CA1156800A - Catalytic titanium component, process for the manufacture thereof, and process for the polymerization of alkenes-1 with application of such a titanium component - Google Patents
Catalytic titanium component, process for the manufacture thereof, and process for the polymerization of alkenes-1 with application of such a titanium componentInfo
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- CA1156800A CA1156800A CA000348650A CA348650A CA1156800A CA 1156800 A CA1156800 A CA 1156800A CA 000348650 A CA000348650 A CA 000348650A CA 348650 A CA348650 A CA 348650A CA 1156800 A CA1156800 A CA 1156800A
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- Prior art keywords
- titanium
- compound
- organic
- aluminium
- halide
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S526/00—Synthetic resins or natural rubbers -- part of the class 520 series
- Y10S526/906—Comminution of transition metal containing catalyst
Abstract
A B S T R A C T
The invention relates to a catalytic titanium component useful for the polymerization of alkenes-1 and for the copolymerization of alkenes-1 with each other or with ethylene, containing a halogenated titanium compound, an electron donor, and a metal halide obtained by conversion of an organic metal compound with a halogenating agent of the formula RXm, wherein R is a hydrocarbon group, ? hydrogen atom or a halogen atom, X is a halogen atom, and m is a whole number from 1-10, The catalytic titanium component according to the invention is characterized in that the metal halide has been obtained by conversion of a combination of an organic aluminium compound and an organic magnesium compound with the halogenating agent into the corresponding metal halide, for instance by means of a reaction with hydrogen chloride or an alkyl chloride.
The titanium component according to the invention considerably improves the activity and the stereospecificity of a catalyst system for the polymerization of alkenes-1, in particular propylene, and moreover a much purer polymer can be obtained.
The invention relates to a catalytic titanium component useful for the polymerization of alkenes-1 and for the copolymerization of alkenes-1 with each other or with ethylene, containing a halogenated titanium compound, an electron donor, and a metal halide obtained by conversion of an organic metal compound with a halogenating agent of the formula RXm, wherein R is a hydrocarbon group, ? hydrogen atom or a halogen atom, X is a halogen atom, and m is a whole number from 1-10, The catalytic titanium component according to the invention is characterized in that the metal halide has been obtained by conversion of a combination of an organic aluminium compound and an organic magnesium compound with the halogenating agent into the corresponding metal halide, for instance by means of a reaction with hydrogen chloride or an alkyl chloride.
The titanium component according to the invention considerably improves the activity and the stereospecificity of a catalyst system for the polymerization of alkenes-1, in particular propylene, and moreover a much purer polymer can be obtained.
Description
o n CATALYTIC TITANIUM COMPOUND, PROCESS FOR THE M~NUFACTURE THEREOF, AND
METHOD FOR THE POLYMERIZATION OF ALKEN~S-l WITH APPLIC~TION OF SUCH
A TITANIUM COMPONENT
me invention relates to a catalytic titanium componentuse~ul ~or the polymerization oi' alkenes-1 and ior tha copolymerization o~
alkenes-l ~lth each other or with ethylene, containing a halogenated titanium compound, an electron donor and a metal halide obtained by convarsion o~ an organic metal compound ~ith a halogenating agent oP
the ~'ormula RXm, wherein R is a hydrocarbon group, a hydrogen atom or a haloge~ atom, X i9 a halogen atom, and m is a whole nu~ber o~ 1 - 10.
Such a titanium component is known from the Dutch 'Terin3age-legging' 7609722, which describes a catalyst system for the polymeri-zation o~ alkenes-1 with a titanium component containing a halogenated titanium compound, an electron donor and a ~agnesium halide as carrier material, obtained, ~or instsnce, by conversion o~ an org~nic magnesium compolmd with silicon chloride. In stead o~ silicon chloride, also, ~cr instance, a hydrogen halide, a halogenated hydrocarbon or a ~re~
halogen can be used as the halogenating agent. In polymerization, this catalytic titanium component i5 used in combination with, ior instance, an organoaluminium component, such as a tri-alkyl aluminium compound o~ a di-alkyl aluminium halide. Such a catalyst system is only moderately active in polymerization oi propylene or other alkenas-l, such as butylene-1, 4-methyl pentylene-1 and other alkenes-1, and also the stereospeciiicity and particularly the purity oi the obtained polymer with respeot to catalyst residues (particularly titanium and halogen) is unsatisi'actory.
It has been iound now tha~ the activity and the stereospeci-~icity o~ such a catalyst system can be consid~rably improved, and mor~over a much purer polymer can be obtained, ii' the metal halide is produced by conversion oi' a combination o~ an organic aluminium compound and an organic ~agn~sium compound with the halogenating agent, for instance by a reaction with hydrogen chloride or an alkyl chlorido.
According to the invention, a catalytic titanium component 1 1~8~0 component useful for polymerization of alkenes-l and for copolymerization of alkenes-l with each other or with ethylene therefor contains a halogenated titanium compound, an electron donor and a metal halide obtained by conversion of an organic metal compound with a halogenating agent of the formula RXm, wherein R is a hydrocarbon group, a hydrogen atom or a halogen atom, X is a halogen atom, and m is a whole number from 1-10, characterized in that -the metal halide has been obtained by conversion of a combination of an organlc aluminium compound and an organic magnesium compound with the halogenating agent to form the corresponding metal halide.
According to a further aspect of the invention there is provided a process for the p~eparation of a titanium cornponent useful for the polymeri-zation of alkenes-l and for the copolymerization of alkenes-l with each other or with ethylene, which titanium component contains a halogenated titanium compound, an electron donor, and a metal halide which process comprises react-ing a combination of an organic aluminium compound and an organic magnesium compound with a halogenating agent of the formula RXm, wherein R is a hydro-carbon group, a hydrogen atom or a halogen atom,Xisa halogen atom, and m is a whole number from 1-10, to form the corresponding metal halide, the process further comprising combining the metal halide so formed with a titanium halide compound of tetravalent titanium and an electron donor.
According to another aspect of the present invention there is provided a process Eor the polymerization of alkenes-l and for the copolymeri-zation of alkenes-l with each other or with ethylene comprising the use of a catalyst system consisting of the above defined titanium component.
It is observed that from the Dutch "Terinzagelegging" No. 7711518 a catalyst for manu:Eacture of polyethylene is known which is prepared by re~
duction of tetra-butyl titanate with a mixed magnesium-aluminium alkyl, followed .~
8~
by de-activation oE any surplus of magnesium alkyl with hydrogen chloride, a~ter which a second quantity of tetra-butyl titanate is added. The Dutch "Terinzagelegging" No. 7605544 describes a similar catalyst product, obtained Q ~e by adding tetra-isopropyl-t~ p*~y~ titanate to the reaction product of a dibutyl magnesium-triethyl aluminium complex and hydrogen chloride. These known catalysts clearly differ from the catalytic titanium component according to the invention, while moreover these publications only give results about the polymerization of ethylene, whereby the stereospecificityof the catalyst is not involved.
The titanium component according to the invention improves the stereospecificity of the polymerization catalyst, at a very high level of activity. With this catalyst, polymers, for instance polypropylene, can be obtained with a very low halogen content, a very low titanium content, good particle size and good particle size distribution. As a result, the polymer has good processing properties and is little corrosive for the processing equipment.
The titanium component may contain any halogenated compound of bi-, tri- or tetravalent titanium, including compounds in which some of the titanium valencies have been taken up by atoms other than halogen atoms. The halogen in the halogenated titanium compound is preferably chlorine, but may also be bromine andlor iodine, for instance. Examples of suitable halogenated titanium compounds are TiC13, TiC13. 1/3 AlC13, TiC14, TiBr4~ TiI~, Ti(isobutoxy)2C12, Ti~phenoxy)C13 -2a-68~
and Ti(o methyl phenoxy)C13.
TiCl3 and TiCl4 are highly suitable, especially TiCl4.
For application in multi-stage polymerization processes, especially those in which more than hali an hour is normally r0quired ~or poly~erization in ths first stage before a second stag~ is started, it is oi special advantage i~ the halogenated titanium compound used is a titanium halide phenolate of the formula Ti X Ab, in which X
represents a halogen atom and A the acid r~ical o~ a phenol, n is a whole n~mher oi at least 1, and a and b are such numbers that a/n and 7G b/n are both 1-3, on the understanding that (a~b)/n is equal to 3-4.
The rate o~ decline ;n the activity of the catalyst is then substan-tially reduced, so t~at in mul~i-stag0 polymerization processes, ~or instance so-called block copolymeri~ations, in which in the iirst sta~e ior inst~noa i'or more than hal~ an hour propylene, butylene-l, 4-methyl pentylen~-1 or another alkene-1 with at least 3 carbon atoms Fer molecule is polym~rized, possibly in the presence o~ a minor quantity o~ ethylene, after which in a second stage another monomer or a monomer mixture oi a dif~erent composition is polymeri7ed in the presence o~ the polymer iormed in the first stage, ~o that block~ oi di~erent monomer composition may be pre~ent in ona polymer molecule, the resultant proportion o~ such bloc~ copolymsr is considerably higher.
The phenolate may be, for in~ance, the acid radical derived ~rom unsubstituted phenol or ~rcm a phenol in which one or more alkyl groups or alkoxy groups with ~or instance 1-6 carbon atoms per group have been substituted, ~or instance crssol, methoxy phenol, xylenol, ethyl phenol, propyl phenol, octyl phenol, dibutyl phenol, cumyl phenol or naphthol. Cresolates a~d methoxy phenolates are particularly ~uitable, while cresolates o~fer the advantage of particularly high stereospeci~icity oi the catalyst system. The benzene nucleus o~ the phenolate may contain other substituents which are non-detrimental in the polymerization reaction, such as one or mors halide substituents.
m e phenolate groups may have, ~or instanoe, 6 to 18 carbon atoms, pre-ierably 6-12 carbon atoms.
The halide phenola~e ratio in the titanium halide phenola~e is pre~erably ~rom 1 : 1 to 3 : 1. Besides the titanium halide phenolata, a phenolate-~ree tit&nium halide can be used in the halogenated titanium 8 ~
compound, i~ so desired. Preferably, a halide phenolate oi tetravalent titanium is used. The value o~ n is mostly 1, but may also be 2 or higher, especially i~ a polyphenolate is used.
Specii'ic examples o~ titanium halide phenolate~ to be used in the catalytic titanium component according to the invention are titanium (IV) trichloride monophenolate, titanium ~IV) dichloride di-phenolats, titanium (IV) trichloride mono-p-cresolate, titanium(III~-dichloride mono-o-cresolate, titanium (IV) monochloride tri-l-naphtholate, titanium (IV) trichloride mono-(p-chlorophenolate), titanium (IV) tribromide mono-p-cresolate, titaniu~ (IV) tribromide mono (xylenolate-isomsr mixture) and titanium (IV) monoiodide trianisolate. Such compounds can be obtained for in tance through conversion o~ the relevant tita~ium halide with the stoechiometric quantity o~ the relevant phenol, in which reaction the ralevant hydrogen halide is liberated, or through double conversion o~ a titanium halide with a metal phenolate, ~or instance an al~ali metal phanolate.
