , ~. by weight of Cl, 8.5% by weight of ethyl benzoate and 3.1% by weight of hexane.
,~ Polymerization:-Propylene was polymerized under the same conditions as in Example 1.
The results are shown in Table 1.
Table 1 .~ Example Amount of Boiling Appar- MI Amount of Amount a white n-hept- ent (g/10 a fine pow- of a powdery ane density min.) dery polymer solvent-,~ polymer residue (g/ml) with a size soluble ~'~ (g) (%) of less than polymer .- 105 microns(g) - _ (wt. %) 2 215.7 95.2 0.35 6.9 14.3 8.2 3 279.2 94.1 0.36 4.4 11.5 12.8 Example 4 ; Preparation of a titanium catalyst component:-; 20 Anhydrous magnesium chloride (4.79 g), 25 ml of n-decane and 18.3 ml of 2-ethyl hexanol were heat-treated a* 130C for 2 hours to form a uniform so-lution. Then, 0.84 ml of ethyl benzoate was added. The solution was added . .~
,:
dropwise with stirring over 20 minutes in 200 ml of titanium tetrachloride cooled at 0C. The temperature was gradually raised, and then 1.39 ml of ethyl benzoate was added at 80C. The mixture was stirred at 80C for 2 hours. The solid portion was collected by filtration, and again suspended in 100 ml of titanium tetrachloride. The suspension was heated at 90C for 2 hours, and then the solid was collected by filtration. The solid was thoroughly washed with purified hexane until no free titanium compound was detected in the weighing.
The resulting titanium catalyst component contained 3.4% by weight of Ti, 20.0% by weight of Mg, 59.0% by weight of Cl and 16.6% by weight of ethyl benzoate, and had a spherical particle shape, an average particle diameter of 5 microns, and a uniformity coefficient of 1.34.
; Drying of the titanium catalyst component:-~ A suspension of 3 g of the titanium catalyst component in 30 ml of i~ hexane was fed into a 300 ml flask fully purged with nitrogen, and then main-tained at 25C. The flask was dipped in a bath, and nitrogen was passed through ;" it for 50 minutes. The resulting dry titanium catalyst component was a solid .,.
. powder having good flowability. By analysis, the solid was found to contain ,.~
16.6% by weight of hexane.
Polymerization:-n 20 A 2-liter autoclave was charged with 0.75 liter of hexane, and the in-side of the autoclave was purged fully with propylene. The polymerization sys-tem was heated to 68C, and 0.50 millimole of triethyl aluminum, 0.25 millimole of ethyl aluminum sesquichloride, 0.15 millimole of methyl toluate, and 0.015 mg-atom, calculated as Ti atom, of the resulting titanium catalyst component were fed into the autoclave. H2 was introduced in an amount of 400 ml, and propylene was charged into it continuously. Propylene was polymerized at 70C
for 2 hours while maintaining the pressure at 7 kg/cm .G. After the polymeriz-ation, the solid component was collected by filtration. There was obtained ~ ` ~
:' ,'~.~,''1 . -' llS335S
197.0 g of white powdery polypropylene having a boiling n-heptane extraction residue of 97.4%, a melt flow index of 4.1 and an apparent density of 0.38 g/ml.
j The polymer was in the form of spherical particles having an average particle diameter of 120 microns and a uniformity coefficient of 1.4. Concentrating the liquid phase afforded 1.7 g of a solvent-soluble polymer.
Example 5 In the preparation of the titanium catalyst component in Example 4, the drying was perfoTmed at 50C for 15 minutes to afford a solid titanium cat-alyst component having a hexane content of 11.6% by weight.
Polymerization:-Propylene was polymerized under the same conditions as in Example 4.
The results are shown in Table 2.
"~ Examp e 6 In the preparation of the titanium catalyst component in Example 4, heptane was used instead of the hexane, and drying was performed at 30C for 4 ' hours under a stream of N2. By analysis, the solid catalyst component was found to have a heptane content of 18.6% by weight.
' Polymerization:-
7 Propylene was polymerized under the same conditions as in Example 4.
The results are shown in Table 2.
E xample 7 ., Synthesis of spherical MgC12.nEtCH
A 3-liter autoclave, fully purged with N2, was charged with 1.5 liters , .
of purified kerosene, 112.5 g of commercially available MgC12, 163 g of ethanol and 5 g of Emasol 320 ~a trademark for surfactants made by Kao-Atlas Co., Ltd.).
