CA1074047A - Process for polymerizing alkenes-1 - Google Patents
Process for polymerizing alkenes-1Info
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- CA1074047A CA1074047A CA258,630A CA258630A CA1074047A CA 1074047 A CA1074047 A CA 1074047A CA 258630 A CA258630 A CA 258630A CA 1074047 A CA1074047 A CA 1074047A
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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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- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
Abstract
ABSTRACT
Process for polymerizing an alkene-1, ethylene or mixtures thereof by employing a catalyst which comprises (1) a titanium component which is a titanium halide supported on a magnesium-dihalide or manganese-dihalide support and (2) an organoaluminum component which comprises (a) a complex of an aluminum trialkyl and an ester of a carboxylic acid and an alcohol and (b) the reaction product of a dialkyl magnesium compound and an alkyl-aluminum dihalide, which results in a polymer of high stereospecificity.
Process for polymerizing an alkene-1, ethylene or mixtures thereof by employing a catalyst which comprises (1) a titanium component which is a titanium halide supported on a magnesium-dihalide or manganese-dihalide support and (2) an organoaluminum component which comprises (a) a complex of an aluminum trialkyl and an ester of a carboxylic acid and an alcohol and (b) the reaction product of a dialkyl magnesium compound and an alkyl-aluminum dihalide, which results in a polymer of high stereospecificity.
Description
This invention relates to a process for polymerizing ~-alkenes to form homopolymers or copolymers in the presence of a polymerization catalyst comlrising a titanium-halide component supported on a water-free magnesium halide or manganese-halide carrier, and an organoaluminum component; and particularly relates to such polymerization processes having an improved organo-aluminum component. The invention also provides shaped articles of polymers thus prepared.
A known catalyst system includes a titanium-halide component con-sisting of a titanium halide on a specially activated, water-free magnesium-halide or manganese-halide carrier, the organoaluminum component being the product of an addition reaction between a trialkyl-aluminUm compound and an ester of an organic acid containing oxygen, and is usually a mixture of a complex of the trialkyl-aluminium compound with the said ester and a free trialkyl-aluminUm compound. A catalyst system of this type is particularly useful in the polymerization of propene, butene-l, 4-methyl pentene-l and other a-alkenes. However the stereospecificity of the polymer product with such a catalyst leaves much to be desired.
The invention provides for the use of a catalyst system of the type hereinbefore referred to, which when used for polymerizing a-alkenes shows a particularly high activity together with a very high stereospecifi-city. Another advantage is that a polymer product is obtained having a large average particle size, which is advantageous when processing the pro-duct to powder.
The invention provides a process for polymerizing an ~-alkene in the presence of a catalyst system comprising a titanium-halide component sup-ported on a water-free magnesium-halide or manganese-halide carrier, and an organo-aluminum component that contains ~a) a complex of a trialkyl-aluminum compound with an ester of a carboxylic acid, and ~b) the reaction product of a dialkyl-magnesium compound and a monoalkyl-aluminùm dihalide.
, ~ ', :107~047 Th~ organo-aluminium component is preferably free of nol~-complexed trialkyl-aluminium compound~ as the presence of non-complexed trialkyl-aluminium compound detracts from the stereospecificity of the catalyst system.
The process according to the in~ention is used in particular in the stereospecific polymerization of C~-C~ oralkenes, e g. propene, butene-1, 4-methyl pentene-l and hexene, and in the copolymerization of such ~-alkenes with each other and/or with ethene. Copolymers with a random distribution of the various monomer units and block copolymers, may be thus prepared.
If ethene is used as comonomer it is usually incorporated in a minor propor-tion e.g. up to 30 %, more particularly between 1 % and 15 ~ by weight, based on the said ~-alkene.
The titanium halide is present in the titanium halide component on a water-free magnesium halide or manganese-halide carrier. The titanium compound used may be any halogenated compound of divalent, trivalent or tetravalent titanium, including compounds in which part of the titanium valences is utilized for compounds other than those with halogen atoms.
The halogen is preferably bromine, iodine and particularly chlorine. Specific examples of such titanium compounds are TiC13, TiC13.1/3 AlC13, TiC14, Ti~r4, TiI4 and Ti(isobutoxy)2C12.
The titanium halide is preferably present as a complex with a Lewis base. The preferred Lewis base is an ester of a carboxylic acid, more particularly esters of aromatic carboxylic acids e.g. ethyl benzoate, ethyl-p-methoxy-benzoate, n-butyl benzoate, methyl toluate, and dimethyl phthalate. Other examples of suitable esters are esters of saturated aliphatic carboxylic acids, e.g. ethyl acetate, amyl propionate and methyl butyrate, and esters of unsaturated aliphatic carboxylic acids, e.g.
methyl methacrylate, ethyl acrylate, and dimethyl maleinate. The acid component of the ester usually contains from 1 to 9 carbon atoms per molecule or is a natural fatty acid, while the alcohol component of the ester usually contains from 1 to 6 carbon atoms per molecule. Other examples of suitable Lewis bases are triethyl amine, pyridine, ethylene diamine, nitrobenzene and diethylether.
