CA1075399A - Process for polymerizing alkenes-1 - Google Patents
Process for polymerizing alkenes-1Info
- Publication number
- CA1075399A CA1075399A CA258,584A CA258584A CA1075399A CA 1075399 A CA1075399 A CA 1075399A CA 258584 A CA258584 A CA 258584A CA 1075399 A CA1075399 A CA 1075399A
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- Prior art keywords
- halide
- ester
- process according
- aluminium
- titanium
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Classifications
-
- 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
-
- 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
- C08F4/00—Polymerisation catalysts
- C08F4/02—Carriers therefor
- C08F4/022—Magnesium halide as support anhydrous or hydrated or complexed by means of a Lewis base for Ziegler-type catalysts
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
Abstract
ABSTRACT
l-Alkenes are polymerized or copolymerized using a catalyst system comprising a titanium halide, optionally complexed with a Lewis base, on an anhydrous magnesium- or manganefe-halide carrier and an organo-aluminum component consisting of a complex of an ester of a carboxylic acid and a trialkyl-aluminum, and a dialkyl-aluminum halide.
l-Alkenes are polymerized or copolymerized using a catalyst system comprising a titanium halide, optionally complexed with a Lewis base, on an anhydrous magnesium- or manganefe-halide carrier and an organo-aluminum component consisting of a complex of an ester of a carboxylic acid and a trialkyl-aluminum, and a dialkyl-aluminum halide.
Description
2772 ~
~'7~
This invention relates to a process for polymerizing ~-alkenes to form homopolymers or copolymers in the presence of a polymerization catalyst comprising a titanium-halide component supported on a water-free magnesium halide or manganese-halide carrier, and an organoaluminium component; and particularly relates to such polymerization proc0sses having an improved organoaluminium component. The invention also provides shaped articles of polymers thus prepared.
A known catalyst system includes a titanium-halide component consisting of a titanium halide on a specially activated, water-free, magnesium-halide or manganese-halide carrier, the organoaluminium compo~
nent being the product of an addition reaction between a trialkyl-aluminium compound and an ester of an organic acid containing oxygen, and is usually a mixture of a complex ot the trialkyl-aluminium compound wi~h the said ester and a free trialkyl-aluminium compound. A catalyst system of this type is particularly useful in the polymerization ol propene, ` butene-1, 4 methyl pentene-1 and other alkenes-1. However the stereo~
specificity of the polymer produ~ct produced with such a catalyst leaves much to be desired.
The invention provides for the use of a catalyst system oi' the type hereinbefore referred to, which when used for polymerizing ~alkenes shows a particularly high activity together with a very high ' stereospecificity. Another advantag0 is that a polymer product is obtained having a large average particle size, which is advantageous when proces-sing the product to powder.
' 25 The invention provides a process for polymerizing an ~-alkene :~
in the presence of a catalyst system comprising a titanium-halide component supported on a water-iree magnesium~halide or manganese-halide carrier, and an organoaluminium component that contains (a) a complex of a trialkyl-aluminium compound with an ester of a carboxylic acid and (b) a dialkyl-aluminium halide.
.
'~' ' .' "
~ 53~
~ The organoaluminium component is preferably free of non-;i 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 invention is used in particular - in the stereospecific polymerization of C3-C6 '~-alkenes, e.g. propene, butene-l, 4-methyl pentene-l and hexene, and in the copolymeriza-tion 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 proportion e.g. up to 30%, more particularly be--- tween 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 titanilml :-. ~, 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 compo-mds are TiC13, TiC13.1/3 AlC13, 1 20 TiC14, TiBr4, TiI4, and Ti(isobutoxy)2CL2.
-- ~ 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 ~; 25 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.
9~
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-free magnesium halide or manganese halide, but in practice the chloride, 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 diifraction lines in the X-ray spectrum compared to the normal, non-activated halide, and which has been activated, ior instance as dascribed in the British Patent speciiication 13~7890. Very favourable results are obtained using a water-iree magnesium dihalide that has been ~ 15 prepared by making a dialkyl-magnesium compound react with an anhydrous ., hydrogan halide in a suitable solvent, e.g. n-heptane or another liquid hydrocarbon.