The mixture was heated with stirring, and stirred at 125C and 600 rpm for 20 minutes. The pressure of the inside of the autoclave was adjusted to 10 kg/cm .G
with N2. A cock of a stainless steel tube having an inside diameter of 3 mm .
. '' :
.
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; 115335S
directly coMected to the audoclave and maintained at 125C was opened to trans-fer the mixture in the autoclave to a 5-liter glass flask (equipped with a stirrer) charged with 3 liters of purified keroscne cooled to -15C. The amount of the mixture transferred was liter, and the time required for the transfer wasabout 20 seconds. The resulting solid was collected by decantation, and washed thoroughly with hexane to afford a carrier. Microscopic examination showed that the carrier was in the form of completely spherical particles.
Preparation of a Ti-containing catalyst component:-A 300 ml glass flask was charged with 150 ml of TiC14, and 7.5 g of the solid obtained as described in the foregoing section suspended in 15 ml of purified kerosene was added with stirring at 20C. Then, 1.83 ml of ethyl benzo-ate was added, and the mixture was heated to 100C. The mixture was stirred at 100C for 2 hours, and then the sitrring was stopped. The supernatant liquid was removed by decantation, and further 150 ml of TiC14 was added. The mixture was stirred at llO~C for 2 hours. The solid portion was collected by hot filtra-tion, and washed thoroughly with hot kerosene and hexane. The resulting titan-ium containing catalyst component containing 4.4/ by weight of Ti, 59.0% by ;
weight of Cl, 19.0% by weight of Mg and 13.0% by weight of ethyl benzoate as - atoms. The catalyst component was in the form of spherical particles having a specific surface area of 207 m /g, an average particle diameter of 13 microns, and a uniformity coefficient of 2.75.
Drying of the titanium catalyst component:-A suspension of 3 g of the catalyst component in 30 liters of hexane was taken into a 300 ml flask fully purged with nitrogen. The flask was placed in a bath kept at 25C, and a stream of nitrogen was passed through it for 30 minutes. The resulting titanium catalyst component was a solid powder having good flowability. By analysis, it was found to have a hexane content of 20.6%.
,.'~
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Polymerization:-; A 2-liter autoclave was charged with 0.75 liter of hexane, and the in-side of the autoclave was fully purged with propylene. Then, 3.75 millimoles of triisobutyl aluminum, 1.75 millimoles of ethyl anisate, and 0.0225 millimole ~'~ calculated as Ti atom of the above catalyst component were fed into -the auto-clave. H2 was introduced in an amount of 400 ml, and the polymerization system was heated to 60C, propylene was fed into the autoclave to maintain the pres-sure at 7 kg/cm2.G, and polymerized at 60C for 2 hours. After the polymeriza-tion, the slurry was filtered to afford 215.9 g of a white powdery polymer hav-ing a boiling n-heptane extraction residue of 96.5%, an apparent density of 0.42g/ml and a melt flow index of 4.8. The polymer was in the form of spherical particles having an average particle diameter of 330 microns and a uniformity coefficient of 2.75. Concentrating the solvent layer afforded 4.6 g of a solvent-soluble polymer.
Comparative Example 4 The titanium catalyst component before drying which was obtained in ,; Example 7 was dried in the same way as in Example 7 except that the drying time ; was changed to 4 hours. The resulting catalyst component had a hexane content of 0.3%.
I 20 Polymerization:-: Propylene was polymerized under the same polymerization conditions as in Example 7. The results are shown in Table 2.
Example 8 Tetraethoxysilane ~0.11 mole) was added dropwise at room temperature to 0.1 mole of commercially available n-butyl magnesium chloride ~n-butyl ether solvent). The mixture was stirred at 60C for 1 hour. The resulting solid was collected by filtration, and washed fully with hexane. The solid was suspended in 30 ml of kerosene, and 0.02 mole of ethyl benzoate was added dropwise and , ' . .
`- 1153355 treated at 60C for 1 hour. The temperature was lowered, and 200 ml of TiC14 was added. The mixture was treated with stirring at 100C for 2 hours. The supernatant liquid was removed by decantation. Then, 200 ml of TiC14 was fur-ther added, and the residue was treated at 100C for 1 hour. The resulting sol-id was collected by hot filtration, and washed thoroughly with hot kerosene and hexane. The resulting titanium catalyst component contained 2.4% by weight of Ti~ 62.0% by weight of Cl, 21.0% by weight of Mg and 7.4% by weight of ethyl benzoate as atoms. The catalyst component was in the form of granules having an average particle diameter of 12 microns and a uniformity coefficient of 2.7.