.
' The titanium halide-Lewis base complexes can be obtained in any known way, e.g. by putting together the components of the complex.
The carrier material used may be any water-Eree magnesium halide or manganese halide, but in practice the ctlloride, particularly magnesium chloride, is pre~erred.
Suitable water-free magnesium chloride can be prepared in known manner by dehydration of MgC12.6 H~0.
Particularly good activity and stereospecificity are obtained in the process of the invention using water-free magnesium halide or manganese halide which has a surface area larger than 3 m /g, and/or shows broadened diffraction lines in the X-ray spectrum compared to the normal, non-acti-vated halide, and which has been activated, for instance as described in the British Patent specification 1387890. Very favourable results are obtained using a water-free magnesium dihalide that has been prepared by making a dialkyl-magnesium compound react with an anhydrous hydrogen halide in a suitable solvent, e.g. n-heptane or another liquid hydrocarbon.
The titanium halide may be put on the carrier for example by simple admixture, preferably by grinding the mixture. If a titanium halide-Lewis base complex is used, it is possible first to form the complex and then to apply it to the carrier, or first to put the urcomplexed titanium halide on the carrier and then to add the Lewis base, either before or after the addition of the organoaluminium component. The titanium content of the ready titanium halide component on the carrier is preferably from-0.1 ~ to 10 % by weight. The Lewis base is present in the titanium halide component in an amount of e.g. C-5 molecules per titanium atom.
The organoaluminium component comprises a complex of a trialkyl-aluminium compound with an ester of a carboxylic acid. Suitable esters are the same esters as used in the titanium-halide component, preferably esters oi aromatic carboxylic acids e.g. as hereinbefore des-cribed. Particularly suitable trialkyl-aluminium compounds are triethyl aluminium, tripropyl aluminium, triisobutyl aluminium, triisoprenyl aluminium~ trihexyl aluminium and trioctyl aluminium. The Al/Ti ratio is preferably between 10 and 1000 and the molecule-atom ratio of the total amount of bound Lewis base in the catalyst to Ti is preferably between 5 and 500.
As hereinbefore described, l;he organoaluminium compound is pre-B 5 ferably free of uncomplexed trialkyl-aluminium compound, and thus ~_pre-ferably a stoichiometric amount of ester with respect to the trialkyl-aluminium compound is used, apart from the amount of ester used as a con-stituent of the titanium-halide component in some instances.
The exact stoichiometric amount of ester with respect to the tri-alkyl-aluminium compound can be determined by means of microwave titration of the trialkyl-aluminium compound with the ester in the way described in Analytical Chemistry 37 (1965), pp. 229-233.
The microwave titration is carried out by observing the change in transmission of microwaves in a resonance cavity during the course of the reaction of the trialkyl-aluminium compound with the ester. The mea-sured energy loss is the sum of the individual losses of the components present in the resonance cavity. One of these components is made up of the new molecules thereby formed. By plotting the transmission potential ~ , which is defined as:
j 20 a =~ V - 1, where VO = initial transmission potenti&l V = transmission potential at the time of measurement, against the concentration or the amount of reagent added, a curve is ob-tained in which the sharp break indicates the composition of the complex.
This titration is particularly suitable for tha determination of the stoichiometry of complexes, in particular, for the determination of the stoichiometric amount of ester with respect to the trialkyl-aluminium com-pound under the conditions of the polymerization reaction according to the invention.
According to T. Mole and B.A. Jeffery, 'Organoaluminium compounds', Elsevier Publ. Co., Amsterdam (1972), p. 302, a trialkylaluminium compound .
: `
-forms a 1 : 1 complex with an ester. It has been found however that by means of microwave titration that under the polymerization conditions used a normal value for the stoichiometric molar amount of ester with _....
respect to the trialkyl-aluminium compound is 1 : l.S. The determined value depends on the level of purity and the concentrations used and may range for example from 1 : 1.0 to 1 : 2.0, in particular from 1 : 1.2 to 1 : 1.6.
It is to be considered surprising that the best combination of activity and stereospecificity can be obtained with the stoichiometric amount of ester with respect to the trialkyl-aluminium compound as determined by the microwave titration, if use is made of an organoaluminium component that also contains the reaction product of a dialkyl-magnesium compound and a monoalkyl dihalide.