Ths catalytic titanium component according to the invention contains a metal halida obtained by conversion oi a combination oP
an organic aluminium compound and an organic magnesiu~ compound with the halogenating agent. In this metal halide the halogen: (aluminium ~-magnesium) atomic ratio is e.g. in the range t2.5 - 5) : 1, pre~erably in the range (4-5) : 1.
The conver~ion o~ the combination oP an organic aluminium compound and an organic magnesium compound to ~orm the corresponding matal halide may be o~fected, ~or instance, by precipitation o~ the metal halide from a solutlon o~ the org~ic motal compounds in a suitable solvent, by means o~ the halogenating agent. Suitable precipitation agents are, i'or instance, the hydrogen halides and aliphatic halogen compounds. The hQlogen in the halogenating agent is pre~erably chlorine, but may also be bromine or iodine, ~or instance.
The hydrogen halides may be introduced in the form o~ water iree gas, ior instance.
Other suitable halogenating agents are aliphatic halogen com-pounds, iorinstance aliphatichalogenatedhydrooarbonswith~ ~orinstance, 1-8 carbon atoms per molecule, in partioular alkyl chlorides. ExampleQ
are methyl chloride, methylene chloride, chloroform, ethyl bromide, ethylene dichlorida, i-propyl chloride, n~butyi iodide, etc, Other suitable precipitation agents are free halogens and interhalogen compounds, ~or instance Cl2, Br2, I2, ICl, IC13 or BrCl.
The organic aluminium compound prei'erably contains one or more hydrocarbon groups bonded diractly to the metal. The hydrocarbon groups preferably contain 1-10 carbon atoms. Examples are trialkyl or trialkenyl aluminium compounds, for instance triethyl aluminium, tri-propyl aluminium, triisobutyl aluminium, triisoprenyl aluminium, trihexyl aluminium and trioctyl aluminium; dialkyl aluminium hydrides, for instance diethyl aluminium hydride or diisobutyl aluminium hydride;
dialkyl aluminium halides, in particular a chloride or a bromide, di ethyl aluminium chloride and bromide being particularly suitable, while di-n-butyl aluminium chloride or methyl-n-butyl aluminium chloride, for instance, may also be used; and (mono)alkyl aluminium dihalides, ~or instance ethyl aluminium dichloride, n-butyl aluminium dichloride or n-hexyl aluminium dibromide. If a halogen-containing organic aluminium compound is used, the halogen is pr~erably the same as that in the halogenating agent used. Trialkyl aluminium compounds are preferrsd.
The organic magnesium compound may be, for instancs, a di-alkyl magn0sium or an alkyl magnesium halide. The hydrocarbon groups pr0ferably contain 1-10 carbon atoms again. Examples are ethyl magnesium chloride, n butyl magnesium chloride, i-propyl magn0sium bromide, 25 n-decyl magnesium iodide, di-n-butyl magnesium, di-i-amyl magnesium and ~i-n-octyl magnesium.
The conversion o~ the organic metal compounds into the metal halide may be e~ected in the absenc0 o~ a solvent, but lt is pr0~era-ble ~or the metal halide to be precipitated ~rom a solution of the orga-30 nic metal compounds in a suitable solvent. Examples oP suitable solventsare aliphatic, cycloaliphatic, aromatic and mixsd aromatic~aliphatic hydrocarbons, with 3-8 carbon atoms per molecule, which are inert under the reaction conditions, for instance butane, i-butana, n-hexane, n-heptane, cyclohexane, benzene, toluene and xylenes. Halogsnated hydro-carbons may also be used.
The temperature during the conversion may be, for instance,250-425 K, if a hydrogen halide is used as halogenating agent preferably about 290-340 K. The pressure is not a critical factor and is, ior instance, 10-1000 kPa. The reaction time may e.g. be 0.5-lO hours, preferably 1-4 hours.
In a suitabls mode oi realization of the process according to the invention, first an alkyl halide, for ins*ance n-butyl chloride, is converted into the alkyl magnesium halide with metallic magnesium in a hydrocarbon solvent, ~or instance n-heptane, ln a manner known in itseli, and subsequently or simultaneously a suitable aluminium co~po~md, for instance a trialkyl aluminium such as tri-n-butyl aluminium, is applied, so that a dissolved comple~ consisting o~ an organoaluminium compound and an alkyl magnesium compound ~ ~ormed.
Instaad o~ a trialkyl aluminium, it is also possible to add another organic aluminium compound, ior instance an alkoxy aluminium compound, an alkyl aluminium halide or the aluminium salt oi an organic acid, or ~tallic aluminium or an aluminium halide, ~or instance aluminium chloride, which is converted in situ into an organic alumini~m compound forming the complex. Th0 resultant solution o~ an organoaluminium~alkyl magnesium complex is subsequently treat0d with a gaseous h~drogen halide, ~or instance hydrogen chloride, or with an alkyl halide so that the metal halide i9 precipitated.
The aluminium: magnesium molar ratio in the combination of organometal compoundq used as starting material may be, ~or instance, 1 : 99 to 1 l.Other molar ratios are possible , but are not advan-tageo~s. This molar ratio is pre~erably 1 : 20 to 1 : 3, more in particular l : 10 to l : 4, When using combinations of organometal compounds with molpercentages organoaluminium compound with respeot to organomagnesium compound rising above 35, the activity o~ the obtainad catalyst systems decreases rapidly with increasing molpercent~ge~
1~ so desired, it is possible to incorporate ~urther metal ions in th0 metal halide, ior instance sodium, tin, silicon or germanium.
In a highly suitable mode o~ realization, the titanium co~po-nent according to the invention is prepared by converting a combination o~ an organic aluminium compound and an organic magnesium compound with the halogenating agent into the corresponding metal halide, which is converted with a titanium halide compound o~ tetravalent titanium.
~ It is observed that aiter the combination of the titanium halide compound with the metal halide used as carrier, the tetravalent 8 V ~ `
titanium may, ii so desired, be reduc~d to titanium o~ a lower valency, for instance tri- or bivalent titanium, in a known manner, so that the titanium component used need not necessarily contain tetravalent titanium.
Besides the halogenated titanium compound and metal halide used as carrier, the titanium component contains an electron donor. It is assumed that this donor is present in the ~orm oi' a complex with the halog3nated titanium coMpound. The elsctron donor used may be one or more oi the compounds used in the known manner in similar catalyst systsms, ~or in~tancs oxygencontaining electron donors such as water, alcohols, phenols, k0tones, aldehydes, acid halides, carboxylic acids, ssters, ethers and amides, or nitrogen-containing electron donors such as ammonia, amines, nitriles, isocyanates and nitro compounds.
Speci~ic 0~amples oi suitable el6ctron donors are alcohols with 1-18 carbon atoms per molecule, for instance methanol, ethanol, propanol, hexanol, stearyl alcohol, benzyl alcohol, phenyl ethyl alcohol or cumyl alcohol; phenols with 6-18 carbon atoms per molecule, ~or instance phenol, cre~ol, xylenol, ethyl phenol, propyl phenol, octyl phenol, dibutyl phenol, cumyl phenol or naphthol; ketones with 3-15 carbon atoms per molecule, ~or instance acetone, me~hyl athyl ketone, mathyl isobutyl ketone, acetophencne or ber~ophenone; aldehydes with
METHOD FOR THE POLYMERIZATION OF ALKEN~S-l WITH APPLIC~TION OF SUCH
A TITANIUM COMPONENT
me invention relates to a catalytic titanium componentuse~ul ~or the polymerization oi' alkenes-1 and ior tha copolymerization o~
alkenes-l ~lth each other or with ethylene, containing a halogenated titanium compound, an electron donor and a metal halide obtained by convarsion o~ an organic metal compound ~ith a halogenating agent oP
the ~'ormula RXm, wherein R is a hydrocarbon group, a hydrogen atom or a haloge~ atom, X i9 a halogen atom, and m is a whole nu~ber o~ 1 - 10.
Such a titanium component is known from the Dutch 'Terin3age-legging' 7609722, which describes a catalyst system for the polymeri-zation o~ alkenes-1 with a titanium component containing a halogenated titanium compound, an electron donor and a ~agnesium halide as carrier material, obtained, ~or instsnce, by conversion o~ an org~nic magnesium compolmd with silicon chloride. In stead o~ silicon chloride, also, ~cr instance, a hydrogen halide, a halogenated hydrocarbon or a ~re~
halogen can be used as the halogenating agent. In polymerization, this catalytic titanium component i5 used in combination with, ior instance, an organoaluminium component, such as a tri-alkyl aluminium compound o~ a di-alkyl aluminium halide. Such a catalyst system is only moderately active in polymerization oi propylene or other alkenas-l, such as butylene-1, 4-methyl pentylene-1 and other alkenes-1, and also the stereospeciiicity and particularly the purity oi the obtained polymer with respeot to catalyst residues (particularly titanium and halogen) is unsatisi'actory.
It has been iound now tha~ the activity and the stereospeci-~icity o~ such a catalyst system can be consid~rably improved, and mor~over a much purer polymer can be obtained, ii' the metal halide is produced by conversion oi' a combination o~ an organic aluminium compound and an organic ~agn~sium compound with the halogenating agent, for instance by a reaction with hydrogen chloride or an alkyl chlorido.
According to the invention, a catalytic titanium component 1 1~8~0 component useful for polymerization of alkenes-l and for copolymerization of alkenes-l with each other or with ethylene therefor contains a halogenated titanium compound, an electron donor and a metal halide obtained by conversion of an organic metal compound with a halogenating agent of the formula RXm, wherein R is a hydrocarbon group, a hydrogen atom or a halogen atom, X is a halogen atom, and m is a whole number from 1-10, characterized in that -the metal halide has been obtained by conversion of a combination of an organlc aluminium compound and an organic magnesium compound with the halogenating agent to form the corresponding metal halide.
According to a further aspect of the invention there is provided a process for the p~eparation of a titanium cornponent useful for the polymeri-zation of alkenes-l and for the copolymerization of alkenes-l with each other or with ethylene, which titanium component contains a halogenated titanium compound, an electron donor, and a metal halide which process comprises react-ing a combination of an organic aluminium compound and an organic magnesium compound with a halogenating agent of the formula RXm, wherein R is a hydro-carbon group, a hydrogen atom or a halogen atom,Xisa halogen atom, and m is a whole number from 1-10, to form the corresponding metal halide, the process further comprising combining the metal halide so formed with a titanium halide compound of tetravalent titanium and an electron donor.
According to another aspect of the present invention there is provided a process Eor the polymerization of alkenes-l and for the copolymeri-zation of alkenes-l with each other or with ethylene comprising the use of a catalyst system consisting of the above defined titanium component.