10 Drying:-A suspension of 3 g of the titanium catalyst component in 30 ml of hexane was taken into a 300 ml flask fully purged with nitrogen. The flask was dipped in a bath maintained at 30C, and nitrogen was passed through it at 30C
for 90 minutes. The dried solid catalyst component had good flowability and contained 18.9% by weight of hexane.
, Polymerization:-Z,J Propylene was polymerized under the same conditions as in Example 7 ~ using the catalyst component prepared as above. The results are shown in Table r 2.
Comparative Example 5 The drying treatment in Example 8 was performed at 20C under reduced pressure for 4 hours. The resulting dry solid contained 0.2% by weight of hex-ane.
Propylene was polymerized under the same conditions as in Example 7 using the resulting dry solid catalyst component. The results are shown in Table 2.
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The results are shown in Table 2.
E xample 7 ., Synthesis of spherical MgC12.nEtCH
A 3-liter autoclave, fully purged with N2, was charged with 1.5 liters , .
of purified kerosene, 112.5 g of commercially available MgC12, 163 g of ethanol and 5 g of Emasol 320 ~a trademark for surfactants made by Kao-Atlas Co., Ltd.).
The mixture was heated with stirring, and stirred at 125C and 600 rpm for 20 minutes. The pressure of the inside of the autoclave was adjusted to 10 kg/cm .G
with N2. A cock of a stainless steel tube having an inside diameter of 3 mm .
. '' :
.
:. ~ .
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; 115335S
directly coMected to the audoclave and maintained at 125C was opened to trans-fer the mixture in the autoclave to a 5-liter glass flask (equipped with a stirrer) charged with 3 liters of purified keroscne cooled to -15C. The amount of the mixture transferred was liter, and the time required for the transfer wasabout 20 seconds. The resulting solid was collected by decantation, and washed thoroughly with hexane to afford a carrier. Microscopic examination showed that the carrier was in the form of completely spherical particles.
Preparation of a Ti-containing catalyst component:-A 300 ml glass flask was charged with 150 ml of TiC14, and 7.5 g of the solid obtained as described in the foregoing section suspended in 15 ml of purified kerosene was added with stirring at 20C. Then, 1.83 ml of ethyl benzo-ate was added, and the mixture was heated to 100C. The mixture was stirred at 100C for 2 hours, and then the sitrring was stopped. The supernatant liquid was removed by decantation, and further 150 ml of TiC14 was added. The mixture was stirred at llO~C for 2 hours. The solid portion was collected by hot filtra-tion, and washed thoroughly with hot kerosene and hexane. The resulting titan-ium containing catalyst component containing 4.4/ by weight of Ti, 59.0% by ;
weight of Cl, 19.0% by weight of Mg and 13.0% by weight of ethyl benzoate as - atoms. The catalyst component was in the form of spherical particles having a specific surface area of 207 m /g, an average particle diameter of 13 microns, and a uniformity coefficient of 2.75.
Drying of the titanium catalyst component:-A suspension of 3 g of the catalyst component in 30 liters of hexane was taken into a 300 ml flask fully purged with nitrogen. The flask was placed in a bath kept at 25C, and a stream of nitrogen was passed through it for 30 minutes. The resulting titanium catalyst component was a solid powder having good flowability. By analysis, it was found to have a hexane content of 20.6%.
,.'~
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Polymerization:-; A 2-liter autoclave was charged with 0.75 liter of hexane, and the in-side of the autoclave was fully purged with propylene. Then, 3.75 millimoles of triisobutyl aluminum, 1.75 millimoles of ethyl anisate, and 0.0225 millimole ~'~ calculated as Ti atom of the above catalyst component were fed into -the auto-clave. H2 was introduced in an amount of 400 ml, and the polymerization system was heated to 60C, propylene was fed into the autoclave to maintain the pres-sure at 7 kg/cm2.G, and polymerized at 60C for 2 hours. After the polymeriza-tion, the slurry was filtered to afford 215.9 g of a white powdery polymer hav-ing a boiling n-heptane extraction residue of 96.5%, an apparent density of 0.42g/ml and a melt flow index of 4.8. The polymer was in the form of spherical particles having an average particle diameter of 330 microns and a uniformity coefficient of 2.75. Concentrating the solvent layer afforded 4.6 g of a solvent-soluble polymer.
Comparative Example 4 The titanium catalyst component before drying which was obtained in ,; Example 7 was dried in the same way as in Example 7 except that the drying time ; was changed to 4 hours. The resulting catalyst component had a hexane content of 0.3%.