The organoaluminium component contains in addition to the complex of trialkyl-aluminium compound and ester, the reaction product of a dialkylmagnesium ¢ompound and a monoalkyl-aluminium dihalide. The alkyl groups of the dialkyl-magnesium compound preferably contain 1-10 carbon atoms per molecule or form a palmityl or stearyl group. Examples of suitable dialkylmagnesium compounds are diethyl magnesium, di-n-butyl magnesium, di-n-hexyl magnesium and di-n-octyl magnesium. The monoalkyl-aluminium dihalide is preferably a chloride or bromide. Ethyl-aluminium dichloride or di-bromide are particularly suitable, but use may also be made of other monoalkyl-aluminium dihalides, preferably with 1-10 carbon atoms in the alkyl group e.g. isopropyl-aluminium dichloride, n-butyl-aluminium dibromide or n-octyl-aluminium dichloride. The reaction product of the dialkyl-magnesium compound and the monoalkyl-aluminium dihalide is preferably added to the reaction product of the titanium-halide component and the complex of the trialkyl-aluminium compound with the ester.
The molar ratio between the dialkyl-magnesium compound and the monoalkyl-aluminium dihalide may for example be in the range 0.1 and 1, preferably between 0.3 and 0.6. Too high molar ratios give rise to ~74~47 insufficiently stereospecific catalysts and too low ratios to insufficient catalyst activity.
The conditions under which +he polym3ri~ation reaction by means of the new catalysts is effected are similar to conditions conventionally used.
Thus the reaction may be carried out in the gaseous phase or in the presence of a liquid vehicle, which may be inert or ~t may be a monomer in liquid form.
Examples of suitable vehicles are aliphatic, cycloaliphatic, aromatic and mixed aromatic/aliphatic hydrocarbons with 3-8 carbon a-toms, for example propene, butene-l~ butane, isobutane, n-hexane, n-heptane, cyclohexane, benzene, toluene and the xylenes.
The polymerization temperature usually is within the range between -80 and 150 C, preferably between ~0 and 100 C. The pressure may for example be between 1 and 30 atmospheres.
If so desired the molecular weight of the polymer may be controlled during the polymerization, e.g. by effecting the polymerization in the presence of hydrogen or another well-known molecular-weight regulator.
To prepare block copolymers, the monomers may be added in any desired order.
The process according to the invention is of particular importance in the preparation of isotactic polypropene, random copolymers of propene with minor amounts of ethene, and block copolymers of propene and ethene.
The following Examples of the invention are provided:
_etermination of the stoichiometrio amount of ester with respect to the trialkyl-aluminium compound 50 ml of water-free gasoline were introduced into a mixing vessel of the apparatus described in Analytical Chemistry 37 (1965), pp. 229-233.
3 ml of a 0.1 M solution of triethyl aluminium in gasoline were than added.
The titration was carried out with a 0.1 M solution of ethyl benzoate in water-free ga~ollne. The scale of the millivolt recorder was set to 20 mV
~n / 0~ V~ D f ~ 30 The ~-value is plotted against the number of ~ ~ 5~.v~
; ethyl benzoate added (n), the break indicating the equivalence point, as shown in the graph of the accompanying drawing. The ~ -value is defined as `` 1~74~:)47 , where V denotes the initial transmission potential and V the transmission potential at the time of measurement.
_ample I
6.5 ml of water-free ethyl ben~oate dissolved in 75 ml of water-free gasoline were added at 0 C to a solution of 5 ml of TiCl4 in 125 ml of gasoline that had been flushed with dry nitrogen, and the resulting complex TiC14.C6H5COOC2H5 precipitated This precipitate was filtered, washed and dried in a water-free nitrogen atmosphere.
0.348 g of the complex TiC14.C6H5COOC2H5 and 4.166 g of water-free magnesium chloride thus obtained were ground together in an agate ball mill for 16 hours in a nitrogen atmosphere. 0.448 g (containing 0.102 mmole of titanium) of the ground mixture was suspended in a solution consisting of 1.23 ml of triethyl aluminium and 0.86 ml of ethyl ben~oate in 50 ml of water-free gasoline and prepared under nitrogen and at room temperature five minutes before (this solution contained amounts of triethyl aluminium and ethyl benzoate corresponding to the stoichiometry determined by the micro-wave titration).
1.8 litre of water-free gasoline were introduced into a stainless-steel 3-litre autoclave equipped with a mechanical stirrer and having previsously been flushed with dry nitrogen. 4.5 ml of a solution of gasoline and the reaction product of 9 mmoles of di-n-butyl magnesium and 18 mmoles of ethyl-aluminium di-chloride were then added, after which the suspension thus obtained was added to the reaction system. The temperature of the autoclave was raised to 65 C and propene introduced therein with vigorous stirring. The propene pressure was controlled at 3 atmospheres durlng the polymerization. After 1 hour the reaction was stopped and the white powdery product filtered off.