It is observed that from the Dutch "Terinzagelegging" No. 7711518 a catalyst for manu:Eacture of polyethylene is known which is prepared by re~
duction of tetra-butyl titanate with a mixed magnesium-aluminium alkyl, followed .~
8~
by de-activation oE any surplus of magnesium alkyl with hydrogen chloride, a~ter which a second quantity of tetra-butyl titanate is added. The Dutch "Terinzagelegging" No. 7605544 describes a similar catalyst product, obtained Q ~e by adding tetra-isopropyl-t~ p*~y~ titanate to the reaction product of a dibutyl magnesium-triethyl aluminium complex and hydrogen chloride. These known catalysts clearly differ from the catalytic titanium component according to the invention, while moreover these publications only give results about the polymerization of ethylene, whereby the stereospecificityof the catalyst is not involved.
The titanium component according to the invention improves the stereospecificity of the polymerization catalyst, at a very high level of activity. With this catalyst, polymers, for instance polypropylene, can be obtained with a very low halogen content, a very low titanium content, good particle size and good particle size distribution. As a result, the polymer has good processing properties and is little corrosive for the processing equipment.
The titanium component may contain any halogenated compound of bi-, tri- or tetravalent titanium, including compounds in which some of the titanium valencies have been taken up by atoms other than halogen atoms. The halogen in the halogenated titanium compound is preferably chlorine, but may also be bromine andlor iodine, for instance. Examples of suitable halogenated titanium compounds are TiC13, TiC13. 1/3 AlC13, TiC14, TiBr4~ TiI~, Ti(isobutoxy)2C12, Ti~phenoxy)C13 -2a-68~
and Ti(o methyl phenoxy)C13.
TiCl3 and TiCl4 are highly suitable, especially TiCl4.
For application in multi-stage polymerization processes, especially those in which more than hali an hour is normally r0quired ~or poly~erization in ths first stage before a second stag~ is started, it is oi special advantage i~ the halogenated titanium compound used is a titanium halide phenolate of the formula Ti X Ab, in which X
represents a halogen atom and A the acid r~ical o~ a phenol, n is a whole n~mher oi at least 1, and a and b are such numbers that a/n and 7G b/n are both 1-3, on the understanding that (a~b)/n is equal to 3-4.
The rate o~ decline ;n the activity of the catalyst is then substan-tially reduced, so t~at in mul~i-stag0 polymerization processes, ~or instance so-called block copolymeri~ations, in which in the iirst sta~e ior inst~noa i'or more than hal~ an hour propylene, butylene-l, 4-methyl pentylen~-1 or another alkene-1 with at least 3 carbon atoms Fer molecule is polym~rized, possibly in the presence o~ a minor quantity o~ ethylene, after which in a second stage another monomer or a monomer mixture oi a dif~erent composition is polymeri7ed in the presence o~ the polymer iormed in the first stage, ~o that block~ oi di~erent monomer composition may be pre~ent in ona polymer molecule, the resultant proportion o~ such bloc~ copolymsr is considerably higher.
The phenolate may be, for in~ance, the acid radical derived ~rom unsubstituted phenol or ~rcm a phenol in which one or more alkyl groups or alkoxy groups with ~or instance 1-6 carbon atoms per group have been substituted, ~or instance crssol, methoxy phenol, xylenol, ethyl phenol, propyl phenol, octyl phenol, dibutyl phenol, cumyl phenol or naphthol. Cresolates a~d methoxy phenolates are particularly ~uitable, while cresolates o~fer the advantage of particularly high stereospeci~icity oi the catalyst system. The benzene nucleus o~ the phenolate may contain other substituents which are non-detrimental in the polymerization reaction, such as one or mors halide substituents.
m e phenolate groups may have, ~or instanoe, 6 to 18 carbon atoms, pre-ierably 6-12 carbon atoms.
The halide phenola~e ratio in the titanium halide phenola~e is pre~erably ~rom 1 : 1 to 3 : 1. Besides the titanium halide phenolata, a phenolate-~ree tit&nium halide can be used in the halogenated titanium 8 ~
compound, i~ so desired. Preferably, a halide phenolate oi tetravalent titanium is used. The value o~ n is mostly 1, but may also be 2 or higher, especially i~ a polyphenolate is used.
Specii'ic examples o~ titanium halide phenolate~ to be used in the catalytic titanium component according to the invention are titanium (IV) trichloride monophenolate, titanium ~IV) dichloride di-phenolats, titanium (IV) trichloride mono-p-cresolate, titanium(III~-dichloride mono-o-cresolate, titanium (IV) monochloride tri-l-naphtholate, titanium (IV) trichloride mono-(p-chlorophenolate), titanium (IV) tribromide mono-p-cresolate, titaniu~ (IV) tribromide mono (xylenolate-isomsr mixture) and titanium (IV) monoiodide trianisolate. Such compounds can be obtained for in tance through conversion o~ the relevant tita~ium halide with the stoechiometric quantity o~ the relevant phenol, in which reaction the ralevant hydrogen halide is liberated, or through double conversion o~ a titanium halide with a metal phenolate, ~or instance an al~ali metal phanolate.
Ths catalytic titanium component according to the invention contains a metal halida obtained by conversion oi a combination oP
an organic aluminium compound and an organic magnesiu~ compound with the halogenating agent. In this metal halide the halogen: (aluminium ~-magnesium) atomic ratio is e.g. in the range t2.5 - 5) : 1, pre~erably in the range (4-5) : 1.
The conver~ion o~ the combination oP an organic aluminium compound and an organic magnesium compound to ~orm the corresponding matal halide may be o~fected, ~or instance, by precipitation o~ the metal halide from a solutlon o~ the org~ic motal compounds in a suitable solvent, by means o~ the halogenating agent. Suitable precipitation agents are, i'or instance, the hydrogen halides and aliphatic halogen compounds. The hQlogen in the halogenating agent is pre~erably chlorine, but may also be bromine or iodine, ~or instance.
The hydrogen halides may be introduced in the form o~ water iree gas, ior instance.
Other suitable halogenating agents are aliphatic halogen com-pounds, iorinstance aliphatichalogenatedhydrooarbonswith~ ~orinstance, 1-8 carbon atoms per molecule, in partioular alkyl chlorides. ExampleQ
are methyl chloride, methylene chloride, chloroform, ethyl bromide, ethylene dichlorida, i-propyl chloride, n~butyi iodide, etc, Other suitable precipitation agents are free halogens and interhalogen compounds, ~or instance Cl2, Br2, I2, ICl, IC13 or BrCl.
The organic aluminium compound prei'erably contains one or more hydrocarbon groups bonded diractly to the metal. The hydrocarbon groups preferably contain 1-10 carbon atoms. Examples are trialkyl or trialkenyl aluminium compounds, for instance triethyl aluminium, tri-propyl aluminium, triisobutyl aluminium, triisoprenyl aluminium, trihexyl aluminium and trioctyl aluminium; dialkyl aluminium hydrides, for instance diethyl aluminium hydride or diisobutyl aluminium hydride;
dialkyl aluminium halides, in particular a chloride or a bromide, di ethyl aluminium chloride and bromide being particularly suitable, while di-n-butyl aluminium chloride or methyl-n-butyl aluminium chloride, for instance, may also be used; and (mono)alkyl aluminium dihalides, ~or instance ethyl aluminium dichloride, n-butyl aluminium dichloride or n-hexyl aluminium dibromide. If a halogen-containing organic aluminium compound is used, the halogen is pr~erably the same as that in the halogenating agent used. Trialkyl aluminium compounds are preferrsd.
The organic magnesium compound may be, for instancs, a di-alkyl magn0sium or an alkyl magnesium halide. The hydrocarbon groups pr0ferably contain 1-10 carbon atoms again. Examples are ethyl magnesium chloride, n butyl magnesium chloride, i-propyl magn0sium bromide, 25 n-decyl magnesium iodide, di-n-butyl magnesium, di-i-amyl magnesium and ~i-n-octyl magnesium.
The conversion o~ the organic metal compounds into the metal halide may be e~ected in the absenc0 o~ a solvent, but lt is pr0~era-ble ~or the metal halide to be precipitated ~rom a solution of the orga-30 nic metal compounds in a suitable solvent. Examples oP suitable solventsare aliphatic, cycloaliphatic, aromatic and mixsd aromatic~aliphatic hydrocarbons, with 3-8 carbon atoms per molecule, which are inert under the reaction conditions, for instance butane, i-butana, n-hexane, n-heptane, cyclohexane, benzene, toluene and xylenes. Halogsnated hydro-carbons may also be used.
The temperature during the conversion may be, for instance,250-425 K, if a hydrogen halide is used as halogenating agent preferably about 290-340 K. The pressure is not a critical factor and is, ior instance, 10-1000 kPa. The reaction time may e.g. be 0.5-lO hours, preferably 1-4 hours.
In a suitabls mode oi realization of the process according to the invention, first an alkyl halide, for ins*ance n-butyl chloride, is converted into the alkyl magnesium halide with metallic magnesium in a hydrocarbon solvent, ~or instance n-heptane, ln a manner known in itseli, and subsequently or simultaneously a suitable aluminium co~po~md, for instance a trialkyl aluminium such as tri-n-butyl aluminium, is applied, so that a dissolved comple~ consisting o~ an organoaluminium compound and an alkyl magnesium compound ~ ~ormed.
Instaad o~ a trialkyl aluminium, it is also possible to add another organic aluminium compound, ior instance an alkoxy aluminium compound, an alkyl aluminium halide or the aluminium salt oi an organic acid, or ~tallic aluminium or an aluminium halide, ~or instance aluminium chloride, which is converted in situ into an organic alumini~m compound forming the complex. Th0 resultant solution o~ an organoaluminium~alkyl magnesium complex is subsequently treat0d with a gaseous h~drogen halide, ~or instance hydrogen chloride, or with an alkyl halide so that the metal halide i9 precipitated.
The aluminium: magnesium molar ratio in the combination of organometal compoundq used as starting material may be, ~or instance, 1 : 99 to 1 l.Other molar ratios are possible , but are not advan-tageo~s. This molar ratio is pre~erably 1 : 20 to 1 : 3, more in particular l : 10 to l : 4, When using combinations of organometal compounds with molpercentages organoaluminium compound with respeot to organomagnesium compound rising above 35, the activity o~ the obtainad catalyst systems decreases rapidly with increasing molpercent~ge~
1~ so desired, it is possible to incorporate ~urther metal ions in th0 metal halide, ior instance sodium, tin, silicon or germanium.
In a highly suitable mode o~ realization, the titanium co~po-nent according to the invention is prepared by converting a combination o~ an organic aluminium compound and an organic magnesium compound with the halogenating agent into the corresponding metal halide, which is converted with a titanium halide compound o~ tetravalent titanium.
~ It is observed that aiter the combination of the titanium halide compound with the metal halide used as carrier, the tetravalent 8 V ~ `
titanium may, ii so desired, be reduc~d to titanium o~ a lower valency, for instance tri- or bivalent titanium, in a known manner, so that the titanium component used need not necessarily contain tetravalent titanium.