I 20 Polymerization:-: Propylene was polymerized under the same polymerization conditions as in Example 7. The results are shown in Table 2.
Example 8 Tetraethoxysilane ~0.11 mole) was added dropwise at room temperature to 0.1 mole of commercially available n-butyl magnesium chloride ~n-butyl ether solvent). The mixture was stirred at 60C for 1 hour. The resulting solid was collected by filtration, and washed fully with hexane. The solid was suspended in 30 ml of kerosene, and 0.02 mole of ethyl benzoate was added dropwise and , ' . .
`- 1153355 treated at 60C for 1 hour. The temperature was lowered, and 200 ml of TiC14 was added. The mixture was treated with stirring at 100C for 2 hours. The supernatant liquid was removed by decantation. Then, 200 ml of TiC14 was fur-ther added, and the residue was treated at 100C for 1 hour. The resulting sol-id was collected by hot filtration, and washed thoroughly with hot kerosene and hexane. The resulting titanium catalyst component contained 2.4% by weight of Ti~ 62.0% by weight of Cl, 21.0% by weight of Mg and 7.4% by weight of ethyl benzoate as atoms. The catalyst component was in the form of granules having an average particle diameter of 12 microns and a uniformity coefficient of 2.7.
10 Drying:-A suspension of 3 g of the titanium catalyst component in 30 ml of hexane was taken into a 300 ml flask fully purged with nitrogen. The flask was dipped in a bath maintained at 30C, and nitrogen was passed through it at 30C
for 90 minutes. The dried solid catalyst component had good flowability and contained 18.9% by weight of hexane.
, Polymerization:-Z,J Propylene was polymerized under the same conditions as in Example 7 ~ using the catalyst component prepared as above. The results are shown in Table r 2.
Comparative Example 5 The drying treatment in Example 8 was performed at 20C under reduced pressure for 4 hours. The resulting dry solid contained 0.2% by weight of hex-ane.
Propylene was polymerized under the same conditions as in Example 7 using the resulting dry solid catalyst component. The results are shown in Table 2.
' :
~, ,, .. ` ' h S o ~, ._ . ..... __.
O O ~ I I
,: , _ ~ h v~
.~ ~ U~ o o ~d-rl a) 5~ ~1 ~ O
h ~ Ei t~ ~ _~
.~ h ,~ ~ ~ h ;' ~ O
., O O _1 ~ ~ ~ U~
'.' ---- .. _ H I~ t~l ~) ~ .
~ 1~
N
,' Q> ~
.1 ~ ~ ~ O -I ,:
E-- h rl ~ ~ ~') ~ ~ ~
~ 4 O o O o O
,, ~
_ _ .~ C
a~ o ~ V
.~ ~ ~ ~ ~U) o 1 o\ r~
O I X ~ ~ a, ~ a~ a~
h ... _ _ _ 4~
: ~ ~ h .- . ~ ~ h c) ~ ,1 v E~ r_ t~ ~D 1` 0 o S ~ ~. t4 ot) ~ oo ~ O OI~ 00 ~L~
¢ ~ ;~
..
h I
h ~ L~) ~ X u~ ~o ~ . .
X Ul O ~rl X ~ X X X LLl 111 . - 26 -,~', ''~
:
.
Claims (35)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A solid titanium catalyst component for the production of an olefin polymer, comprising titanium, magnesium, a halogen and an electron donor as essential ingredients, said component further comprising an inert liquid hydrocarbon in an amount of, based on the weight of the component, of about 1 to about 10% when the component has a uniformity coefficient of at least 4, or about 1 to about 25% when the component has a uniformity coefficient of less than 4.
2. A solid titanium catalyst component of claim 1, wherein the content of the inert liquid hydrocarbon is attained by subjecting a solid titanium catalyst component containing the inert liquid hydrocarbon to a drying treat-ment.
3 A solid titanium catalyst component of claim 1, wherein the content of the inert liquid hydrocarbon is about 1 to about 6% by weight based on the weight of said solid titanium catalyst component when the component has a un-iformity coefficient of at least 4.
4. A solid titanium catalyst component of claim 1, wherein the halogen/
titanium mole ratio is more than about 4, the magnesium/titanium mole ratio is not less than about 3, and the electron donor/titanium mole ratio is from about 0.2 to about 6.
titanium mole ratio is more than about 4, the magnesium/titanium mole ratio is not less than about 3, and the electron donor/titanium mole ratio is from about 0.2 to about 6.