The yield of polypropene was 59,000 g per g of titanium compound used (calculated as titanium). The content of isotactic material that is 30 not soluble in gasoline of 65 C was 96.2 % by weight. 50 % by weight of the polymer parti¢les had a diameter of over 220 ~ m. -Example II
The procedure of Example I was followed, except that only 3 mmoles of di-n-butyl magnesium and 6 mmoles of ethyl-aluminium dichloride were used, instead of 9 and 18 mmoles, respectively.
The yield of polypropene was 31,2~0 g per g of ti-tanium used.
The content of isotactic material that is not soluble in gasoline of 65 C
was 96.6 % by weight.
Comparative Experiments The following comparative experiments were carried out in a way analogous to that described in Example I, except for the alterations speci-fied in the accompanying ~ ; wherein DBM denotes di-n-butyl magnesium;
MEAC denotes tmono)ethyl-aluminium dichloride and TEA denotes triethyl aluminium.
Exp. molar amount of amount of yield g isotactic ) molar TEA/ethyl Al/Ti DBM mmoles ~ mmoles per g of % by w. benzoate ratio ratio ~ titanium A 180 0 0 41,500 87.4 3.4 B 76 0 0 11,500 92.4 1.5 ) C 76 9 0 13,900 65.4 1.52) 1) insoluble in gasoline of 65 C
A known catalyst system includes a titanium-halide component con-sisting of a titanium halide on a specially activated, water-free magnesium-halide or manganese-halide carrier, the organoaluminum component being the product of an addition reaction between a trialkyl-aluminUm compound and an ester of an organic acid containing oxygen, and is usually a mixture of a complex of the trialkyl-aluminium compound with the said ester and a free trialkyl-aluminUm compound. A catalyst system of this type is particularly useful in the polymerization of propene, butene-l, 4-methyl pentene-l and other a-alkenes. However the stereospecificity of the polymer product with such a catalyst leaves much to be desired.
The invention provides for the use of a catalyst system of the type hereinbefore referred to, which when used for polymerizing a-alkenes shows a particularly high activity together with a very high stereospecifi-city. Another advantage is that a polymer product is obtained having a large average particle size, which is advantageous when processing the pro-duct to powder.
The invention provides a process for polymerizing an ~-alkene in the presence of a catalyst system comprising a titanium-halide component sup-ported on a water-free magnesium-halide or manganese-halide carrier, and an organo-aluminum component that contains ~a) a complex of a trialkyl-aluminum compound with an ester of a carboxylic acid, and ~b) the reaction product of a dialkyl-magnesium compound and a monoalkyl-aluminùm dihalide.
, ~ ', :107~047 Th~ organo-aluminium component is preferably free of nol~-complexed trialkyl-aluminium compound~ as the presence of non-complexed trialkyl-aluminium compound detracts from the stereospecificity of the catalyst system.
The process according to the in~ention is used in particular in the stereospecific polymerization of C~-C~ oralkenes, e g. propene, butene-1, 4-methyl pentene-l and hexene, and in the copolymerization of such ~-alkenes with each other and/or with ethene. Copolymers with a random distribution of the various monomer units and block copolymers, may be thus prepared.
If ethene is used as comonomer it is usually incorporated in a minor propor-tion e.g. up to 30 %, more particularly between 1 % and 15 ~ by weight, based on the said ~-alkene.
The titanium halide is present in the titanium halide component on a water-free magnesium halide or manganese-halide carrier. The titanium compound used may be any halogenated compound of divalent, trivalent or tetravalent titanium, including compounds in which part of the titanium valences is utilized for compounds other than those with halogen atoms.
The halogen is preferably bromine, iodine and particularly chlorine. Specific examples of such titanium compounds are TiC13, TiC13.1/3 AlC13, TiC14, Ti~r4, TiI4 and Ti(isobutoxy)2C12.
The titanium halide is preferably present as a complex with a Lewis base. The preferred Lewis base is an ester of a carboxylic acid, more particularly esters of aromatic carboxylic acids e.g. ethyl benzoate, ethyl-p-methoxy-benzoate, n-butyl benzoate, methyl toluate, and dimethyl phthalate. Other examples of suitable esters are esters of saturated aliphatic carboxylic acids, e.g. ethyl acetate, amyl propionate and methyl butyrate, and esters of unsaturated aliphatic carboxylic acids, e.g.
methyl methacrylate, ethyl acrylate, and dimethyl maleinate. The acid component of the ester usually contains from 1 to 9 carbon atoms per molecule or is a natural fatty acid, while the alcohol component of the ester usually contains from 1 to 6 carbon atoms per molecule. Other examples of suitable Lewis bases are triethyl amine, pyridine, ethylene diamine, nitrobenzene and diethylether.