Besides the halogenated titanium compound and metal halide used as carrier, the titanium component contains an electron donor. It is assumed that this donor is present in the ~orm oi' a complex with the halog3nated titanium coMpound. The elsctron donor used may be one or more oi the compounds used in the known manner in similar catalyst systsms, ~or in~tancs oxygencontaining electron donors such as water, alcohols, phenols, k0tones, aldehydes, acid halides, carboxylic acids, ssters, ethers and amides, or nitrogen-containing electron donors such as ammonia, amines, nitriles, isocyanates and nitro compounds.
Speci~ic 0~amples oi suitable el6ctron donors are alcohols with 1-18 carbon atoms per molecule, for instance methanol, ethanol, propanol, hexanol, stearyl alcohol, benzyl alcohol, phenyl ethyl alcohol or cumyl alcohol; phenols with 6-18 carbon atoms per molecule, ~or instance phenol, cre~ol, xylenol, ethyl phenol, propyl phenol, octyl phenol, dibutyl phenol, cumyl phenol or naphthol; ketones with 3-15 carbon atoms per molecule, ~or instance acetone, me~hyl athyl ketone, mathyl isobutyl ketone, acetophencne or ber~ophenone; aldehydes with
2-15 carbon atoms per molecule, ior instance ethanal, propanal, heptanal, ben~.aldehyde, tolualdehyde or naphthaldehyde; acid halies with 2-lS carbon atoms per molecule, ~or instance acetyl chloride, benzoyl chloride or toluyl chlorlde; acid amides with 2-15 carbon atoms par molecule, ~or instance formamide, acetamido, benzamide or toluamide;
amines with 2-18 carbon atoms per molecule, ~or instance methylamine;
ethylamine, diethylamine, triethylamins, tributylamine, pipsridine, tribenzylamine, aniline, pyridine, picoline or ethylene diamine;
nitrilss with 2-15 carbon atoms per molecule, ~or instance aca*onitrile, benzonitril~ or tolunitrile; or nitro compounds, ~or instance nitro-benzane. Pre~erence is given to ethers with 2-20 carbon atoms per molecule, ~or lnstance dimethyl ether, dlethyl ether, di-n-butyl ether, di-i-amyl ether, tetrahydro~uran, anisol0 or diph0nyl ether, and in particular organic esters with 2-40, in particular 2-18, carbon atom~
per molecule. The acid component o~ the 0ster mostly contain~ 1-9 carbon atoms per molecule or is a natural ~atty acid, while the alcohol 8 ~
component mostly contains 1-6 carbon atoms per molacul00 Example~ oi' suitable esters are methyl formate, cyclohexyl formate, ethyl ac0tate, vinyl acetate, amyl acetate, 2-ethyl h0xyl acetate, cyclohaxyl ac0tate, ethyl propionate, amyl propionate, methyl butyrate, ethyl v~leriate, methyl chloroacstate, athyl di-chloroacetate, methyl methacrylate, ethyl acrylate, n-butyl acrylate, ethyl crotonate, dimethyl maleate, ethyl cyclohexane carboxylata, methyl benzoate, ethyl baffzoate, i-butyl benzoate, octyl benzoate, cyclohexyl benzoate, phenyl benzoate, benzyl benzoate, phenyl ethyl benzoate, me~hyl toluate, 0thyl toluate, i-amyl toluate, methyl anisate, ethyl anisate, ~-butyrolacton, &~caprolacton, coumarin, phthalide and ethylene carbonate.
Particular preXerence iq given to esters derived ~rom aromatic acids, in particular estsrs o~ benzoic acid, sub~tituted or not with alkyl or alkoxy groups. Alkyl esters with 1-4 carbon atom3 per alkyl group, in particular methyl or ethyl esters oi' benzoic ,acid, o- or p-toluene carboxylic acid, p-msthoxy benzoic acid or ~ acid, are pre~erred in particular.
The various constituent elements of the titanium component may be combined in any known manner. Preferably, first a complex o~
the titanium halide compound and the alectron donor is prepa~ed.
The complexe~ of the titanium ha:Lid~ compound and the electron donor may be obtained in any know~ manner, i'or inatance by bringing tha co~ponents of th0 complex into contact with each other.
Th3 titanium halide compound may be applied to the carrier material in any known manner, for instance by simple mixing, pre~erably by grinding tvgether, for ins~ance in a ball ~ill, a vibratlon mill or r O, n beatsr mill. The mixing may he dona in the co-presence o~ an~3~i ~e or organic filler, i~or instance lithium chloride, calcium carbonate, calcium chloride, chromium(II)chloride, barium chloride, ~odium sulphate, sodium carbonate, titanium dioxide, sodium tetraborate, calcium orthophosphate, calcium sulphate, barium carbonate, aluminium sulphate, borium trioxids, aluminium oxida, silicon oxide, polyethylene, polypropylene or polystyrene. The fillar may also have been takan up in the carrier material beforehand. It is possible to first form a complex o~ the titanium halide compound and the electron donor and apply it ~^~ to the carrier, or al~o to first apply the non-complsxed titanium halide compound to the carrier and add the electron donor afterwards, t ~
either be~ore or after addition oP the organoaluminium component used in the complete catalyst. It may be advantageous to treat the titanium component with a halogen or an interhalogen compound, for instance bromium, preferably in the absence of an inactive solvent.
The tit~nium content o~ the titanium component on the carrier usually amounts to between 0.1 and 10 % by wt. m0 titanium : magnesium :
aluminium weight ratio preferably is 1 : (0.5-20):~0.1-5~, more in particular 1 : (0.5-2.5~:(0.2-l). Preferably, the 01ectron donor i9 presen~ in the titanium component in a quantity of ~or instance ~ to 5 molecules per titanium atom. A typical example of the composition o~
the titanium component, although varying in dependence on the circum-st~ces o~ the catalyst preparation, is: 2-10 % by wt. of titanium, 16-25 % by ~t. o~ magnesium, 1.5-10 % by wt: of aluminium, 45-65 by wt. o~ halogen and 5 25 % by wt. of the electron donor.
The titanium component in the prepared polymerization catalyst i9 used in combination with an organometallic component derivsd ~rom a metal of one o~ the groups I-III of the PerLodic System with a hydro-carbon radical bonded directly to the metal.
Examples are trialkyl aluminium compounds, alkyl aluminium alkoxides, alkyl aluminium hydrides, alkyl aluminium halides, dialkyl zlnc compounds and dialkyl magn0sium compounds, of which the organo-aluminium compounds are particularly suitabLe. Examples of the organo-aluminium compounds are trialkyl or trialkellyl aluminium compounds, for instance triethyl aluminium9 tripropyl aluminium, triisobutyl aluminium~
tri-isoprenyl aluminium, trihexyl aluminium and trioctyl aluminium;
alkyl aluminium compounds in which a number o~ the aluminium atoms are connected via an oxygan or nitrogen atom, ior instance ~5)2AlOAl(C2H5)2, (i-C H ) AlOAl(i-C4Hg)2 or ~C2H5)2AINHA ( 2 5 2 aluminium hydrides such as diethyl aluminium hydride or diisobutyl aluminium hydride; dialkyl aluminium halides, in particular a chlorida or a bro~ide, diathyl aluminium chloride and bromide being particularly suitable, while also other dialkyl aluminiu~ halides with pre~erably 1-10 carbon atoms in the alkyl group, such as for instance di-n-butyl aluminium chloride and methyl-n-butyl aluminium chloride, can be used;
and dialkyl aluminium alkoxides or phenoxides, for instance diethyl _ ethoxy aluminium or di~thyl phsnoxy aluminium. The trialkyl aluminium compounds deserve most pre~erencs.
The organometal compound may also contain a trialkyl aluminium compound as well as a dialkyl aluminium halide or a mixture o~ a dialkyl magnesium compound and a mono-alkyl aluminium dihalide. The alkyl groups of the organoaluminium compounds preferably contain 1-10 carbon atoms each. The alkyl groupq o~ the dialkyl magnesium compound prei'erably contain 1-10 carbon atoms each or are a palmityl or stearyl group. Examples o~ suitable dialkyl magnesium compounds are diethyl magne3ium, di-n-butyl magnesium, di-n-hexyl magne3ium and di-n-octyl magnesium. The mono-alkyl aluminium dihalide pre~erably is a chloride or a bromide. Ethyl aluminium dichloride or bromide is particularly ~uitable, but also other monoalkyl alum nium dihalides with pre~erably 1-10 carbon atoms in the alkyl group may be u~ed, such as isopropyl aluminium dichloride, n-butyl aluminium dibromide or n-octyl aluminium dichloride. The molar ratio between the dialkyl magnesium compound and the monoalkyl aluminium dihalide may be betwesn, i'or ~nstance, 0.1 and 1, pref*rably between 0.3 and 0.6. Too high a mole ratio leads to insu~i'iciently stereospeci~ic catalysts, while insu~icient catalyst activity result~ i~ it is too low.
The organometal component pre~erably contains a comple~ o~
an organic metal compound, in particular a trialkyl aluminium compound, wi~h an es~er o~ an oxygen-containing organic acid. Suitable esters are the same e~ter3 as may ba used in the titanium halids com-ponerlt, in particular again the esters oi' a;romatic carboxylic acids.
For brevity's sake, re~erence is made to the ~oregoing. Pre~erably, part o~ the organic metal compound, i'or instance 50-80 %, is present in a non-complex condition.
The Al:Ti atom ra*io is generally betwaen 10 and 1000; the molecule-atom ratio o~ Lewis base bonded in total in the eatalyst to Ti i3 in general between 5 and 500.
The method according to the inventlon is used in particular in stereospeci~ic polymerization oi alkenes-1 with 3~6 carbon atoms p0r molecule, such as propylane, butylane-1, 4-methyl pentylene-1 and hexylene-1, and in the copolymerization o~ the~e alkeneq-l with each o~her and/or with ethylene. Copolymers with random arrangement o~ the various monomer units as well as block copolymers can be manu~actured.
I~ ethylene is used as a comonomer, it is normally ~Ised in minor quantities, ~or in~tance 30 % by wt. at most, more in particular between 8 ~ ~) 1 and lS % by wt.~ is incorporated in th~ polymer. The process according to the invention is o~ importance in particular ~or manufacture o~
isotactic po~ypropylene, random copolym~rs oi' propylene with minor quan~ities o~ ethylene and block copolymers of propylane and ethylene.
For the manu~acture o~ block copolymers, any desired sequence of monomer addltion may be applied.
The circumstances under ~hich the polymerization reaction with the catalytic titanium componant according to the invention is carriad out do not deviate i'rom those ~nown in the art. The reaction may bo carried ou* in ths gas phaqe or in the presence oi~ a dispersan~. The dispersant may be inert or also a monomer in liquid ~orm. Examples o~
suitable dispersants are aliphatic, cycloaliphatic, aromatlc and mixed aromatic/aliphatic hydrocarbons wlth 3-8 carbon atoms per molecule, such as propylene, butylene-1, butane, iqobutane, n-hexane, n-heptane, lS cyclohexane, benzene, toluen0 and the xylenes.