5. A solid titanium catalyst component of claim 1 or 4, wherein the inert liquid hydrocarbon is a member selected from the group consisting of aliphatic hydrocarbons, alicyclic hydrocarbons, aromatic hydrocarbons, and mixtures of at least two of these hydrocarbons.
6. A solid titanium catalyst component of claim 1 or 4, wherein the electron donor is an oxygen-containing electron donor or a nitrogen-containing electron donor.
7. A solid titanium catalyst component for the production of olefin polymers or copolymers, comprising titanium, magnesium, a halogen, an oxygen-containing electron donor and an inert liquid hydrocarbon selected from the group consisting of an aliphatic, alicyclic and aromatic hydrocarbon in an amount based on the weight of the component, of about 1 to about 10% when the component has a uniformity coefficient of at least 4, or about 1 to about 25% when the component has a uniformity coefficient of less than 4, wherein the halogen/titaninium mole ratio is more than about 4, the magnesium/titanium mole ratio is not less than about 3 and the electron donor/titanium mole ratio is from about 0.2 to about 6.
8. A solid titanium catalyst component of claim 7, wherein the electron donor is an alcohol having 1 to 18 carbon atoms, a phenol having 6 to 15 carbon atoms, a ketone having 3 to 15 carbon atoms, an aldehyde having 2 to 15 carbon atoms, an organic acid ester having 2 to 18 carbon atoms, an inorganic acid ester, an acid halide, an ether having 2 to 20 carbon atoms or an acid amide.
9. A solid titanium catalyst component of claim 8, wherein the electron donor does not contain active hydrogen.
10. A solid titanium catalyst component of claim 8, wherein the electron donor is an aromatic carboxylic acid ester having 8 to 18 carbon atoms or an alkyl-containing ether having 4 to 20 carbon atoms.
11. A solid titanium catalyst component of claim 1, 7 or 10, wherein the halogen/titanium mole ratio is about 8 to 100, the magnesium/titanium mole ratio is about 5 to 50 and the electron donor/titanium mole ratio is about 0.4 to 3.
12. A solid titanium catalyst component of claim 1, 7 or 10, wherein the uniformity coefficient is less than 4 and the content of the inert liquid hydrocarbon is 1 to 20%.
13. A solid titanium catalyst component of claim 1, 7 or 10, wherein the uniformity coefficient is at least 4 and the content of the inert liquid hydrocarbon is 1 to 6%.
14. A solid titanium catalyst component of claim 1, 7 or 10 wherein the specific surface area of the component is at least 40 m2/g.
15. A solid titanium catalyst component of claims 1, 7 or 10, wherein the halogen is chlorine.
16. A method of preparing a solid titanium catalyst component for the production of an olefin polymer, which comprises;
(a) intimately contacting (i) a magnesium compound or magnesium metal, (ii) a titanium compound wherein either the titanium compound or the magnesium compound contains a halogen and (iii) an electron donor in such a manner that the resulting titanium catalyst component contains halogen, titanium, magnesium and the electron donor, (b) washing the thus obtained titanium catalyst component with an inert liquid hydrocarbon, and (c) drying the wet component so that the amount of the inert liquid hydrocarbon in the titanium catalyst component reaches, based on the weight of the component, about 1 to about 10% when the component has a uniformity coefficient of at least 4, or about 1 to about 25% when the component has a uniformity coefficient of less than 4.
(a) intimately contacting (i) a magnesium compound or magnesium metal, (ii) a titanium compound wherein either the titanium compound or the magnesium compound contains a halogen and (iii) an electron donor in such a manner that the resulting titanium catalyst component contains halogen, titanium, magnesium and the electron donor, (b) washing the thus obtained titanium catalyst component with an inert liquid hydrocarbon, and (c) drying the wet component so that the amount of the inert liquid hydrocarbon in the titanium catalyst component reaches, based on the weight of the component, about 1 to about 10% when the component has a uniformity coefficient of at least 4, or about 1 to about 25% when the component has a uniformity coefficient of less than 4.
17. A method of claim 16, wherein the inert liquid hydrocarbon is an aliphatic, alicyclic or aromatic hydrocarbon.
18. A method of claim 16 or 17,wherein the wet component is dried under relatively mild temperature conditions.
19. A method of claim 16, wherein the wet component is dried at a temperature of not more than about 80°C in an atmosphere of an inert gas.
20. A method of claim 16 or 17,wherein the wet component is dried at about 0°C to about 60°C in an atmosphere of nitrogen gas.
21. A method of claim 16 or 17, wherein the wet component is dried at a temperature of not more than about 80°C in an atmosphere of an inert gas at atmospheric pressure or reduced pressure.