.
' The titanium halide-Lewis base complexes can be obtained in any known way, e.g. by putting together the components of the complex.
The carrier material used may be any water-Eree magnesium halide or manganese halide, but in practice the ctlloride, particularly magnesium chloride, is pre~erred.
Suitable water-free magnesium chloride can be prepared in known manner by dehydration of MgC12.6 H~0.
Particularly good activity and stereospecificity are obtained in the process of the invention using water-free magnesium halide or manganese halide which has a surface area larger than 3 m /g, and/or shows broadened diffraction lines in the X-ray spectrum compared to the normal, non-acti-vated halide, and which has been activated, for instance as described in the British Patent specification 1387890. Very favourable results are obtained using a water-free magnesium dihalide that has been prepared by making a dialkyl-magnesium compound react with an anhydrous hydrogen halide in a suitable solvent, e.g. n-heptane or another liquid hydrocarbon.
The titanium halide may be put on the carrier for example by simple admixture, preferably by grinding the mixture. If a titanium halide-Lewis base complex is used, it is possible first to form the complex and then to apply it to the carrier, or first to put the urcomplexed titanium halide on the carrier and then to add the Lewis base, either before or after the addition of the organoaluminium component. The titanium content of the ready titanium halide component on the carrier is preferably from-0.1 ~ to 10 % by weight. The Lewis base is present in the titanium halide component in an amount of e.g. C-5 molecules per titanium atom.
The organoaluminium component comprises a complex of a trialkyl-aluminium compound with an ester of a carboxylic acid. Suitable esters are the same esters as used in the titanium-halide component, preferably esters oi aromatic carboxylic acids e.g. as hereinbefore des-cribed. Particularly suitable trialkyl-aluminium compounds are triethyl aluminium, tripropyl aluminium, triisobutyl aluminium, triisoprenyl aluminium~ trihexyl aluminium and trioctyl aluminium. The Al/Ti ratio is preferably between 10 and 1000 and the molecule-atom ratio of the total amount of bound Lewis base in the catalyst to Ti is preferably between 5 and 500.
As hereinbefore described, l;he organoaluminium compound is pre-B 5 ferably free of uncomplexed trialkyl-aluminium compound, and thus ~_pre-ferably a stoichiometric amount of ester with respect to the trialkyl-aluminium compound is used, apart from the amount of ester used as a con-stituent of the titanium-halide component in some instances.
The exact stoichiometric amount of ester with respect to the tri-alkyl-aluminium compound can be determined by means of microwave titration of the trialkyl-aluminium compound with the ester in the way described in Analytical Chemistry 37 (1965), pp. 229-233.
The microwave titration is carried out by observing the change in transmission of microwaves in a resonance cavity during the course of the reaction of the trialkyl-aluminium compound with the ester. The mea-sured energy loss is the sum of the individual losses of the components present in the resonance cavity. One of these components is made up of the new molecules thereby formed. By plotting the transmission potential ~ , which is defined as:
j 20 a =~ V - 1, where VO = initial transmission potenti&l V = transmission potential at the time of measurement, against the concentration or the amount of reagent added, a curve is ob-tained in which the sharp break indicates the composition of the complex.
This titration is particularly suitable for tha determination of the stoichiometry of complexes, in particular, for the determination of the stoichiometric amount of ester with respect to the trialkyl-aluminium com-pound under the conditions of the polymerization reaction according to the invention.
According to T. Mole and B.A. Jeffery, 'Organoaluminium compounds', Elsevier Publ. Co., Amsterdam (1972), p. 302, a trialkylaluminium compound .
: `
-forms a 1 : 1 complex with an ester. It has been found however that by means of microwave titration that under the polymerization conditions used a normal value for the stoichiometric molar amount of ester with _....
respect to the trialkyl-aluminium compound is 1 : l.S. The determined value depends on the level of purity and the concentrations used and may range for example from 1 : 1.0 to 1 : 2.0, in particular from 1 : 1.2 to 1 : 1.6.
It is to be considered surprising that the best combination of activity and stereospecificity can be obtained with the stoichiometric amount of ester with respect to the trialkyl-aluminium compound as determined by the microwave titration, if use is made of an organoaluminium component that also contains the reaction product of a dialkyl-magnesium compound and a monoalkyl dihalide.