In the case ott polymerization in the liquid phase, it is preierable i'or the concentration o~ tha tltanium component to be set i ~ at 0.001-0.5 mmole, calculated as titanium ~ om, and the concentration oi the organometal compound at about 0.1-6~ mmole, both per litre oi liquid phase~
The polymerization temperature is mostly between 190 and 475 K, preierably between 310 and 375 K. The pressure may be betwaen 100 and 3000 kPa, ~or instance.
If so desired~ it is possible to control the molecular weight o$ the polyner during the polymerization proce ~, ~or inRtance through the presence o~ hydrogen or another known molecular weight reFulator.
The polymerlzation reaction may ba carried out as a batch process or as a continuous procass.
It has been ~ound that a ~urther considerable reduction o~ the catalyst reYidue3 content, espeoially that o~ halogen, can be achieved by carrying out the separation o~ the solid polymer ai'ter completion of the polymeri~atio~ under exclusion o~ the air.
The invention will now be elucidated by means o~ the i'ollowing non-rastrictive examples and the comparative experiment.
8 ~ ~
Examples and com~ativa experiment Example I
A. Preparation of_t_e catalytic titanium component At 273 R 6.5 ml oi' water-i'ree ethyl benzoate (EB)~ dissolved 5 in 75 ml o~ water-~rae gasoline, is introduced into a solution o~ 5 ml o~ TiC14 in 125 ml of gasolina, ~lushed with dry nitrogen.
The rasultan~ precipitata o TiC14.EB is separated of~ by ~iltration and dried.
100 ml oi' a solution containing 0.3 mole o~ dibutyl magnes~um 10 and 0003 mole o~ triethyl aluminium per litre o~ hexane i9 introduced into a three-nec~ flask, ~lushed with nitrogen and provided with a mechanical agitator and a re~lux condensor. A i'low o~ dry HCl gas is introduced, resulting in the ~ormation o~ a yellowish precipitate.
During the reaction, the ~emperature rised. The gas ~low i9 maintained 15 ~or 1 hour a~ter the temperature has reached its ma~imu~.
The precipitate o~ metal chlorlde ls separatsd o~ by ~iltration, washad with hexane and dried. Ths composition o~ thiq product is: 20,1 % o~ ~g, 1.9 % o~ Al, 61.1 ~ o~ Cl and 16.5 % of organic ma~erial (in % by wt.).
amines with 2-18 carbon atoms per molecule, ~or instance methylamine;
ethylamine, diethylamine, triethylamins, tributylamine, pipsridine, tribenzylamine, aniline, pyridine, picoline or ethylene diamine;
nitrilss with 2-15 carbon atoms per molecule, ~or instance aca*onitrile, benzonitril~ or tolunitrile; or nitro compounds, ~or instance nitro-benzane. Pre~erence is given to ethers with 2-20 carbon atoms per molecule, ~or lnstance dimethyl ether, dlethyl ether, di-n-butyl ether, di-i-amyl ether, tetrahydro~uran, anisol0 or diph0nyl ether, and in particular organic esters with 2-40, in particular 2-18, carbon atom~
per molecule. The acid component o~ the 0ster mostly contain~ 1-9 carbon atoms per molecule or is a natural ~atty acid, while the alcohol 8 ~
component mostly contains 1-6 carbon atoms per molacul00 Example~ oi' suitable esters are methyl formate, cyclohexyl formate, ethyl ac0tate, vinyl acetate, amyl acetate, 2-ethyl h0xyl acetate, cyclohaxyl ac0tate, ethyl propionate, amyl propionate, methyl butyrate, ethyl v~leriate, methyl chloroacstate, athyl di-chloroacetate, methyl methacrylate, ethyl acrylate, n-butyl acrylate, ethyl crotonate, dimethyl maleate, ethyl cyclohexane carboxylata, methyl benzoate, ethyl baffzoate, i-butyl benzoate, octyl benzoate, cyclohexyl benzoate, phenyl benzoate, benzyl benzoate, phenyl ethyl benzoate, me~hyl toluate, 0thyl toluate, i-amyl toluate, methyl anisate, ethyl anisate, ~-butyrolacton, &~caprolacton, coumarin, phthalide and ethylene carbonate.
Particular preXerence iq given to esters derived ~rom aromatic acids, in particular estsrs o~ benzoic acid, sub~tituted or not with alkyl or alkoxy groups. Alkyl esters with 1-4 carbon atom3 per alkyl group, in particular methyl or ethyl esters oi' benzoic ,acid, o- or p-toluene carboxylic acid, p-msthoxy benzoic acid or ~ acid, are pre~erred in particular.
The various constituent elements of the titanium component may be combined in any known manner. Preferably, first a complex o~
the titanium halide compound and the alectron donor is prepa~ed.
The complexe~ of the titanium ha:Lid~ compound and the electron donor may be obtained in any know~ manner, i'or inatance by bringing tha co~ponents of th0 complex into contact with each other.
Th3 titanium halide compound may be applied to the carrier material in any known manner, for instance by simple mixing, pre~erably by grinding tvgether, for ins~ance in a ball ~ill, a vibratlon mill or r O, n beatsr mill. The mixing may he dona in the co-presence o~ an~3~i ~e or organic filler, i~or instance lithium chloride, calcium carbonate, calcium chloride, chromium(II)chloride, barium chloride, ~odium sulphate, sodium carbonate, titanium dioxide, sodium tetraborate, calcium orthophosphate, calcium sulphate, barium carbonate, aluminium sulphate, borium trioxids, aluminium oxida, silicon oxide, polyethylene, polypropylene or polystyrene. The fillar may also have been takan up in the carrier material beforehand. It is possible to first form a complex o~ the titanium halide compound and the electron donor and apply it ~^~ to the carrier, or al~o to first apply the non-complsxed titanium halide compound to the carrier and add the electron donor afterwards, t ~
either be~ore or after addition oP the organoaluminium component used in the complete catalyst. It may be advantageous to treat the titanium component with a halogen or an interhalogen compound, for instance bromium, preferably in the absence of an inactive solvent.
The tit~nium content o~ the titanium component on the carrier usually amounts to between 0.1 and 10 % by wt. m0 titanium : magnesium :
aluminium weight ratio preferably is 1 : (0.5-20):~0.1-5~, more in particular 1 : (0.5-2.5~:(0.2-l). Preferably, the 01ectron donor i9 presen~ in the titanium component in a quantity of ~or instance ~ to 5 molecules per titanium atom. A typical example of the composition o~
the titanium component, although varying in dependence on the circum-st~ces o~ the catalyst preparation, is: 2-10 % by wt. of titanium, 16-25 % by ~t. o~ magnesium, 1.5-10 % by wt: of aluminium, 45-65 by wt. o~ halogen and 5 25 % by wt. of the electron donor.
The titanium component in the prepared polymerization catalyst i9 used in combination with an organometallic component derivsd ~rom a metal of one o~ the groups I-III of the PerLodic System with a hydro-carbon radical bonded directly to the metal.
Examples are trialkyl aluminium compounds, alkyl aluminium alkoxides, alkyl aluminium hydrides, alkyl aluminium halides, dialkyl zlnc compounds and dialkyl magn0sium compounds, of which the organo-aluminium compounds are particularly suitabLe. Examples of the organo-aluminium compounds are trialkyl or trialkellyl aluminium compounds, for instance triethyl aluminium9 tripropyl aluminium, triisobutyl aluminium~
tri-isoprenyl aluminium, trihexyl aluminium and trioctyl aluminium;
alkyl aluminium compounds in which a number o~ the aluminium atoms are connected via an oxygan or nitrogen atom, ior instance ~5)2AlOAl(C2H5)2, (i-C H ) AlOAl(i-C4Hg)2 or ~C2H5)2AINHA ( 2 5 2 aluminium hydrides such as diethyl aluminium hydride or diisobutyl aluminium hydride; dialkyl aluminium halides, in particular a chlorida or a bro~ide, diathyl aluminium chloride and bromide being particularly suitable, while also other dialkyl aluminiu~ halides with pre~erably 1-10 carbon atoms in the alkyl group, such as for instance di-n-butyl aluminium chloride and methyl-n-butyl aluminium chloride, can be used;
and dialkyl aluminium alkoxides or phenoxides, for instance diethyl _ ethoxy aluminium or di~thyl phsnoxy aluminium. The trialkyl aluminium compounds deserve most pre~erencs.
The organometal compound may also contain a trialkyl aluminium compound as well as a dialkyl aluminium halide or a mixture o~ a dialkyl magnesium compound and a mono-alkyl aluminium dihalide. The alkyl groups of the organoaluminium compounds preferably contain 1-10 carbon atoms each. The alkyl groupq o~ the dialkyl magnesium compound prei'erably contain 1-10 carbon atoms each or are a palmityl or stearyl group. Examples o~ suitable dialkyl magnesium compounds are diethyl magne3ium, di-n-butyl magnesium, di-n-hexyl magne3ium and di-n-octyl magnesium. The mono-alkyl aluminium dihalide pre~erably is a chloride or a bromide. Ethyl aluminium dichloride or bromide is particularly ~uitable, but also other monoalkyl alum nium dihalides with pre~erably 1-10 carbon atoms in the alkyl group may be u~ed, such as isopropyl aluminium dichloride, n-butyl aluminium dibromide or n-octyl aluminium dichloride. The molar ratio between the dialkyl magnesium compound and the monoalkyl aluminium dihalide may be betwesn, i'or ~nstance, 0.1 and 1, pref*rably between 0.3 and 0.6. Too high a mole ratio leads to insu~i'iciently stereospeci~ic catalysts, while insu~icient catalyst activity result~ i~ it is too low.
The organometal component pre~erably contains a comple~ o~
an organic metal compound, in particular a trialkyl aluminium compound, wi~h an es~er o~ an oxygen-containing organic acid. Suitable esters are the same e~ter3 as may ba used in the titanium halids com-ponerlt, in particular again the esters oi' a;romatic carboxylic acids.
For brevity's sake, re~erence is made to the ~oregoing. Pre~erably, part o~ the organic metal compound, i'or instance 50-80 %, is present in a non-complex condition.
The Al:Ti atom ra*io is generally betwaen 10 and 1000; the molecule-atom ratio o~ Lewis base bonded in total in the eatalyst to Ti i3 in general between 5 and 500.
The method according to the inventlon is used in particular in stereospeci~ic polymerization oi alkenes-1 with 3~6 carbon atoms p0r molecule, such as propylane, butylane-1, 4-methyl pentylene-1 and hexylene-1, and in the copolymerization o~ the~e alkeneq-l with each o~her and/or with ethylene. Copolymers with random arrangement o~ the various monomer units as well as block copolymers can be manu~actured.