22. A method of claim 16 or 17, wherein the wet component is dried at room temperature in an atmosphere of an inert gas at under reduced pressure.
23. A method of claim 16, 17 or 19, wherein the step (a) is carried out by (a-l). reacting a magnesium compound of the formula;
Mg(OR)nX2-n wherein R represents a hydrocarbon group, n is a number represented by 0?n?2, and X is a halogen atom with an electron donor or an adduct of an electron donor with a halogen containing aluminum compound, or pulverizing strongly mechanically a mixture composed thereof, and (a-2). reacting the resulting reaction product or pulverized product with a titanium halide.
Mg(OR)nX2-n wherein R represents a hydrocarbon group, n is a number represented by 0?n?2, and X is a halogen atom with an electron donor or an adduct of an electron donor with a halogen containing aluminum compound, or pulverizing strongly mechanically a mixture composed thereof, and (a-2). reacting the resulting reaction product or pulverized product with a titanium halide.
24. A method of claim 16, 17 or 19, wherein the step (a) is carried out by first pulverizing a mixture containing magnesium chloride and an aromatic carboxylic acid ester, and then contacting the pulverized product with a titanium halide.
25. A method of claim 16, 17 or 19, wherein the step (a) is carried out by (a-3). reacting a halogen-containing magnesium compound with an active hydrogen containing electron donor and an electron donor free from active hydrogen, and (a-4). reacting the reaction product with a titanium compound.
26. A method of claim 16, 17 or 19, wherein the step (a) is carried out by first reacting magnesium chloride with an alcohol and an aromatic carboxylic acid ester, then reacting the product with titanium tetrachloride.
27. A method of claim 16, 17 or 19, wherein the step (a) is carried out by reacting an oxygen-containing magnesium compound or a complex of a magnesium compound and an electron donor having a particle diameter of about 1 to about 200 microns and a uniformity coefficient of less than about 4, with a titanium halide which is liquid under the reaction conditions, so as to obtain the titanium catalyst component having a uniformity coefficient of less than 4.
28. A method of claim 16, 17 or 19, wherein the step (a) is carried out by reacting a complex of a magnesium halide and an alcohol, with an aromatic carboxylic acid ester and titanium tetrachloride so as to obtain the titanium catalyst component having a uniformity coefficient of less than 4.
29. A method of claim 16, 17 or 19, wherein the step (a) is carried out by reacting a reaction product of an organic magnesium compound and a siloxane with an electron donor and a titanium halide which is liquid under the reaction conditions so as to obtain a titanium catalyst component having a uniformity coefficient of less than 4.
30. A method of claim 16, 17 or 19, wherein the step (a) is carried out by reacting first tetraethoxy silane with n-butyl magnesium chloride, then reacting the reaction product with an aromatic carboxylic acid ester and titanium tetrachloride so as to obtain a titanium catalyst component having a uniformity coefficient of less than 4.
31. A process for the production of an olefin polymer which comprises polymerizing an olefin having 2 to 8 carbon atoms in the presence of a catalytic amount of the solid titanium catalyst component as defined in claim 1 and an organometallic compound of a metal of group I to III of the periodic table.
32. A process of claim 31, wherein the olefin is homopolymerized or is co-polymerized with a conjugated or non-conjugated diene.
33. A process for the production of an olefin polymer which comprises;
polymerizing an alpha-olefin having 3 to 8 carbon atoms in the liquid phase in the presence of about 0.0001 to about 1 millimole, calculated as titanium atom, of the titanium catalyst component as defined in claim 7, and about 0.1 to about 50 millimoles, calculated as aluminum atom, both per liter of the liquid phase; of an organoaluminum compound of the formula R1mA1(OR2) nHpXq; wherein each R1 and R2 are a hydrocarbon group having 1 to 15 carbon atoms X is a halogen m is a number represented by 0 < m ? 3, n is a number represented by 0 ? n < 3, p is a number represented by 0 ? p < 3, q is a number represented by 0 ? q < 3, with the proviso that m+n+p+q - 3, or a complex alkylated aluminum compound of the formula M1A1R14;
wherein M' is li, Na or K and R1 is a hydrocarbon group having 1 to 15 carbon atoms, providing the aluminum/titanium atomic ratio is about 1:1 to about 100:1.