The titanium halide may be put on the carrier for exampla by simple admixture, pre~erably by grinding the mixture. -If a titanium halide~Lewis base complex is used, it iS possible first to i'orm the complex and then to apply it to the carrier, or first to put the uncomplexed titanium halide on the carrier and then to add the Lewis base, either before or after the addition o~ the organoaluminium component. The titanium content oi the ready titanium halide component on the carrier . ~ 25 i9 pre~erably from 0.1% to 10% by weight. The Lewis base is present in the titanium halid0 component in an amount of e.g. 0-5 molecules per titanium atom.
The organoaluminium component comprises a complex oi' a trial~yl-- aluminium compound with an ester oi' a carboxylic acid. Suitable esters are the same esters a9 used in the titanium-halide component, prei'erably ester~ ~ aromatic carboxyllc acids eOg. as hereinbei'ore described.
- Particularly suitable trialkyl-aluminium compounds are triethyl aluminium, ~3~
~075~
tripropyl aluminium, triisobutyl aluminium, triisoprenyl aluminium, tri-hexyl aluminium and trioctyl aluminium.
The Al/Ti ratio is preferably between 10 and 1000 and the molecule-atom ratio of -the total amount of bou~d Lewis base in the catalyst to Ti is pre~erably between 5 and 500.
As hereinbefore described, the organoaluminium compound is pre-ferably free of uncomplexed trialkyl-aluminium compound, and than prefe-rably a stoichiometric amount of ester with respect to the trialkyl-: i ; aluminium compound is used, apart from the amount of ester used as a constituent of the titanium~halide component in some instances.
,:
The exact stoichiometric amount of ester with respect to the trialkyl-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 - m~asured 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 Q, ` which is defined as ,_ ~ = ~ - - 1, where VO s initial transmission potential V - transmission potential at the time of measurement, against the concentration or the amount of reagent added, a curve is obtained - in which the sharp break indicates the composition of the complex.
This titration is particularly suitable for the determination of the stoichiometry of complexes, in particular, for the determination of the stoichiometric amount of ester with respect to the trialkyl-- 30 aluminium oompound under the conditions of the polymerization reaction according to the invention.
~' '_ .:
~t7~3~
According to T. Mole and E. A. Jeffery, "Organoaluminium ; Compounds7", Elsevier Publ. Co., Amsterdam (1972~, p. 302, a trialkyl-aluminium compound forms a 1:1 complex with an ester. It has been found however 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 : 1.5.
The determined value found depends on the leval of purity and the concen-trations used and may range for examplefrom l : 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 stoichio-metric amount of ester with respect to the trialkyl-aluminium compound as determined by the microwave titration, if use is made of an organo-aluminium component that also contains a dialkyl-aluminium halide.
The organoaluminium component contains in addition tc the complex of trialkyl-aluminium compound and ester, a dialkyl-aluminium halide, particularly a chloride or bromide. Diethyl-aluminium chloride and -bromide are particularly suitable, but use may also be made of other dlalkyl-aluminium halides with, preferably, l-lO carbon atoms in the alkyl group, such as, e.g., di-n-butyl-aluminium chloride and methyl-n-butyl-aluminium chloride. The dialkyl-aluminium halide is preferably added to the reaction product of the titanium-halide component and the complex of the trialkyl-aluminium compound with the ester.
:-The conditions under which the polymerization 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 pre-sence of a liquid vehicle, which may be inert or it may be a monomer in liquid form. Examples of suitable vehicles are aliphatic, cycloaliphatic, - 30 aromatic and mixed aromatic/aliphatic hydrocarbons with 3-8 carbon atoms, e.g. propene, butene-l, butane, isobutane, n-hexane, n-heptane, cyclohexane, :
53~
benzene, toluel~e and the xylenes.
The polymerization temperature usually is within the range between -80 and 150 C, pxeferably between 40 and 100 C. The pressure . may for exampl0 be between 1 and 30 atmospheres.
If so desired the molecular weight of the polymer may be con-trolled 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 inven-tion 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:
; 15 Determination of the stoichiometric 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, : 20 3 ml of a 0.1 M solution of triethyl aluminium in gasoline were then added.