I~ ethylene is used as a comonomer, it is normally ~Ised in minor quantities, ~or in~tance 30 % by wt. at most, more in particular between 8 ~ ~) 1 and lS % by wt.~ is incorporated in th~ polymer. The process according to the invention is o~ importance in particular ~or manufacture o~
isotactic po~ypropylene, random copolym~rs oi' propylene with minor quan~ities o~ ethylene and block copolymers of propylane and ethylene.
For the manu~acture o~ block copolymers, any desired sequence of monomer addltion may be applied.
The circumstances under ~hich the polymerization reaction with the catalytic titanium componant according to the invention is carriad out do not deviate i'rom those ~nown in the art. The reaction may bo carried ou* in ths gas phaqe or in the presence oi~ a dispersan~. The dispersant may be inert or also a monomer in liquid ~orm. Examples o~
suitable dispersants are aliphatic, cycloaliphatic, aromatlc and mixed aromatic/aliphatic hydrocarbons wlth 3-8 carbon atoms per molecule, such as propylene, butylene-1, butane, iqobutane, n-hexane, n-heptane, lS cyclohexane, benzene, toluen0 and the xylenes.
In the case ott polymerization in the liquid phase, it is preierable i'or the concentration o~ tha tltanium component to be set i ~ at 0.001-0.5 mmole, calculated as titanium ~ om, and the concentration oi the organometal compound at about 0.1-6~ mmole, both per litre oi liquid phase~
The polymerization temperature is mostly between 190 and 475 K, preierably between 310 and 375 K. The pressure may be betwaen 100 and 3000 kPa, ~or instance.
If so desired~ it is possible to control the molecular weight o$ the polyner during the polymerization proce ~, ~or inRtance through the presence o~ hydrogen or another known molecular weight reFulator.
The polymerlzation reaction may ba carried out as a batch process or as a continuous procass.
It has been ~ound that a ~urther considerable reduction o~ the catalyst reYidue3 content, espeoially that o~ halogen, can be achieved by carrying out the separation o~ the solid polymer ai'ter completion of the polymeri~atio~ under exclusion o~ the air.
The invention will now be elucidated by means o~ the i'ollowing non-rastrictive examples and the comparative experiment.
8 ~ ~
Examples and com~ativa experiment Example I
A. Preparation of_t_e catalytic titanium component At 273 R 6.5 ml oi' water-i'ree ethyl benzoate (EB)~ dissolved 5 in 75 ml o~ water-~rae gasoline, is introduced into a solution o~ 5 ml o~ TiC14 in 125 ml of gasolina, ~lushed with dry nitrogen.
The rasultan~ precipitata o TiC14.EB is separated of~ by ~iltration and dried.
100 ml oi' a solution containing 0.3 mole o~ dibutyl magnes~um 10 and 0003 mole o~ triethyl aluminium per litre o~ hexane i9 introduced into a three-nec~ flask, ~lushed with nitrogen and provided with a mechanical agitator and a re~lux condensor. A i'low o~ dry HCl gas is introduced, resulting in the ~ormation o~ a yellowish precipitate.
During the reaction, the ~emperature rised. The gas ~low i9 maintained 15 ~or 1 hour a~ter the temperature has reached its ma~imu~.
The precipitate o~ metal chlorlde ls separatsd o~ by ~iltration, washad with hexane and dried. Ths composition o~ thiq product is: 20,1 % o~ ~g, 1.9 % o~ Al, 61.1 ~ o~ Cl and 16.5 % of organic ma~erial (in % by wt.).
3.1 g o~ the metal chloride obtained and 3.4 g of the TiC14.EB co~plex obtained are succe3sively lntroduced into a stainless steel ball mill with 8 balls. 'rhs mixture i9 ground for 17 hours in a nltrogen atmosphere.
B. Polym~rization 1.3 1 of gasoline, 2.5 ml o~ triiqobutyl aluminium (TI~A~, 0.25 ml oi sthyl benzoate and 0.07 g o~ the titanium component obtained as described under A ar~ introduced into a stainles3 steel reactor, llushed with dry nitrogen and provided ~lth a mechanical agitator. '~he pressure i~ raiced to and maintainad at 700 kPa by leading in propylene.
30 The temperature ls raised to and maintained at 333 K. A~ter a polymari-zation time o~ 2 hours, the supply o~ propylene i5 stoppad, the pressure is released and the polymar suspension is rsmoved ~ro~ the reactor. The polymer is separated o~ by filtration under exclu-~ion o~
the air.
o rn~le A The polymerization activity amounts to 1110 g PP/~o Ti.h and the soluble polymer content is 4.0 %. The average particle diametsr (d50~ i5 700 ~mO The polymar con~ains 7 wt. ppm o~ ~itanium and 115 wt. ppm o~ chlorine. PP stands ~or polypropylene here.
Example II
-The polymerization is carried out in a manner analogous to that in exa~ple IB, but 'llOW O.5 Nl o~ H2 is introduced into the reactor prior tc supplying propylene.
The polymerization activity amount9 to 1070 g PP/mmole Ti.h and the soluble polymer content i~ 4.3 ~. The average particle diameter is 680 ~m.
E~ample III
Th9 polymerization is carried out in a manner analogous to that in example IB, but now OO~S ml of ethyl benzoate i~ used in the TI~ co-catalyst.
The polymerization activity now amounts to 660 g PP/mmole Ti.h and the solubls polymer content is 2.4 %. The average particle diameter (d50) is 590~ m.
Comparative e~periment A. Pre~aration o~ the titanium component Anhydrous MgC12, commercially availa~le, is treated with CO
and C12 at 670 K in order to remove residual H20 and MgO. 3.0 g oi' $his MgCl2 and 30~ g of TiCl4.E~ are ground ~or 17 hour~ in a stainless steel ball mill in an atmo.sphexe o~ dry nitrogen.
B. Polymerizatlon The polymerization ~s carried out in a manner analogous to ~hat in example IB, but now 0.075 g oi' the titanium component obtained as described under A o~ this comparative experiment i9 used Ths poly~erization activity amounts to 810 g PP/~rTi.h and the soluble polymer content i8 6.8 ~. The average partlcle diameter (d50) amounts to 400 ~m. The titanium content of th0 polymer ~lltered oi~ amounts to 12 ~t. ppm and the chlorine content is 200 wt. ppm.
Example IV
A, Prepa~ation o~ ths titanium component 100 ml o~ a solution contalning 003 mole of dibutyl magnssium and 0.06 mole o~ triethyl aluminium per litre is introduced into a S three-neck -~lask ~lushed with nitrogan and providad with a mechanical agitator and a re~lux condensor. A ~low o~ dry HCl gas is introduc~d, resulting in the ~ormation oi a yellowish precipitate. During the reaction, the temperature rijes and ~he gas $10w is maintained for one hour ai'ter the temperature has reached it~ maximum. The precipitate o~
metal chloride i5 separated oi'~ by ~iltration, washed and dried. The composition of this product is 19.4 % o~ Mg, 3.6 % o~ Al and 62.3 %
o~ Cl.
3.2 g of the metal chloride obtain~d and 3.4 g o~ the TiCl4;
ethyl b0nzoate complex are introduced into a stainless steel ball mill.
This mixture is ground ~or 17 hours in a nitrogen a~mosphere.
B. Polyms i ation The polymerization ls carrled out ~n a manner analogous to that in ex~mple IB, but now O.G~5 g oi the titanlum component o~
axampl~ IV A i8 ussd.
i' ~ ~n~ot~
The polymerization activity amounts to 1170 g PP/~l~ Ti.h and the dissolved polymer cont~nt i5 4 . 3 %. The aYeraga particle diametsr (d50) o~ the poly~er is 700 ~m. The titanium content o~ the polymer i'iltered o~ amounts to 7 ~t. ppm and the chlorine content i9 110 Wt.
ppm.
Example V
A, Preparation o~ ths titani m componen_ The metal chloride is prepared in the ~ame manner a4 de~crlbed in example IV A, but now 0.075 mole of triethyl aluminium iq used.
3.1 g oi the metal chloride obtained and 3.4 g o~ TiCl~.ethyl benzoate are introduced into a stainless steel ball mill. This mixture is ground ~or 17 hours in a nitrogen atmosphsre.
B. Polymerization The polymerization i9 carried out in a manner analogous to that in example IB, but now 0.068 g o~ ~he titanium component o~ sxample 1 ~5~8~) V A is used.
The polymexization activity amounts to 1560 g PP/m~ole Ti.h and the dissolved polymer content amounts to 4.1 %. The averago paxticle diameter of the polymer is 725 ~m.
Example VI
A. Prep~ration o~ the titaniu _ component The me*al chlorid0 is prepared in the same manner as doscribed in e~ample IV A, but now 0.09 mols of triethyl aluminit~ is used.
3.2 g o~ ~e metal chloride obtained and 3.4 g of TiCl4.ethyl benzoate are introduced into a stainless steel ball mill. This mixture is ground i'or 17 hours in a nitrogen atmosphere.
B. Polymerization The polymerlzation iq carried out in a manner analogous to that in example IB, but no~ 0.070 g oi the titanium component of exampla VI A i9 usod.
The polymerization activity amounts to 1400 g PP/Ee~Ti.h and the dissolved polymer content is 4.3 %. The average particle diamster o~ the polymer i9 700 ~m. The titanium content o~ the polymer ~iltered of~ amounts to 6 wt. ppm and the c,hlorine content ls 75 wt. ppm.
20 ~9~
1.3 1 o~ gasoline, 2rS ml 0~ TIBA, 0.25 ml o~ ethyl benzoate, 0.070 g o~ the tltanium component ~rom example VI A and 250 N ml o~
hydrogen are introduced into a stainless steel reactor, ~lushed wlth dry nitro~en and provlded ~lth a mechanical agitator. The pressure is raisad to and maintained at 700 kPa by leading in propylene. The temperature is raised to and maintained at 333 K. A~t~r a polymerization time oP 2 hours, the pressure is relea3ed to 100 kPa, 500 N ml o~ hydrogen are added, and then a mix~re o~ 17 vol. % o~ propylene and 83 vol. % o~ ethylene is led in, whereby tha pressure i~ raised to 150 kPa. The pol~merization is continued during 2 hours at 333 K and 150 kPa. Therea~ter ~he polymerization is stoppod and the polymer isolatad by ~iltration under e~clusion o~ ~he air.
360 g oi polymer are obtained, with an ethylens content o~
13 wt. % (measured by means o~ in~rared spectroscopy); the soluble polymer content amounts to ~.1 % with respect ~o total polymer ~ormed.
B. Polym~rization 1.3 1 of gasoline, 2.5 ml o~ triiqobutyl aluminium (TI~A~, 0.25 ml oi sthyl benzoate and 0.07 g o~ the titanium component obtained as described under A ar~ introduced into a stainles3 steel reactor, llushed with dry nitrogen and provided ~lth a mechanical agitator. '~he pressure i~ raiced to and maintainad at 700 kPa by leading in propylene.