The organoaluminium component contains in addition to the complex of trialkyl-aluminium compound and ester, the reaction product of a dialkylmagnesium ¢ompound and a monoalkyl-aluminium dihalide. The alkyl groups of the dialkyl-magnesium compound preferably contain 1-10 carbon atoms per molecule or form a palmityl or stearyl group. Examples of suitable dialkylmagnesium compounds are diethyl magnesium, di-n-butyl magnesium, di-n-hexyl magnesium and di-n-octyl magnesium. The monoalkyl-aluminium dihalide is preferably a chloride or bromide. Ethyl-aluminium dichloride or di-bromide are particularly suitable, but use may also be made of other monoalkyl-aluminium dihalides, preferably with 1-10 carbon atoms in the alkyl group e.g. isopropyl-aluminium dichloride, n-butyl-aluminium dibromide or n-octyl-aluminium dichloride. The reaction product of the dialkyl-magnesium compound and the monoalkyl-aluminium dihalide is preferably added to the reaction product of the titanium-halide component and the complex of the trialkyl-aluminium compound with the ester.
The molar ratio between the dialkyl-magnesium compound and the monoalkyl-aluminium dihalide may for example be in the range 0.1 and 1, preferably between 0.3 and 0.6. Too high molar ratios give rise to ~74~47 insufficiently stereospecific catalysts and too low ratios to insufficient catalyst activity.
The conditions under which +he polym3ri~ation reaction by means of the new catalysts is effected are similar to conditions conventionally used.
Thus the reaction may be carried out in the gaseous phase or in the presence of a liquid vehicle, which may be inert or ~t may be a monomer in liquid form.
Examples of suitable vehicles are aliphatic, cycloaliphatic, aromatic and mixed aromatic/aliphatic hydrocarbons with 3-8 carbon a-toms, for example propene, butene-l~ butane, isobutane, n-hexane, n-heptane, cyclohexane, benzene, toluene and the xylenes.
The polymerization temperature usually is within the range between -80 and 150 C, preferably between ~0 and 100 C. The pressure may for example be between 1 and 30 atmospheres.
If so desired the molecular weight of the polymer may be controlled during the polymerization, e.g. by effecting the polymerization in the presence of hydrogen or another well-known molecular-weight regulator.
To prepare block copolymers, the monomers may be added in any desired order.
The process according to the invention is of particular importance in the preparation of isotactic polypropene, random copolymers of propene with minor amounts of ethene, and block copolymers of propene and ethene.
The following Examples of the invention are provided:
_etermination of the stoichiometrio amount of ester with respect to the trialkyl-aluminium compound 50 ml of water-free gasoline were introduced into a mixing vessel of the apparatus described in Analytical Chemistry 37 (1965), pp. 229-233.
3 ml of a 0.1 M solution of triethyl aluminium in gasoline were than added.
The titration was carried out with a 0.1 M solution of ethyl benzoate in water-free ga~ollne. The scale of the millivolt recorder was set to 20 mV
~n / 0~ V~ D f ~ 30 The ~-value is plotted against the number of ~ ~ 5~.v~
; ethyl benzoate added (n), the break indicating the equivalence point, as shown in the graph of the accompanying drawing. The ~ -value is defined as `` 1~74~:)47 , where V denotes the initial transmission potential and V the transmission potential at the time of measurement.
_ample I
6.5 ml of water-free ethyl ben~oate dissolved in 75 ml of water-free gasoline were added at 0 C to a solution of 5 ml of TiCl4 in 125 ml of gasoline that had been flushed with dry nitrogen, and the resulting complex TiC14.C6H5COOC2H5 precipitated This precipitate was filtered, washed and dried in a water-free nitrogen atmosphere.
0.348 g of the complex TiC14.C6H5COOC2H5 and 4.166 g of water-free magnesium chloride thus obtained were ground together in an agate ball mill for 16 hours in a nitrogen atmosphere. 0.448 g (containing 0.102 mmole of titanium) of the ground mixture was suspended in a solution consisting of 1.23 ml of triethyl aluminium and 0.86 ml of ethyl ben~oate in 50 ml of water-free gasoline and prepared under nitrogen and at room temperature five minutes before (this solution contained amounts of triethyl aluminium and ethyl benzoate corresponding to the stoichiometry determined by the micro-wave titration).
1.8 litre of water-free gasoline were introduced into a stainless-steel 3-litre autoclave equipped with a mechanical stirrer and having previsously been flushed with dry nitrogen. 4.5 ml of a solution of gasoline and the reaction product of 9 mmoles of di-n-butyl magnesium and 18 mmoles of ethyl-aluminium di-chloride were then added, after which the suspension thus obtained was added to the reaction system. The temperature of the autoclave was raised to 65 C and propene introduced therein with vigorous stirring. The propene pressure was controlled at 3 atmospheres durlng the polymerization. After 1 hour the reaction was stopped and the white powdery product filtered off.
The yield of polypropene was 59,000 g per g of titanium compound used (calculated as titanium). The content of isotactic material that is 30 not soluble in gasoline of 65 C was 96.2 % by weight. 50 % by weight of the polymer parti¢les had a diameter of over 220 ~ m. -Example II
The procedure of Example I was followed, except that only 3 mmoles of di-n-butyl magnesium and 6 mmoles of ethyl-aluminium dichloride were used, instead of 9 and 18 mmoles, respectively.
