CA1105440A - PROCESS FOR THE LOW PRESSURE POLYMERISATION AND COPOLYMERISATION OF .alpha.-OLEFINS - Google Patents
PROCESS FOR THE LOW PRESSURE POLYMERISATION AND COPOLYMERISATION OF .alpha.-OLEFINSInfo
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- CA1105440A CA1105440A CA288,180A CA288180A CA1105440A CA 1105440 A CA1105440 A CA 1105440A CA 288180 A CA288180 A CA 288180A CA 1105440 A CA1105440 A CA 1105440A
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- catalyst
- compound
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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
Abstract
ABSTRACT OF THE DISCLOSURE
This invention describes a low pressure process for the homo- or copolymerisation of olefines containing 2 to 10 carbon atoms in the molecule. In particular, it des-cribes a polymerisation catalyst formed from a compound of a Group IV, V or VI heavy metal (Periodic Table of Mendeleev) and an organic metal compound of a metal of Group I, II or III; said catalyst being supported on an aluminium compound of the formula AlKX(3? - n)-nOH, where X is a halogen atom or an inorganic oxygenated anion, m is the valency of the individual group X, K is the number of the aluminium atoms and n is a number varying from 0.01 to 3. As the melt index of the homo and copolymers obtained by the invention can vary over a very wide range, these polymers are suitable for many types of operations.
This invention describes a low pressure process for the homo- or copolymerisation of olefines containing 2 to 10 carbon atoms in the molecule. In particular, it des-cribes a polymerisation catalyst formed from a compound of a Group IV, V or VI heavy metal (Periodic Table of Mendeleev) and an organic metal compound of a metal of Group I, II or III; said catalyst being supported on an aluminium compound of the formula AlKX(3? - n)-nOH, where X is a halogen atom or an inorganic oxygenated anion, m is the valency of the individual group X, K is the number of the aluminium atoms and n is a number varying from 0.01 to 3. As the melt index of the homo and copolymers obtained by the invention can vary over a very wide range, these polymers are suitable for many types of operations.
Description
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An object o~ the present invention is to provide supports particularly suitable for the production of catalysts for the low pressure polymerisation and copolymerisation of ~-olefines. In such processes, the catalytic system generally consists of a Ziegler catalyst, for example a halogen of a transition metal and an organic metal compound.
The transition metal may notably be fixed onto a support such as A1203, aluminium silicates, SiO2, MgO, MgC03 or Mg(OH)2-Said low pressure polymerisation processes may also be executed in the presence of catalytic complexes of the TiC13. 1/3 AlC13 type, as described in British patent 1,268,415, and in U.S.A. patent 3,639,377.
Processes of this type have the advantage of easy control of the average molecular weight of the product polymers. However, they have a considerable drawback in that the polymers generally require washing with alcoholic solutions to separate them from the harmful residues of the catalytic system.
Halogenation of the supports, for example A1203, SiO2, MgO or SiO2.A1203, lead to a considerable increase in the activity of the catalyst system, such that it i5 possible to avoid the costly final wash of the polymer (see for example, British patents 1,31~,78~, and 1,315,770).
Such catalysts however do not allow easy control of the average molecular weight of the polymer, and the products are therefore often difficult to work, having, in general, very high average molecular weights and melt indices approximately equal to zero (measured by the ASTM
D 1238 method, with a weight of 2.16 Kg).
We have now discovered a process for the polymerisation and copolymerisation of ~-olefines, which combines the advantages of both the aforementioned types of catalyst, .e.:
a) high catalytic activity in polymerisation such that it is possible to dispense with any washing of the polymers obtained;
b) easy control of the average molecular weights of the polymers.
The catalyst support used in this process, which before use is reacted with a Ziegler catalyst, consists of an aluminium compound of the formula (I).
lK (3K _ n) nH (I) where:
X is a halogen atom or an inorganic oxygenated anion such as a sulphate or nitrate);
m is the valency of the individual group X;
K is the number of aluminium atoms;
n is an integer from 0.01 to 3, and preferably from 0.05 to 3.
This support may be obtained from the corresponding nonhydroxylated aluminium compound by subjecting it to partial hydrolysis by the method described in detail below.
It may be mentioned that the best results are obtained starting from aluminium halides, in particular AlF3.
Aluminium fluoride exists in three different allotropic forms: ~-rhombic, ~-hexagonal and ~-tetragonal.
All three forms are very suitable for the preparation of highly active supports. However, particularly good ~' ~
results have been obtained from the ~-hexagonal form.