30 The temperature ls raised to and maintained at 333 K. A~ter a polymari-zation time o~ 2 hours, the supply o~ propylene i5 stoppad, the pressure is released and the polymar suspension is rsmoved ~ro~ the reactor. The polymer is separated o~ by filtration under exclu-~ion o~
the air.
o rn~le A The polymerization activity amounts to 1110 g PP/~o Ti.h and the soluble polymer content is 4.0 %. The average particle diametsr (d50~ i5 700 ~mO The polymar con~ains 7 wt. ppm o~ ~itanium and 115 wt. ppm o~ chlorine. PP stands ~or polypropylene here.
Example II
-The polymerization is carried out in a manner analogous to that in exa~ple IB, but 'llOW O.5 Nl o~ H2 is introduced into the reactor prior tc supplying propylene.
The polymerization activity amount9 to 1070 g PP/mmole Ti.h and the soluble polymer content i~ 4.3 ~. The average particle diameter is 680 ~m.
E~ample III
Th9 polymerization is carried out in a manner analogous to that in example IB, but now OO~S ml of ethyl benzoate i~ used in the TI~ co-catalyst.
The polymerization activity now amounts to 660 g PP/mmole Ti.h and the solubls polymer content is 2.4 %. The average particle diameter (d50) is 590~ m.
Comparative e~periment A. Pre~aration o~ the titanium component Anhydrous MgC12, commercially availa~le, is treated with CO
and C12 at 670 K in order to remove residual H20 and MgO. 3.0 g oi' $his MgCl2 and 30~ g of TiCl4.E~ are ground ~or 17 hour~ in a stainless steel ball mill in an atmo.sphexe o~ dry nitrogen.
B. Polymerizatlon The polymerization ~s carried out in a manner analogous to ~hat in example IB, but now 0.075 g oi' the titanium component obtained as described under A o~ this comparative experiment i9 used Ths poly~erization activity amounts to 810 g PP/~rTi.h and the soluble polymer content i8 6.8 ~. The average partlcle diameter (d50) amounts to 400 ~m. The titanium content of th0 polymer ~lltered oi~ amounts to 12 ~t. ppm and the chlorine content is 200 wt. ppm.
Example IV
A, Prepa~ation o~ ths titanium component 100 ml o~ a solution contalning 003 mole of dibutyl magnssium and 0.06 mole o~ triethyl aluminium per litre is introduced into a S three-neck -~lask ~lushed with nitrogan and providad with a mechanical agitator and a re~lux condensor. A ~low o~ dry HCl gas is introduc~d, resulting in the ~ormation oi a yellowish precipitate. During the reaction, the temperature rijes and ~he gas $10w is maintained for one hour ai'ter the temperature has reached it~ maximum. The precipitate o~
metal chloride i5 separated oi'~ by ~iltration, washed and dried. The composition of this product is 19.4 % o~ Mg, 3.6 % o~ Al and 62.3 %
o~ Cl.
3.2 g of the metal chloride obtain~d and 3.4 g o~ the TiCl4;
ethyl b0nzoate complex are introduced into a stainless steel ball mill.
This mixture is ground ~or 17 hours in a nitrogen a~mosphere.
B. Polyms i ation The polymerization ls carrled out ~n a manner analogous to that in ex~mple IB, but now O.G~5 g oi the titanlum component o~
axampl~ IV A i8 ussd.
i' ~ ~n~ot~
The polymerization activity amounts to 1170 g PP/~l~ Ti.h and the dissolved polymer cont~nt i5 4 . 3 %. The aYeraga particle diametsr (d50) o~ the poly~er is 700 ~m. The titanium content o~ the polymer i'iltered o~ amounts to 7 ~t. ppm and the chlorine content i9 110 Wt.
ppm.
Example V
A, Preparation o~ ths titani m componen_ The metal chloride is prepared in the ~ame manner a4 de~crlbed in example IV A, but now 0.075 mole of triethyl aluminium iq used.
3.1 g oi the metal chloride obtained and 3.4 g o~ TiCl~.ethyl benzoate are introduced into a stainless steel ball mill. This mixture is ground ~or 17 hours in a nitrogen atmosphsre.
B. Polymerization The polymerization i9 carried out in a manner analogous to that in example IB, but now 0.068 g o~ ~he titanium component o~ sxample 1 ~5~8~) V A is used.
The polymexization activity amounts to 1560 g PP/m~ole Ti.h and the dissolved polymer content amounts to 4.1 %. The averago paxticle diameter of the polymer is 725 ~m.
Example VI
A. Prep~ration o~ the titaniu _ component The me*al chlorid0 is prepared in the same manner as doscribed in e~ample IV A, but now 0.09 mols of triethyl aluminit~ is used.
3.2 g o~ ~e metal chloride obtained and 3.4 g of TiCl4.ethyl benzoate are introduced into a stainless steel ball mill. This mixture is ground i'or 17 hours in a nitrogen atmosphere.
B. Polymerization The polymerlzation iq carried out in a manner analogous to that in example IB, but no~ 0.070 g oi the titanium component of exampla VI A i9 usod.
The polymerization activity amounts to 1400 g PP/Ee~Ti.h and the dissolved polymer content is 4.3 %. The average particle diamster o~ the polymer i9 700 ~m. The titanium content o~ the polymer ~iltered of~ amounts to 6 wt. ppm and the c,hlorine content ls 75 wt. ppm.
20 ~9~
1.3 1 o~ gasoline, 2rS ml 0~ TIBA, 0.25 ml o~ ethyl benzoate, 0.070 g o~ the tltanium component ~rom example VI A and 250 N ml o~
hydrogen are introduced into a stainless steel reactor, ~lushed wlth dry nitro~en and provlded ~lth a mechanical agitator. The pressure is raisad to and maintained at 700 kPa by leading in propylene. The temperature is raised to and maintained at 333 K. A~t~r a polymerization time oP 2 hours, the pressure is relea3ed to 100 kPa, 500 N ml o~ hydrogen are added, and then a mix~re o~ 17 vol. % o~ propylene and 83 vol. % o~ ethylene is led in, whereby tha pressure i~ raised to 150 kPa. The pol~merization is continued during 2 hours at 333 K and 150 kPa. Therea~ter ~he polymerization is stoppod and the polymer isolatad by ~iltration under e~clusion o~ ~he air.
360 g oi polymer are obtained, with an ethylens content o~
13 wt. % (measured by means o~ in~rared spectroscopy); the soluble polymer content amounts to ~.1 % with respect ~o total polymer ~ormed.
Claims (28)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. Catalytic titanium component useful for the polymerization of alkenes-1 and for the copolymerization of alkenes-1 with each other or with ethylene, which titanium component contains a halogenated titanium compound, an electron donor, and a metal halide obtained by conversion of an organic metal compound with a halogenating agent of the formula RXm, wherein R is a hydrocarbon group, a hydrogen atom or a halogen atom, X is a halogen atom, and m is a whole number from 1-10, characterized in that the metal halide has been obtained by conversion of a combination of an organic aluminium com-pound and an organic magnesium compound with the halogenating agent into the corresponding metal halide.
2. Titanium component according to claim 1, characterized in that the halogenated titanium compound is TiC13 or TiC14.
3. Titanium component according to claim 1, characterized in that the halogenated titanium compound is a titanium halide phenolate of the formula TinXaAb, in which X represents a halogen atom and A the acid radical of a phenol, n is a whole number of at least 1, and a and b are such numbers that a/n and b/n are both 1-3, on the understanding that (a+b)/n is equal to 3-4.
4. Titanium component according to claim 3, characterized in that the titanium halide phenolate is a titanium (IV) trichloride monophenolate.
5. Titanium component according to claim 1, 2 or 3, characterized in that the aluminium:magnesium molar ratio in the metal halide is 1:99 to 1:1.
6. Titanium component according to claim 1, 2 or 3, characterized in that the aluminium:magnesium molar ratio in the metal halide is 1:10 to 1:4.
7. Titanium component according to claim 1, 2 or 3, characterized in that the electron donor is an ether with 2-20 carbon atoms per molecule.
8. Titanium component according to claim 1, 2 or 3, characterized in that the electron donor is an ester, the acid component of which contains 1-9 carbon atoms per molecule or is a natural fatty acid, while the alcohol component contains 1-6 carbon atoms per molecule.
9. Titanium component according to claim 1, 2 or 3, characterized in that the electron donor is an ester derived from an aromatic acid.
10. Titanium component according to claim 1, 2 or 3, characterized in that the electron donor is an alkyl ester with 1-4 carbon atoms per alkyl group of benzoic acid, o- or p-toluene carboxylic acid, p-methoxy benzoic acid or phthalic acid.
11. Titanium component according to claim 1, 2 or 3, characterized in that the titanium:magnesium:aluminium weight ratio is 1:(0.5-20):(0.1-5).
12. Titanium component according to claim 1, 2 or 3, characterized in that the titanium:magnesium:aluminium weight ratio is 1:(0.5-2.5):(0.2-1).
13. Process for the preparation of a titanium component useful for the polymerization of alkenes-l and for the copolymerization of alkenes-1 with each other or with ethylene, which titanium component contains a halogenated titanium compound, an electron donor, and a metal halide which process comprises reacting a combination of an organic aluminium compound and an organic mag-nesium compound with a halogenating agent of the formula RXm, wherein R is a hydrocarbon group, a hydrogen atom or a halogen atom, X is a halogen atom, and m is a whole number from 1-10, to form the corresponding metal halide, the process further comprising combining the metal halide so formed with a titanium halide compound of tetravalent titanium and an electron donor.
14. Process according to claim 13, characterized in that the reaction of the combination of organic metal compounds to form the metal halide is effected through precipitation of the metal halide from a solution of the combination of organic metal compounds.
15. Process according to claim 13 or 14, characterized in that the combination of organic metal compounds is reacted with a hydrogen halide.
16. Process according to claim 13 or 14, characterized in that the combination of organic metal compounds is reacted with hydrogen chloride.
17. Process according to claim 13 or 14, characterized in that the combination of organic metal compounds is reacted with an aliphatic halogen compound.
18. Process according to claim 13 or 14, characterized in that the combination of organic metal compounds is reacted with an aliphatic halogenated hydrocarbon with 1-8 carbon atoms per molecule.
19. Process according to claim 13 or 14, characterized in that the combination of organic metal compounds is reacted with an alkyl chloride with 1-8 carbon atoms per molecule.
20. Process according to claim 13 or 14, characterized in that the combination of organic metal compounds is reacted with a free halogen or an interhalogen compound.
21. Process according to claim 13 or 14, characterized in that the organic aluminium compound contains one or more hydrocarbon radicals with 1-10 carbon atoms bonded directly to the metal.
22. Process according to claim 13 or 14, characterized in that the organic aluminium compound is a trialkyl aluminium.
23. Process according to claim 13 or 14, characterized in that the organic magnesium compound is a dialkyl magnesium or an alkyl magnesium chloride with 1-10 carbon atoms per alkyl radical.