The titration was carried out with a 0.1 M solution of ethyl benzoate in water-free gasoline. The scale of the millivolt recorder was set to 20 mV.
The ~-value is plotted against the number of ml o~ solution of ethyl benzoate added (n), the break in the graph indicating the equivalence point as shown in the graph of the accompanying drawing.
; The ~-value is defined as ~ 1, where V denotes the initial transmission potential and V the transmission potential at the time of measurement.
E~xample I
6.5 ml of water-free ethyl benzoate dissolved in 75 ml of water-free gasoline were added at 0 C to a solution of 5 ml of TiC1~ in 125 ml of gasoline that had been flushed with dry nitrogen, and the resulting complex TiCl~.C6H5cOOc2H5 precipitated. This precipitate was ~7S3~
iil~ered, washed and dried in a water-lree nitrogen atmosphere.
0.348 g of the complex TiC14.C6l-l5C()OC2il5 and 4.166 g oE water-free magnesium chloride thus ob-tained with a surface area of over 3 m /g 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 benzoate 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 ' ~ 10 to the stoichiometry determined by the microwave titration).
.. .~
' 1.8 litre water~free gasoline were introduced into a stainless-~- ste01 3-litre autoclave equipped with a mechanical stirrer and having previously bee~ flushed with dry nitrogen. 4.5 ml of a 2-molar solution of diethyl aluminium chloride in gasoline were then added to the autoclave, 15 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 a-t 3 atmospheres during the polymerization. After 1 hour the reaction was stopped and the white powdery product filtered off.
The yield of polypropene was 50.000 g per g of titanium compound used ~calculated as titanium). The content of isotactic material that is not soluble in gasoline of 65 C was 9i.0% by weight. 50% by weight ; of the polymer particles had a diameter of over 200 ~,n.
Example II
` 25 The procedure of Example I was followed, except that 1.40 ml of ethyl benzoate was used in the formation of the complex with the triethyl aluminium.
The yield of polypropene was 22.000 g of polymer per g of titanium.
The content of isotactic material that is not soluble in gasoline of 65 C
- 30 was 95.0% by weight.
'`,' : ' ' ' ' ' ~
. .
~'7S39~
Example III
0-372 g of the TiC14.C6H5COOC2H5 complex and 4.304 g of water~
free magnesium chloride were ground together in the way described in ~- Example I.
4.5 ml of a 1-molar solution of diethyl aluminium chloride in gasoline were - added to 0.372 g of this ground mixture. The mixture thus obtained was then suspended in a freshly prepared solution of 1.23 ml of triethyl aluminium and 0.86 ml of ethyl ben~oate (stoichiometric amounts according to microwave titration) in 50 ml of water-free gasoline.
1.8 ml of water-free gasoline we~e introduced into a stainless-steel autoclave that had been flushed with dry nitrogen. After 4.5 ml of a l~molar solution of diethyl aluminium chloride in gasoline had also been .
introduced into the autoclave, the suspension was added ~o the reaction system. The process then proceeded asdescribed in Example I.
The yield of polypropene was 41.000 g per g titaniurr. used. The content of isotactic material that is insoluble in gasoline of 65 C
was 96.5% by weight.
_amples IV to IX
The Examples IV to IX were analogous to Example I, except for the alterations specified in the accompanying Table 1. The molar triethyl aluminium/ethyl ben~oate ratio was equal to the stoichiometric ratio detexmined by means of microwave titration.
Table 1 .~ _ Example molar molar Temp. yield g isotactic Mg/Ti Al/Ti1) C per g of material ratio ratio titanium % by w.
- .. ..
- IV 45 180 65 48,500 97.0 V 45 180 30 39,000 97~2 VI 22.6 180 65 29,000 96.7 30 VII 11 180 65 31,500 93.0 VIII 36 90 65 42,000 94.1 IX 45 45 65 38,500 97.4 f 107~39~
1) Tlle molar T~/DEAC ratio is 1 : 1 in each experiment.
TEA here denotes triethylaluminium; DEAC denotes diethyl aluminium chloride . 2) Insoluble in gasoline at 65 C.
' :
Comparative Experiments A to C
The following comparative experiments illustrate the importance :.