polymerizing an alpha-olefin having 3 to 8 carbon atoms in the liquid phase in the presence of about 0.0001 to about 1 millimole, calculated as titanium atom, of the titanium catalyst component as defined in claim 7, and about 0.1 to about 50 millimoles, calculated as aluminum atom, both per liter of the liquid phase; of an organoaluminum compound of the formula R1mA1(OR2) nHpXq; wherein each R1 and R2 are a hydrocarbon group having 1 to 15 carbon atoms X is a halogen m is a number represented by 0 < m ? 3, n is a number represented by 0 ? n < 3, p is a number represented by 0 ? p < 3, q is a number represented by 0 ? q < 3, with the proviso that m+n+p+q - 3, or a complex alkylated aluminum compound of the formula M1A1R14;
wherein M' is li, Na or K and R1 is a hydrocarbon group having 1 to 15 carbon atoms, providing the aluminum/titanium atomic ratio is about 1:1 to about 100:1.
34. A process for the production of polypropylene, which comprises;
polymerizing propylene in the liquid phase in the presence of about 0.0001 to about 1 millimole, calculated as titanium atom, of the titanium catalyst component as defined in claim 7, and about 0.1 to about 50 millimoles, calculated as aluminum atom, both per liter of the liquid phase, of a trialkyl aluminum or an alkyl aluminum halide in which the alkyl group has 1 to 15 carbon atoms, wherein the aluminum/titanium atomic ratio is about 1:1 to about 1000:1.
polymerizing propylene in the liquid phase in the presence of about 0.0001 to about 1 millimole, calculated as titanium atom, of the titanium catalyst component as defined in claim 7, and about 0.1 to about 50 millimoles, calculated as aluminum atom, both per liter of the liquid phase, of a trialkyl aluminum or an alkyl aluminum halide in which the alkyl group has 1 to 15 carbon atoms, wherein the aluminum/titanium atomic ratio is about 1:1 to about 1000:1.
35. A process of claim 31 or 33, wherein the olefin is polymerized in the presence of an aromatic carboxylic acid ester.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP43,494/79 | 1979-04-10 | ||
| JP4349479A JPS55143588A (en) | 1979-04-10 | 1979-04-10 | Pattern display system |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1153355A true CA1153355A (en) | 1983-09-06 |
Family
ID=12665259
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000349576A Expired CA1153355A (en) | 1979-04-10 | 1980-04-10 | Solid titanium catalyst component for production of an olefin polymer or copolymer |
Country Status (5)
| Country | Link |
|---|---|
| US (2) | US4360804A (en) |
| EP (1) | EP0017257B1 (en) |
| JP (1) | JPS55143588A (en) |
| CA (1) | CA1153355A (en) |
| DE (1) | DE3068655D1 (en) |
Families Citing this family (26)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4383296A (en) * | 1980-05-16 | 1983-05-10 | Apple Computer, Inc. | Computer with a memory system for remapping a memory having two memory output buses for high resolution display with scrolling of the displayed characters |
| US4533909A (en) * | 1980-05-16 | 1985-08-06 | Apple Computer, Inc. | Computer with color display |
| US4451840A (en) * | 1981-11-25 | 1984-05-29 | Rca Corporation | Picture control for television receiver on-screen display |
| US4578673A (en) * | 1983-07-08 | 1986-03-25 | Franklin Computer Corporation | Video color generator circuit for computer |
| JPS60247692A (en) * | 1984-05-24 | 1985-12-07 | 株式会社 アスキ− | Display controller |
| JPH0786743B2 (en) * | 1984-05-25 | 1995-09-20 | 株式会社アスキー | Display controller |
| US4703319A (en) * | 1985-09-06 | 1987-10-27 | High Resolution Sciences, Inc | Select switch box for white on black and black on white CRT data display |
| US4794383A (en) * | 1986-01-15 | 1988-12-27 | Karel Havel | Variable color digital multimeter |
| US6310590B1 (en) | 1986-01-15 | 2001-10-30 | Texas Digital Systems, Inc. | Method for continuously controlling color of display device |
| US5122733A (en) | 1986-01-15 | 1992-06-16 | Karel Havel | Variable color digital multimeter |
| US5057768A (en) * | 1986-07-07 | 1991-10-15 | Karel Havel | Measuring device with variable color display |
| US5003247A (en) * | 1986-07-07 | 1991-03-26 | Karel Havel | Measuring device with variable color background |