24. Process according to claim 13 or 14, characterized in that the combination of an organic aluminium compound and an organic magnesium compound is formed by reacting an alkyl halide with metallic magnesium in a hydrocarbon solvent, with subsequent or simultaneous application of a suitable aluminium compound, to form a complex consisting of an organoaluminium compound and an alkyl magnesium compound.
25. Process according to claim 13 or 14, characterized in that the titanium component is prepared by first forming a complex of the titanium halide compound and the electron donor and then grinding this complex with the metal halide to be used as carrier.
26. Process for the polymerization of alkenes-1 and for the copolymeri-zation of alkenes-1 with each other or with ethylene, with application of a catalyst system consisting of a titanium component, containing a halogenated titanium compound, an electron donor, and a metal halide obtained by conversion of an organic metal compound with a halogenating agent of the formula RXm, wherein R is a hydrocarbon group, a hydrogen atom or a halogen atom, X is a halogen atom, and m is a whole number from 1-10, and an organometal component derived from a metal of one of the groups I-III of the Periodic System of the Elements, characterized in that a titanium component according to claim 1 is used.
27. Process according to claim 26, characterized in that the organo-metal component contains a complex of an organic metal compound with an ester of an oxygen-containing organic acid.
28. Process according to claim 26 or 27, characterized in that after the polymerization the insoluble polymer is separated from the dispersant under exclusion of air.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| NL7902535 | 1979-04-01 | ||
| NL7902535 | 1979-04-01 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1156800A true CA1156800A (en) | 1983-11-08 |
Family
ID=19832901
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000348650A Expired CA1156800A (en) | 1979-04-01 | 1980-03-28 | Catalytic titanium component, process for the manufacture thereof, and process for the polymerization of alkenes-1 with application of such a titanium component |
Country Status (14)
| Country | Link |
|---|---|
| US (1) | US4670525A (en) |
| JP (1) | JPS55131005A (en) |
| AT (1) | AT368528B (en) |
| BE (1) | BE882543A (en) |
| BR (1) | BR8001974A (en) |
| CA (1) | CA1156800A (en) |
| DE (1) | DE3012272A1 (en) |
| ES (2) | ES490140A0 (en) |
| FR (1) | FR2453183B1 (en) |
| GB (1) | GB2047255B (en) |
| IT (1) | IT1188921B (en) |
| PT (1) | PT71039A (en) |
| SE (1) | SE449361B (en) |
| ZA (1) | ZA801724B (en) |
Families Citing this family (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| ZA801724B (en) * | 1979-04-01 | 1981-03-25 | Stamicarbon | Catalytic titanium compound,process for the manufacture thereof,and process for the polymerization of lakenes-1 with application of such a titanium component |
| US4350612A (en) * | 1981-01-13 | 1982-09-21 | Stauffer Chemical Company | Method for preparing a magnesium halide support for catalysts |
| NL8201574A (en) * | 1982-04-15 | 1983-11-01 | Stamicarbon | PROCESS FOR PREPARING A FIXED CATALYTIC TITAN COMPONENT AND METHOD FOR POLYMERIZING OLEFINS-1 USING SUCH A TITAN COMPONENT |
| FR2529207A1 (en) | 1982-06-24 | 1983-12-30 | Bp Chimie Sa | PROCESS FOR THE PREPARATION OF CATALYST SUPPORTS FOR THE POLYMERIZATION OF ALPHA-OLEFINS AND SUPPORTS OBTAINED |
| FR2546522B1 (en) * | 1983-05-25 | 1985-07-26 | Ato Chimie | PROCESS FOR THE PREPARATION OF A TRANSITIONAL METAL COMPONENT FOR A CATALYTIC SYSTEM FOR OLEFIN POLYMERIZATION |
| EP0136742A3 (en) * | 1983-08-23 | 1986-08-27 | Stamicarbon B.V. | Process of preparing a solid catalytic titanium component and process for the polymerization of 1-alkenes using such a titanium component |
| NL8500521A (en) * | 1985-02-23 | 1986-09-16 | Stamicarbon | METHOD FOR PREPARING A FIXED CATALYTIC TITAN COMPONENT AND METHOD FOR POLYMERIZING OLEFINS-1 USING SUCH A TITAN COMPONENT |
| FR2596396B1 (en) * | 1986-03-27 | 1988-11-18 | Atochem | SPHERICAL CATALYST SUPPORT FOR THE POLYMERIZATION OF ALPHA-OLEFINS CATALYSTS OBTAINED FROM SUCH SUPPORTS |
| DE3620060A1 (en) * | 1986-06-14 | 1987-12-17 | Hoechst Ag | METHOD FOR PRODUCING A POLYOLEFIN |
| US5349033A (en) * | 1986-06-14 | 1994-09-20 | Hoechst Aktiengesellschaft | Process for the preparation of polyolefin |
| US5139985A (en) * | 1988-05-31 | 1992-08-18 | Himont Incorporated | Components and catalyst for the polymerization olefins |
| DE4306382A1 (en) * | 1993-03-02 | 1994-09-08 | Hoechst Ag | Process for the preparation of a poly-1-olefin |
| CA2234189C (en) * | 1998-04-07 | 2006-08-29 | Nova Chemicals Ltd. | Heat treatment of ziegler-natta catalysts to increase polymer molecular weight in solution polymerization |
| US20040137811A1 (en) * | 2003-01-09 | 2004-07-15 | L & P Property Management Company | Elastomeric seating composite |
Family Cites Families (21)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| NL139981B (en) * | 1969-06-04 | 1973-10-15 | Stamicarbon | PROCESS FOR THE PREPARATION OF SOLUBLE COMPLEXES OF MAGNESIUM DIALKYLES AND ORGANO-ALUMINUM COMPOUNDS. |
| NL7114641A (en) * | 1970-10-29 | 1972-05-03 | ||
| US4107413A (en) * | 1971-06-25 | 1978-08-15 | Montedison S.P.A. | Process for the stereoregular polymerization of alpha olefins |
| US4156063A (en) * | 1971-06-25 | 1979-05-22 | Montecanti Edison, S.p.A. | Process for the stereoregular polymerization of alpha olefins |
| NL160286C (en) * | 1971-06-25 | |||
| JPS565404B2 (en) * | 1975-02-14 | 1981-02-04 | ||
| ES448189A1 (en) * | 1975-05-27 | 1977-07-01 | Dow Chemical Co | Catalyst for polymerizing olefins |
| JPS5287489A (en) * | 1976-01-19 | 1977-07-21 | Mitsui Petrochem Ind Ltd | Polymerization of olefins |
| JPS52104593A (en) * | 1976-03-01 | 1977-09-02 | Mitsui Petrochem Ind Ltd | Polymerization of olefins |
| JPS53123488A (en) * | 1977-04-04 | 1978-10-27 | Mitsui Toatsu Chem Inc | Polymerization of alpha-olefin |
| US4175171A (en) * | 1976-08-02 | 1979-11-20 | Mitsui Toatsu Chemicals, Inc. | Catalyst for polymerizing α-olefins |
| JPS6042244B2 (en) * | 1976-08-02 | 1985-09-20 | 三井東圧化学株式会社 | Polymerization method of α-olefin |
| JPS5812888B2 (en) * | 1976-08-27 | 1983-03-10 | 三井化学株式会社 | Method for manufacturing polyolefin |
| DE2742586A1 (en) * | 1976-09-28 | 1978-03-30 | Asahi Chemical Ind | NEW POLYMERIZATION CATALYSTS AND THEIR USE (II) |
| US4120820A (en) * | 1976-12-01 | 1978-10-17 | The Dow Chemical Company | High efficiency catalyst for polymerizing olefins |
| JPS5379984A (en) * | 1976-12-24 | 1978-07-14 | Mitsui Petrochem Ind Ltd | Copolymer and production |
| US4222235A (en) * | 1977-07-25 | 1980-09-16 | General Electric Company | Variable cycle engine |
| US4198315A (en) * | 1978-09-05 | 1980-04-15 | The Dow Chemical Company | High efficiency catalyst for polymerizing olefins |
| IT1099416B (en) * | 1978-10-23 | 1985-09-18 | Montedison Spa | COMPONENTS AND CATALYSTS FOR THE POLYMERIZATION OF OLEFINS |
| US4252670A (en) * | 1979-01-10 | 1981-02-24 | Imperial Chemical Industries Limited | Olefine polymerization catalyst |
| ZA801724B (en) * | 1979-04-01 | 1981-03-25 | Stamicarbon | Catalytic titanium compound,process for the manufacture thereof,and process for the polymerization of lakenes-1 with application of such a titanium component |
-
1980
- 1980-03-24 ZA ZA00801724A patent/ZA801724B/en unknown
- 1980-03-26 GB GB8010223A patent/GB2047255B/en not_active Expired
- 1980-03-28 CA CA000348650A patent/CA1156800A/en not_active Expired
- 1980-03-29 DE DE19803012272 patent/DE3012272A1/en not_active Withdrawn
- 1980-03-31 FR FR8007199A patent/FR2453183B1/en not_active Expired
- 1980-03-31 ES ES490140A patent/ES490140A0/en active Granted
- 1980-03-31 AT AT0172880A patent/AT368528B/en not_active IP Right Cessation
- 1980-03-31 BR BR8001974A patent/BR8001974A/en unknown
- 1980-03-31 PT PT71039A patent/PT71039A/en unknown
- 1980-03-31 BE BE0/200043A patent/BE882543A/en not_active IP Right Cessation
- 1980-04-01 JP JP4274780A patent/JPS55131005A/en active Pending
- 1980-04-01 SE SE8002497A patent/SE449361B/en not_active IP Right Cessation
- 1980-04-01 IT IT48313/80A patent/IT1188921B/en active
- 1980-05-27 ES ES491861A patent/ES491861A0/en active Granted
-
1982
- 1982-09-30 US US06/428,705 patent/US4670525A/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| AT368528B (en) | 1982-10-25 |
| BE882543A (en) | 1980-09-30 |
| ES8101085A1 (en) | 1980-12-01 |
| SE8002497L (en) | 1980-10-02 |
| JPS55131005A (en) | 1980-10-11 |
| FR2453183B1 (en) | 1985-11-22 |
| DE3012272A1 (en) | 1980-10-09 |
| ZA801724B (en) | 1981-03-25 |
| GB2047255B (en) | 1983-12-21 |
| IT8048313A1 (en) | 1981-10-01 |
| PT71039A (en) | 1980-04-01 |
| BR8001974A (en) | 1980-11-25 |
| FR2453183A1 (en) | 1980-10-31 |
| GB2047255A (en) | 1980-11-26 |
| ES8102154A1 (en) | 1980-12-16 |
| IT1188921B (en) | 1988-01-28 |
| ES491861A0 (en) | 1980-12-16 |
| ATA172880A (en) | 1982-02-15 |
| US4670525A (en) | 1987-06-02 |
| SE449361B (en) | 1987-04-27 |
| IT8048313A0 (en) | 1980-04-01 |
| ES490140A0 (en) | 1980-12-01 |
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