. of the use of stoichiometric amounts of the trialkyl aluminium compound and the ester in the formation of the complex and of the use of the dialkyl-aluminium halide. These experiments were carried out in the way described in Example I, except for the alterations specified in Table 2.
Table 2 Exp. molar molar DEAC Temp. yield g isotactic molar Mg/Ti Al/Ti1) concentr. C per g of material TEA/ethyl ratio ratio mmoles/1 titanium % by 2 benzoate weight ) ratio A 45 180 0 65 41,500 87.4 3.4 B 45 76 0 65 11,500 92.4 1.5 ) C 45 180 5 65 30,500 89.5 3.4 1) The molar TEA/DEAC ratio in e~periment C is 1 : 1
~'7~
This invention relates to a process for polymerizing ~-alkenes to form homopolymers or copolymers in the presence of a polymerization catalyst comprising a titanium-halide component supported on a water-free magnesium halide or manganese-halide carrier, and an organoaluminium component; and particularly relates to such polymerization proc0sses having an improved organoaluminium component. The invention also provides shaped articles of polymers thus prepared.
A known catalyst system includes a titanium-halide component consisting of a titanium halide on a specially activated, water-free, magnesium-halide or manganese-halide carrier, the organoaluminium compo~
nent being the product of an addition reaction between a trialkyl-aluminium compound and an ester of an organic acid containing oxygen, and is usually a mixture of a complex ot the trialkyl-aluminium compound wi~h the said ester and a free trialkyl-aluminium compound. A catalyst system of this type is particularly useful in the polymerization ol propene, ` butene-1, 4 methyl pentene-1 and other alkenes-1. However the stereo~
specificity of the polymer produ~ct produced with such a catalyst leaves much to be desired.
The invention provides for the use of a catalyst system oi' the type hereinbefore referred to, which when used for polymerizing ~alkenes shows a particularly high activity together with a very high ' stereospecificity. Another advantag0 is that a polymer product is obtained having a large average particle size, which is advantageous when proces-sing the product to powder.
' 25 The invention provides a process for polymerizing an ~-alkene :~
in the presence of a catalyst system comprising a titanium-halide component supported on a water-iree magnesium~halide or manganese-halide carrier, and an organoaluminium component that contains (a) a complex of a trialkyl-aluminium compound with an ester of a carboxylic acid and (b) a dialkyl-aluminium halide.
.
'~' ' .' "
~ 53~
~ The organoaluminium component is preferably free of non-;i 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 invention is used in particular - in the stereospecific polymerization of C3-C6 '~-alkenes, e.g. propene, butene-l, 4-methyl pentene-l and hexene, and in the copolymeriza-tion 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 proportion e.g. up to 30%, more particularly be--- tween 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 titanilml :-. ~, 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 compo-mds are TiC13, TiC13.1/3 AlC13, 1 20 TiC14, TiBr4, TiI4, and Ti(isobutoxy)2CL2.
-- ~ 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 ~; 25 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.
9~
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-free magnesium halide or manganese halide, but in practice the chloride, 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 diifraction lines in the X-ray spectrum compared to the normal, non-activated halide, and which has been activated, ior instance as dascribed in the British Patent speciiication 13~7890. Very favourable results are obtained using a water-iree magnesium dihalide that has been ~ 15 prepared by making a dialkyl-magnesium compound react with an anhydrous ., hydrogan halide in a suitable solvent, e.g. n-heptane or another liquid hydrocarbon.
The titanium halide may be put on the carrier for exampla by simple admixture, pre~erably by grinding the mixture. -If a titanium halide~Lewis base complex is used, it iS possible first to i'orm the complex and then to apply it to the carrier, or first to put the uncomplexed titanium halide on the carrier and then to add the Lewis base, either before or after the addition o~ the organoaluminium component. The titanium content oi the ready titanium halide component on the carrier . ~ 25 i9 pre~erably from 0.1% to 10% by weight. The Lewis base is present in the titanium halid0 component in an amount of e.g. 0-5 molecules per titanium atom.
The organoaluminium component comprises a complex oi' a trial~yl-- aluminium compound with an ester oi' a carboxylic acid. Suitable esters are the same esters a9 used in the titanium-halide component, prei'erably ester~ ~ aromatic carboxyllc acids eOg. as hereinbei'ore described.