The catalytic hydroxylated support is formed by treating an aluminium hydride or an oxygenated inorganic salt of aluminium (such as sulphate or nitrate) with any compound able to partially hydrolyse it and thus introduce hydroxyl groups therein. Water or aqueous ammonia are preferred ~or this purpose, but other organic or inorganic substances, either pure or in solution, have been found to give good results.
The reaction between the aluminium compound of formula AlX3 and the compound which is to introduce hydroxyl groups therein may be carried out in a fixed or fluidised bed.
In general, an inert gas is added. Examples include-nitrogen; helium; argon; and air~ These gasses may be completely or only partially saturated with the hydrolysing compound. The critical conditions of the partial hydrolysis reaction of the compound AlX3 are the temperature and duration of treatment. By varying these, the value of n varies in the following manner: as the temperature and duration of treatment increase, n tends to decrease until it reaches zero.
In the operating conditions of the invention the zero value is never reached.
The treatment temperature may vary from 100 to 800C, and preferably from 200 to 600C.
The duration of treatment may vary from l to 24 hours and preferably from 4 to 12 hours.
The present invention provides a method for preparing a wide range of catalytic supports for which the specific activity of the final catalytic system, expressed as kg of obtained polymer/g transition metal/hour/atmosphere of olefine, varies as the value of n varies. A simultaneous variation in the properties of the product polymer (such as specific density, crystallinity, average molecular weight and melt index) occurs enabling the preparation of a wide variety of polymers having, for example, a specific density which varies from 0.93 to 0.97 and a melt index which can reach 20 lmeasured by the ASTM D 1238 method, with a weight of 2.16 kg).
The catalytic system according to the present invention is prepared by reacting the hydroxylated aluminium support with a compound of a heavy metal of Group IV to Group VI of the Periodic Table, and subsequently activating the catalyst component thus formed by treating it with an organic metal compound of a metal of Group I to Group III of the Periodic Table.
Heavy metal compounds which are shown to be par~icularly suitable are halides, oxyhalides and alkoxyhalides.
Preferred heavy metals are titanium, vanadium and chromium.
Suitable compounds are, therefore: TiC14, TiBr4, VCl4, VOC13, V0Br3, CrO2C12, Ti(O_c2H5)3cl and Ti(O-isoC4Hg)2Cl2. However, best results are obtained with TiC14.
The conditions required for the reaction between the hydroxylated aluminium support and the heavy metal compound are not critical, and they may vary over a wide range. The reaction temperature may vary from 0 to 300C, and the duration of the reaction from l to 4 hours. The heavy metal compound may be used in its pure ~.~
state or in mixture with an anhydrous organic solvent.
It is pxeferable to use an excess of heavy metal compound with respect to the hydroxylated aluminium support.
Examples of organic metal compounds which may be used include: metal alkyls, halides or hydrides of metal alkyls; and Grignard compounds.
Examples of the relative metals are: aluminium; Zn;
Mg; Na; and Li. Thus, examples of suitable compounds are:
trimethylaluminium; monochlorodiethylaluminium; aluminium diisobutylhydride; (C2H5)MgBr; and ethylaluminiumsesquichloride.
However, best results are generally obtained with aluminium alkyls or halides of alkyl aluminium. In particular triethylaluminium and triisobutylaluminium are excellent.
The quantity of organic metal compound to be used is not critical. Preferably however, the compound should be present in molar excess with respect to the heavy metal contained in the support.
The catalytic system according to the present invention is applicable to homo or copolymerisation of ~-olefines r for example ethylene, propylene, butene.1, pentene.l, he~ene.l and 4-methyl-pentane.l.
It is particularly advantageous when used for the preparation of homo or copolymers of ethylene. The homo or copolymerisation of olefines may be carried out by any of the usual methods, either in the gaseous phase or in solution. In this second case, inert solvents are used, for example, aliphatic or cyclo-aliphatic hydrocarbons.
The average molecular weight of the polymer to be \, ,~ . . .
obtained may be controlled either b~ the choice of the hydroxylated support, prepared in accordance with the invention, or by the addition of one or more molecular weight regulators, such as hydrogen, alcohols, CO2, Zn alkyls or Cd alkyls.
The density of the product polymers may be controlled by adding to the polymerisation reaction mixture an alkoxide of a ~etal from Group IV or V of the Periodic Table. Alkoxides of titanium or vanadium, for example Ti (i-butoxy)4 are preferred.
As the melt index of the homo and coplymers obtained by the present invention can vary over a very wide range, these polymers are suitable for many types of operation, such as extrusion or blow moulding.