The yield of polypropene was 31,2~0 g per g of ti-tanium used.
The content of isotactic material that is not soluble in gasoline of 65 C
was 96.6 % by weight.
Comparative Experiments The following comparative experiments were carried out in a way analogous to that described in Example I, except for the alterations speci-fied in the accompanying ~ ; wherein DBM denotes di-n-butyl magnesium;
MEAC denotes tmono)ethyl-aluminium dichloride and TEA denotes triethyl aluminium.
Exp. molar amount of amount of yield g isotactic ) molar TEA/ethyl Al/Ti DBM mmoles ~ mmoles per g of % by w. benzoate ratio ratio ~ titanium A 180 0 0 41,500 87.4 3.4 B 76 0 0 11,500 92.4 1.5 ) C 76 9 0 13,900 65.4 1.52) 1) insoluble in gasoline of 65 C
2) stoichiometry determined by microwave titration.
Experiment A shows that a catalyst system that contains non-complexed trialkyl aluminium but no reaction product of a dialkyl-magnesium and a monoalkyl-aluminium dihalide, can provide a high catalyst activity as manifested by the yleld per gram of titanium, but the stereo-specificity of the catalyst is low. Almost 13 % of the propene monomer used was converted into undesired atactic polymer.
In experiment B, the stoichiometric trialkyl-aluminium compound/
ester ratio is used, but the catalyst does not contain any reaction product of a dialkyl-magnesium and a monoalkyl-aluminium dihalide. The activity o$
such a catalyst system is low.
1074~47 If a stoichiometric trialkyl-aluminium compound/ester ratio is us~d, but only dialkyl magnesium is used instead of the reaction product of a dialkyl-magnesium and a mono-alkyl-aluminium dihalide, the stereo-specificity of the catalyst is very poor (Experiment C).
Experiment A shows that a catalyst system that contains non-complexed trialkyl aluminium but no reaction product of a dialkyl-magnesium and a monoalkyl-aluminium dihalide, can provide a high catalyst activity as manifested by the yleld per gram of titanium, but the stereo-specificity of the catalyst is low. Almost 13 % of the propene monomer used was converted into undesired atactic polymer.
In experiment B, the stoichiometric trialkyl-aluminium compound/
ester ratio is used, but the catalyst does not contain any reaction product of a dialkyl-magnesium and a monoalkyl-aluminium dihalide. The activity o$
such a catalyst system is low.
1074~47 If a stoichiometric trialkyl-aluminium compound/ester ratio is us~d, but only dialkyl magnesium is used instead of the reaction product of a dialkyl-magnesium and a mono-alkyl-aluminium dihalide, the stereo-specificity of the catalyst is very poor (Experiment C).
Claims (19)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A process for polymerizing an .alpha.-alkene in the presence of a cata-lyst system comprising a titanium-halide component supported on a water-free magnesium-halide or manganese-halide carrier, and an organo-aluminum component that contains (a) a complex of a trialkyl-aluminum compound with an ester of a carboxylic acid, and (b) the reaction product of a dialkyl-magnesium compound and a monoalkyl-aluminum dihalide.
2. A process according to claim 1 wherein the organo-aluminum component is free of non-complexed trialkyl-aluminum compound.
3. A process according to claim 1 wherein the titanium-halide component is a complex of a halogenated titanium compound with a Lewis base on a water-free magnesium-chloride carrier.
4. A process according to claim 2 wherein the titanium-halide component is a complex of a halogenated titanium compound with a Lewis base on a water-free magnesium-chloride carrier.
5. A process according to claim 3 wherein the said Lewis base is an ester of a carboxylic acid.
6. A process according to claim 4 wherein the said Lewis base is an ester of a carboxylic acid.
7. A process according to any of claims 1, 2 or 3 wherein the said ester is an ester of an aromatic carboxylic acid.
8. A process according to claim 4 wherein the said ester is an ester of an aromatic carboxylic acid.
9. A process according to any of claims 1, 2 or 3 wherein the said carrier is an activated magnesium-halide or an activated manganese-halide each of which has a surface area larger than 3 m2/g, and/or shows broadened diffraction lines in the X-ray spectrum compared to the normal, non-activated halide.
10. A process according to claim 8 wherein the said carrier is an activated magnesium-halide or an activated manganese-halide each of which has a surface area larger than 3 m2/g, and/or shows broadened diffraction lines in the X-ray spectrum compared to the normal, non-activated halide.