- Particularly suitable trialkyl-aluminium compounds are triethyl aluminium, ~3~
~075~
tripropyl aluminium, triisobutyl aluminium, triisoprenyl aluminium, tri-hexyl aluminium and trioctyl aluminium.
The Al/Ti ratio is preferably between 10 and 1000 and the molecule-atom ratio of -the total amount of bou~d Lewis base in the catalyst to Ti is pre~erably between 5 and 500.
As hereinbefore described, the organoaluminium compound is pre-ferably free of uncomplexed trialkyl-aluminium compound, and than prefe-rably a stoichiometric amount of ester with respect to the trialkyl-: i ; aluminium compound is used, apart from the amount of ester used as a constituent of the titanium~halide component in some instances.
,:
The exact stoichiometric amount of ester with respect to the trialkyl-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 - m~asured 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 Q, ` which is defined as ,_ ~ = ~ - - 1, where VO s initial transmission potential V - transmission potential at the time of measurement, against the concentration or the amount of reagent added, a curve is obtained - in which the sharp break indicates the composition of the complex.
This titration is particularly suitable for the determination of the stoichiometry of complexes, in particular, for the determination of the stoichiometric amount of ester with respect to the trialkyl-- 30 aluminium oompound under the conditions of the polymerization reaction according to the invention.
~' '_ .:
~t7~3~
According to T. Mole and E. A. Jeffery, "Organoaluminium ; Compounds7", Elsevier Publ. Co., Amsterdam (1972~, p. 302, a trialkyl-aluminium compound forms a 1:1 complex with an ester. It has been found however 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 : 1.5.
The determined value found depends on the leval of purity and the concen-trations used and may range for examplefrom l : 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 stoichio-metric amount of ester with respect to the trialkyl-aluminium compound as determined by the microwave titration, if use is made of an organo-aluminium component that also contains a dialkyl-aluminium halide.
The organoaluminium component contains in addition tc the complex of trialkyl-aluminium compound and ester, a dialkyl-aluminium halide, particularly a chloride or bromide. Diethyl-aluminium chloride and -bromide are particularly suitable, but use may also be made of other dlalkyl-aluminium halides with, preferably, l-lO carbon atoms in the alkyl group, such as, e.g., di-n-butyl-aluminium chloride and methyl-n-butyl-aluminium chloride. The dialkyl-aluminium halide is preferably added to the reaction product of the titanium-halide component and the complex of the trialkyl-aluminium compound with the ester.
:-The conditions under which the polymerization 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 pre-sence of a liquid vehicle, which may be inert or it may be a monomer in liquid form. Examples of suitable vehicles are aliphatic, cycloaliphatic, - 30 aromatic and mixed aromatic/aliphatic hydrocarbons with 3-8 carbon atoms, e.g. propene, butene-l, butane, isobutane, n-hexane, n-heptane, cyclohexane, :
53~
benzene, toluel~e and the xylenes.
The polymerization temperature usually is within the range between -80 and 150 C, pxeferably between 40 and 100 C. The pressure . may for exampl0 be between 1 and 30 atmospheres.
If so desired the molecular weight of the polymer may be con-trolled 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 inven-tion 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:
; 15 Determination of the stoichiometric 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, : 20 3 ml of a 0.1 M solution of triethyl aluminium in gasoline were then added.
The titration was carried out with a 0.1 M solution of ethyl benzoate in water-free gasoline. The scale of the millivolt recorder was set to 20 mV.
The ~-value is plotted against the number of ml o~ solution of ethyl benzoate added (n), the break in the graph indicating the equivalence point as shown in the graph of the accompanying drawing.
; The ~-value is defined as ~ 1, where V denotes the initial transmission potential and V the transmission potential at the time of measurement.
E~xample I
6.5 ml of water-free ethyl benzoate dissolved in 75 ml of water-free gasoline were added at 0 C to a solution of 5 ml of TiC1~ in 125 ml of gasoline that had been flushed with dry nitrogen, and the resulting complex TiCl~.C6H5cOOc2H5 precipitated. This precipitate was ~7S3~
iil~ered, washed and dried in a water-lree nitrogen atmosphere.