| US5561365A (en) | 1986-07-07 | 1996-10-01 | Karel Havel | Digital color display system |
| US5059955A (en) * | 1987-09-02 | 1991-10-22 | Hudson Soft Co. Ltd. | Apparatus for producing video signals |
| GB8800503D0 (en) * | 1988-01-11 | 1988-02-10 | Crosfield Electronics Ltd | Apparatus for generating two-dimensional coloured display |
| CA2131414A1 (en) * | 1993-09-22 | 1995-03-23 | Michael Abrash | Fast drawing of 256-color character output with a vga-type adapter |
| US5748344A (en) * | 1995-09-25 | 1998-05-05 | Xerox Corporation | System and method for determining a location and orientation in a black and white digital scanner |
| US6965205B2 (en) | 1997-08-26 | 2005-11-15 | Color Kinetics Incorporated | Light emitting diode based products |
| US6777891B2 (en) | 1997-08-26 | 2004-08-17 | Color Kinetics, Incorporated | Methods and apparatus for controlling devices in a networked lighting system |
| US7132804B2 (en) * | 1997-12-17 | 2006-11-07 | Color Kinetics Incorporated | Data delivery track |
| US6414662B1 (en) | 1999-10-12 | 2002-07-02 | Texas Digital Systems, Inc. | Variable color complementary display device using anti-parallel light emitting diodes |
| US7303300B2 (en) | 2000-09-27 | 2007-12-04 | Color Kinetics Incorporated | Methods and systems for illuminating household products |
| US7598681B2 (en) | 2001-05-30 | 2009-10-06 | Philips Solid-State Lighting Solutions, Inc. | Methods and apparatus for controlling devices in a networked lighting system |
| JP2003110380A (en) * | 2001-06-26 | 2003-04-11 | Koninkl Philips Electronics Nv | Large output current amplifier |
| US7358929B2 (en) * | 2001-09-17 | 2008-04-15 | Philips Solid-State Lighting Solutions, Inc. | Tile lighting methods and systems |
| WO2006093889A2 (en) | 2005-02-28 | 2006-09-08 | Color Kinetics Incorporated | Configurations and methods for embedding electronics or light emitters in manufactured materials |
Family Cites Families (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DD92589A (en) * | ||||
| US3911418A (en) * | 1969-10-08 | 1975-10-07 | Matsushita Electric Ind Co Ltd | Method and apparatus for independent color control of alphanumeric display and background therefor |
| US3603962A (en) * | 1970-03-18 | 1971-09-07 | Rca Corp | Color display for computer terminal |
| JPS5228530B2 (en) * | 1972-08-24 | 1977-07-27 | ||
| JPS4967530U (en) * | 1972-09-27 | 1974-06-12 | ||
| GB1452489A (en) * | 1973-12-20 | 1976-10-13 | Int Computers Ltd | Colour display apparatus |
| JPS559742B2 (en) * | 1974-06-20 | 1980-03-12 | ||
| JPS5326534A (en) * | 1976-08-25 | 1978-03-11 | Hitachi Ltd | Vi deo display device |
| US4139838A (en) * | 1977-04-06 | 1979-02-13 | Hitachi, Ltd. | Color pattern and alphanumeric character generator for use with raster-scan display devices |
| US4136359A (en) * | 1977-04-11 | 1979-01-23 | Apple Computer, Inc. | Microcomputer for use with video display |
| US4149184A (en) * | 1977-12-02 | 1979-04-10 | International Business Machines Corporation | Multi-color video display systems using more than one signal source |
| US4149152A (en) * | 1977-12-27 | 1979-04-10 | Rca Corporation | Color display having selectable off-on and background color control |
| US4183046A (en) * | 1978-08-17 | 1980-01-08 | Interpretation Systems Incorporated | Electronic apparatus for converting digital image or graphics data to color video display formats and method therefor |
| US4232311A (en) * | 1979-03-20 | 1980-11-04 | Chyron Corporation | Color display apparatus |
-
1979
- 1979-04-10 JP JP4349479A patent/JPS55143588A/en active Granted
-
1980
- 1980-04-07 US US06/137,800 patent/US4360804A/en not_active Ceased
- 1980-04-10 CA CA000349576A patent/CA1153355A/en not_active Expired
- 1980-04-10 DE DE8080101903T patent/DE3068655D1/en not_active Expired
- 1980-04-10 EP EP80101903A patent/EP0017257B1/en not_active Expired
-
1984
- 1984-11-19 US US06/673,135 patent/USRE32749E/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| EP0017257B1 (en) | 1984-07-25 |
| JPS6231353B2 (en) | 1987-07-08 |
| US4360804A (en) | 1982-11-23 |
| DE3068655D1 (en) | 1984-08-30 |
| JPS55143588A (en) | 1980-11-08 |
| EP0017257A1 (en) | 1980-10-15 |
| USRE32749E (en) | 1988-09-13 |
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