11. A process according to any of claims 1, 2 or 3 wherein the said reaction product of the dialkyl-magnesium compound with the monoalkyl-aluminum dihalide is added to the reaction product of the titanium halide component and the complex of the trialkyl-aluminum compound with the ester.
12. A process according to claim 10 wherein the said reaction product of the dialkyl-magnesium compound with the monoalkyl-aluminum dihalide is added to the reaction product of the titanium halide component and the complex of the trialkyl-aluminum compound with the ester.
13. A process according to any of claims 1, 2 or 3 wherein the molar ratio of dialkyl-magnesium compound to monoalkyl-aluminum dihalide is between 0.1 : 1 and 1 : 1.
14. A process according to claim 12 wherein the molar ratio of dialkyl-magnesium compound to monoalkyl-aluminum dihalide is between 0.1 ? 1 and 1 : 1.
15. A process according to any of claims 1, 2 or 3 wherein the molar ratio of dialkyl-magnesium compound to monoalkyl-aluminum dihalide is between 0.3 : 1 and 0.6 : 1.
16. A process according to claim 12 wherein the molar ratio of dialkyl-magnesium compound to monoalkyl-aluminum dihalide is between 0.3:1 and 0.6:1.
17. A process according to any of claims 1, 2 or 3 wherein a polymer of a C3-C6 alkene is prepared, optionally with up to 30% by weight of ethene.
18. A process according to claim 14 wherein a polymer of a C3-C6 alkene is prepared, optionally With up to 30% by weight of ethene.
19. A process according to claim 16 wherein a polymer of a C3-C6 alkene is prepared, optionally with up to 30% by weight of ethene.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| NL7509736A NL7509736A (en) | 1975-08-15 | 1975-08-15 | PROCESS FOR POLYMERIZING ALKINES-1. |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1074047A true CA1074047A (en) | 1980-03-18 |
Family
ID=19824304
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA258,630A Expired CA1074047A (en) | 1975-08-15 | 1976-08-06 | Process for polymerizing alkenes-1 |
Country Status (11)
| Country | Link |
|---|---|
| JP (1) | JPS5224293A (en) |
| AT (1) | AT342863B (en) |
| AU (1) | AU502770B2 (en) |
| BE (1) | BE844900A (en) |
| CA (1) | CA1074047A (en) |
| DE (1) | DE2636193A1 (en) |
| ES (1) | ES450726A1 (en) |
| FR (1) | FR2320956A1 (en) |
| GB (1) | GB1547886A (en) |
| IT (1) | IT1066276B (en) |
| NL (1) | NL7509736A (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1777130A1 (en) | 1999-05-25 | 2007-04-25 | Toshio Murakami | Method and device for wiping |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| IT967867B (en) * | 1972-09-26 | 1974-03-11 | Montedison Spa | PROCEDURE FOR THE STEREOSPECIFICATION OF THE ALPHA OLE FINE |
| GB1492618A (en) * | 1974-02-01 | 1977-11-23 | Mitsui Petrochemical Ind | Process for preparing highly stereoregular polyolefins and catalyst used therefor |
-
1975
- 1975-08-15 NL NL7509736A patent/NL7509736A/en not_active Application Discontinuation
-
1976
- 1976-08-05 BE BE169570A patent/BE844900A/en not_active IP Right Cessation
- 1976-08-06 CA CA258,630A patent/CA1074047A/en not_active Expired
- 1976-08-06 GB GB3288776A patent/GB1547886A/en not_active Expired
- 1976-08-11 DE DE19762636193 patent/DE2636193A1/en not_active Ceased
- 1976-08-12 FR FR7624606A patent/FR2320956A1/en active Granted
- 1976-08-12 AT AT600776A patent/AT342863B/en not_active IP Right Cessation
- 1976-08-12 AU AU16806/76A patent/AU502770B2/en not_active Expired
- 1976-08-13 IT IT5089176A patent/IT1066276B/en active
- 1976-08-14 ES ES450726A patent/ES450726A1/en not_active Expired
- 1976-08-14 JP JP9740776A patent/JPS5224293A/en active Pending
Also Published As
| Publication number | Publication date |
|---|---|
| AT342863B (en) | 1978-04-25 |
| FR2320956B1 (en) | 1982-11-19 |
| ATA600776A (en) | 1977-08-15 |
| IT1066276B (en) | 1985-03-04 |
| JPS5224293A (en) | 1977-02-23 |
| FR2320956A1 (en) | 1977-03-11 |
| GB1547886A (en) | 1979-06-27 |
| ES450726A1 (en) | 1977-09-01 |
| DE2636193A1 (en) | 1977-02-24 |
| AU502770B2 (en) | 1979-08-09 |
| NL7509736A (en) | 1977-02-17 |
| BE844900A (en) | 1977-02-07 |
| AU1680676A (en) | 1978-02-16 |
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