0.348 g of the complex TiC14.C6l-l5C()OC2il5 and 4.166 g oE water-free magnesium chloride thus ob-tained with a surface area of over 3 m /g 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 benzoate 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 ' ~ 10 to the stoichiometry determined by the microwave titration).
.. .~
' 1.8 litre water~free gasoline were introduced into a stainless-~- ste01 3-litre autoclave equipped with a mechanical stirrer and having previously bee~ flushed with dry nitrogen. 4.5 ml of a 2-molar solution of diethyl aluminium chloride in gasoline were then added to the autoclave, 15 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 a-t 3 atmospheres during the polymerization. After 1 hour the reaction was stopped and the white powdery product filtered off.
The yield of polypropene was 50.000 g per g of titanium compound used ~calculated as titanium). The content of isotactic material that is not soluble in gasoline of 65 C was 9i.0% by weight. 50% by weight ; of the polymer particles had a diameter of over 200 ~,n.
Example II
` 25 The procedure of Example I was followed, except that 1.40 ml of ethyl benzoate was used in the formation of the complex with the triethyl aluminium.
The yield of polypropene was 22.000 g of polymer per g of titanium.
The content of isotactic material that is not soluble in gasoline of 65 C
- 30 was 95.0% by weight.
'`,' : ' ' ' ' ' ~
. .
~'7S39~
Example III
0-372 g of the TiC14.C6H5COOC2H5 complex and 4.304 g of water~
free magnesium chloride were ground together in the way described in ~- Example I.
4.5 ml of a 1-molar solution of diethyl aluminium chloride in gasoline were - added to 0.372 g of this ground mixture. The mixture thus obtained was then suspended in a freshly prepared solution of 1.23 ml of triethyl aluminium and 0.86 ml of ethyl ben~oate (stoichiometric amounts according to microwave titration) in 50 ml of water-free gasoline.
1.8 ml of water-free gasoline we~e introduced into a stainless-steel autoclave that had been flushed with dry nitrogen. After 4.5 ml of a l~molar solution of diethyl aluminium chloride in gasoline had also been .
introduced into the autoclave, the suspension was added ~o the reaction system. The process then proceeded asdescribed in Example I.
The yield of polypropene was 41.000 g per g titaniurr. used. The content of isotactic material that is insoluble in gasoline of 65 C
was 96.5% by weight.
_amples IV to IX
The Examples IV to IX were analogous to Example I, except for the alterations specified in the accompanying Table 1. The molar triethyl aluminium/ethyl ben~oate ratio was equal to the stoichiometric ratio detexmined by means of microwave titration.
Table 1 .~ _ Example molar molar Temp. yield g isotactic Mg/Ti Al/Ti1) C per g of material ratio ratio titanium % by w.
- .. ..
- IV 45 180 65 48,500 97.0 V 45 180 30 39,000 97~2 VI 22.6 180 65 29,000 96.7 30 VII 11 180 65 31,500 93.0 VIII 36 90 65 42,000 94.1 IX 45 45 65 38,500 97.4 f 107~39~
1) Tlle molar T~/DEAC ratio is 1 : 1 in each experiment.
TEA here denotes triethylaluminium; DEAC denotes diethyl aluminium chloride . 2) Insoluble in gasoline at 65 C.
' :
Comparative Experiments A to C
The following comparative experiments illustrate the importance :.
. of the use of stoichiometric amounts of the trialkyl aluminium compound and the ester in the formation of the complex and of the use of the dialkyl-aluminium halide. These experiments were carried out in the way described in Example I, except for the alterations specified in Table 2.
Table 2 Exp. molar molar DEAC Temp. yield g isotactic molar Mg/Ti Al/Ti1) concentr. C per g of material TEA/ethyl ratio ratio mmoles/1 titanium % by 2 benzoate weight ) ratio A 45 180 0 65 41,500 87.4 3.4 B 45 76 0 65 11,500 92.4 1.5 ) C 45 180 5 65 30,500 89.5 3.4 1) The molar TEA/DEAC ratio in e~periment C is 1 : 1
2) Insoluble in gasoline of 65 C.
3) Stoichiometry determined by microwave -titration.
Experiment A shows that a ca-talyst system that contains non-complexed trialkyl-aluminium compound but no dialkyl-aluminium halide can give a hlgh catalyst activity as manifested by the yield per gram of titanium, it is true, but the stereospecificity of the catalyst is low. Almost 13% of the propene monomer used was converted into undesired atactic polymer.
Addition of a dialkyl-aluminium halide as an addition aluminium component ~.- .
- in the presence of non-complexed trialkyl-aluminium compound gave little .. . .
improvement of the stereospecificity, but gives rise to a considerable decrease of the catalyst activity (~ee experiment C).
. In experiment B, the stoichiometric trialkyl-aluminium compound/
i 30 ester ratio is used, but the cata~lyst does not contain a dialkyl-aluminium halide.
The activity of such a catalyst system is low.
. ,:
,.,~
_g_ ,, ,, ~ . .
. . ~
.
Experiment A shows that a ca-talyst system that contains non-complexed trialkyl-aluminium compound but no dialkyl-aluminium halide can give a hlgh catalyst activity as manifested by the yield per gram of titanium, it is true, but the stereospecificity of the catalyst is low. Almost 13% of the propene monomer used was converted into undesired atactic polymer.
Addition of a dialkyl-aluminium halide as an addition aluminium component ~.- .
- in the presence of non-complexed trialkyl-aluminium compound gave little .. . .
improvement of the stereospecificity, but gives rise to a considerable decrease of the catalyst activity (~ee experiment C).
. In experiment B, the stoichiometric trialkyl-aluminium compound/
i 30 ester ratio is used, but the cata~lyst does not contain a dialkyl-aluminium halide.
The activity of such a catalyst system is low.
. ,:
,.,~
_g_ ,, ,, ~ . .
. . ~
.
Claims (17)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A process for polymerizing an .alpha.-alkene in the presence of a catalyst system comprising a titanium-halide component supported on a water-free magnesium-halide or manganese-halide carrier, and an organo-aluminium com-ponent that contains (a) a complex of a trialkyl-aluminium compound with an ester of a carboxylic acid, and (b) a dialkyl-aluminium halide.
2 A process according to claim 1, wherein the organo-aluminium com-ponent is free of non-complexed trialkyl-aluminium compound.
3. A process according to claim 1 wherein the titanium-halide com-ponent 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 com-ponent 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 claim 5, wherein the said ester is an ester of an aromatic carboxylic acid.
8 A process according to claim 6, wherein the said ester is an ester of an aromatic carboxylic acid.
9. A process according to claim 7, wherein the said carrier is an activated magnesium_halide or manganese-halide, which has a surface area larger than 3 m2/g, or shows broadened diffraction lines in the X-ray spectrum compared to the normal, non-activated halide or has both of the foregoing properties.
10. A process according to claim 8, wherein the said carrier is an activated magnesium-halide or manganese halide which has a surface area larger than 3 m2/g, or shows broadened diffraction lines in the X-ray spectrum compared to the normal, non-activated halide or has both of the foregoing properties.
11. A process according to claim 9, wherein the dialkyl-aluminium halide is added to the reaction product of the titanium-halide component and the complex of the trialkyl-aluminium compound with the ester.
12. A process according to claim 10, wherein the dialkyl-aluminium halide is added to the reaction product of the titanium-halide component and the complex of the trialkyl-aluminium compound with the ester.
13. A process as claimed in claim 11, wherein a polymer of a C3-C6 alkene is prepared,
14 A process as claimed in claim 12, wherein a polymer of a C3-C6 alkene is prepared.
15. A process according to claim 13 or 14 wherein the copolymer is prepared which comprises at least 70% by weight a C3-C6 alkene and the balance ethylene.
16. A process according to claim 7, 9 or 11, wherein the ester is selected from the group etllyl benzoate, ethyl-p-methoxy-benzoate, n-butyl benzoate, methyl toluate, and dimethyl phthalate.
17. A process according to claim 8, 10,or 12, wherein the ester is selected from the group ethyl acetate, amyl propionate,lmethyl butyrate, methyl methacrylate, ethyl acrylate, and dimethyl maleinate.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| NL7509735A NL7509735A (en) | 1975-08-15 | 1975-08-15 | PROCESS FOR POLYMERIZING ALKINES-1. |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1075399A true CA1075399A (en) | 1980-04-08 |
Family
ID=19824303
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA258,584A Expired CA1075399A (en) | 1975-08-15 | 1976-08-06 | Process for polymerizing alkenes-1 |
Country Status (11)
| Country | Link |
|---|---|
| JP (1) | JPS5223188A (en) |
| AT (1) | AT342862B (en) |
| AU (1) | AU503326B2 (en) |
| BE (1) | BE844899A (en) |
| CA (1) | CA1075399A (en) |
| DE (1) | DE2636125A1 (en) |
| ES (1) | ES450725A1 (en) |
| FR (1) | FR2320955A1 (en) |
| GB (1) | GB1549793A (en) |
| IT (1) | IT1062672B (en) |
| NL (1) | NL7509735A (en) |
Families Citing this family (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4234710A (en) * | 1976-07-08 | 1980-11-18 | Phillips Petroleum Company | Catalyst and a polymerization process employing the catalyst |
| JPS5812889B2 (en) * | 1975-09-05 | 1983-03-10 | 日石三菱株式会社 | Polyethylene material |
| NL7711974A (en) * | 1977-11-01 | 1979-05-03 | Stamicarbon | PROCESS FOR POLYMERIZING ALKINES-1. |
| US4260708A (en) * | 1978-09-01 | 1981-04-07 | Phillips Petroleum Company | Phosphite in MgX2 supported TiX3 /AlCl3 catalyst system |
| NL7909333A (en) * | 1979-12-28 | 1981-07-16 | Stamicarbon | METHOD FOR PREPARING A FIXED CATALYTIC TITAN COMPONENT AND METHOD FOR POLYMERIZING OLEFINS-1 USING SUCH A TITAN COMPONENT |
| DK324084A (en) * | 1983-07-21 | 1985-01-22 | Stauffer Chemical Co | OLEPHINE POLYMERIZATION CATALYST AND PROCEDURE |
| JPS6067508A (en) * | 1983-09-22 | 1985-04-17 | Toa Nenryo Kogyo Kk | Polymerization of olefin |
| JPS6281838U (en) * | 1985-10-31 | 1987-05-25 | ||
| JPS63254310A (en) * | 1987-04-11 | 1988-10-21 | Shigeharu Endo | Refuse incinerating device |
| US4851488A (en) * | 1987-04-23 | 1989-07-25 | Shell Oil Company | Process for altering hydrogenated polymer compositions from high melt flow to low melt flow |
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 NL7509735A patent/NL7509735A/en not_active Application Discontinuation
-
1976
- 1976-08-05 BE BE169569A patent/BE844899A/en not_active IP Right Cessation
- 1976-08-06 CA CA258,584A patent/CA1075399A/en not_active Expired
- 1976-08-06 GB GB3288676A patent/GB1549793A/en not_active Expired
- 1976-08-11 DE DE19762636125 patent/DE2636125A1/en not_active Withdrawn
- 1976-08-12 FR FR7624605A patent/FR2320955A1/en active Granted
- 1976-08-12 AT AT600676A patent/AT342862B/en not_active IP Right Cessation
- 1976-08-12 AU AU16805/76A patent/AU503326B2/en not_active Expired
- 1976-08-13 IT IT5089076A patent/IT1062672B/en active
- 1976-08-14 JP JP9740676A patent/JPS5223188A/en active Pending
- 1976-08-14 ES ES450725A patent/ES450725A1/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| IT1062672B (en) | 1984-10-20 |
| FR2320955A1 (en) | 1977-03-11 |
| ATA600676A (en) | 1977-08-15 |
| FR2320955B1 (en) | 1980-05-16 |
| AU1680576A (en) | 1978-02-16 |
| AT342862B (en) | 1978-04-25 |
| BE844899A (en) | 1977-02-07 |
| JPS5223188A (en) | 1977-02-21 |
| DE2636125A1 (en) | 1977-02-24 |
| NL7509735A (en) | 1977-02-17 |
| ES450725A1 (en) | 1977-09-16 |
| GB1549793A (en) | 1979-08-08 |
| AU503326B2 (en) | 1979-08-30 |
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