Some examples are given hereinafter for purposes of illustration. In no case are they to be considered as limiting the invention. All melt index measurements were made in accordance with the ASTM D 1238 method, with a weight of 2.16 Kg.
5 g of ~-rhombic AlF3 are treated with 75 cc of pure li~uid TiC14 and heated under reflux and strong a~itation for one hour at a temperature of 136C. The solid reaction product is separated, washed firstly with TiC14 and then ~ith anhydrous n-heptane until free chloride has completely disappeared from the wash solvent. It is then dried.
The catalyst component thus prepared has a titanium content of 1.5% by weight with respect to the support.
Polymerisation is then carried out in the following manner:
0.2 g of the catalyst component are added to a solution of l g of triethylaluminium in 1500 cc of anhydrous n-heptane. The entire mlxture is then transferred under anhydrous nitrogen into a 51.steel autoclave provided with a bladed stirrer having a stirring speed variable from 500 to 2000 r.p.m. The autoclave is heated to a temperature of 90C and kept at this temperature during polymerisation (l hour).
The pressure is raised to 4 Kg/cm2 with hydrogen and then to 14 Kg/cm with ethylene. During polymerisationr the partial pressure of the ethylene is kept constant by continuously adding new ethylene. After one hour the autoclave is degassed and the product discharged. The yield is 180 g of polyethylene/g catalyst/h/atmosphere of ethylene.
The specific activity of the catalyst component in terms of the quantity of titanium contained in it is 12.0 kg of polyethylene/g Ti/h/atmosphere of ethylene.
The polymer has a melt index of 0.00 y/lO minutes.
E~AMPI,E l 5 g of ~-rhombic AlF3 are treated in a fluidised bed with nitrogen saturated with lNl aqueous ammonia at a temperature of 200C for 4 hours.
The compound thus obtained is treated with TiC14 to prepare the catalyst component, using the same method as ~escribed in comparative example l. The catalyst component thus prepared has a titanium content of 1. 8% by weight with respect to the support.
Polymerisation is carried out as described in comparative example l.
The yield is 610 g of polyethylene/g catalyst/h/atmosphere of ethylene.
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,.
The specific activity of the catalyst component is 33.88 kg of polyethylene/g Ti/h/atmosphere of ethylene.
The polymer has a melt index of 4.0 g/10 minutes.
5 g of ~-hexagonal AlF3 are treated with TiC14 to prepare the catalyst component using the same method as described in comparative example 1. The catalyst component thus prepared has a titanium content of 0.45% by weight with respect to the support.
Polymerisation is carried out as described in comparative example 1.
The yield is 67 g of polyethylene/g catalyst/h/atmosphere of ethylene.
The specific activity of the catalyst component is 14.88 kg of polyethylene/g Ti/h/atmosphere of e-thylene.
The polymer has a melt index of 0.1 g/10 minutes.
5 g of ~-hexagonal AlF3 are treated in a fluidised bed with helium saturated with water, at a temperature of 500C for 4 hours.
The compound thus obtained is treated with TiCl~ to prepare the catalyst component, using the same method as described in comparative example 1. The catalyst component thus prepared has a titanium content of 0.65~ by weight with respect to the support.
Polymerisation is carried out as described in comparative example 1.
The yield is 193 g of polyethylene/g catalyst/h/atmosphere of ethylene.
The specific activity of the catalyst component is 29.7 kg of polyethylene/g Ti/h/atmosphere of ethylene.
~r The polymer has a melt index of 2.6 g/10 minutes.
5 g of ~-hexagonal AlF3 are treated in a fluidised bed with helium saturated with water, at a temperature of 300C for 4 hours.
The compound thus obtained ls treated with TiC14 to prepare the catalyst component, using the same method as described in comparative example 1. The catalyst component thus prepared shows a titanium content of 0.9%
by weight with respect to the support.
Polymerisation is carried out as described in comparative example 1, except that instead of using aluminium triethyl, an equal quantity (1 g) of aluminium triisobutyl is used.
The yield is 315 g of polyethylene/g catalyst/h/atmosphere of ethylene.
The specific activity of the catalyst component is 35.0 kg of polyethylene/g Ti/h/atmosphere of ethylene.
The polymer has a melt index of 1~5 9/10 minutes.
5 9 of ~-hexagonal AlF3 are treated in a fluidised bed with nitrogen saturated with an aqueous solution containing 3 g equivalent/litre of NH40H, at a temperature o 200C for 4 hours.
The compound thus obtained is treated with TiC14 to prepare the catalyst component, using the same method as described in comparative example 1. The catalyst thus prepared has a titanium content of 2.5~ by weight with respect to the support.
Polymerisation is carried out as described in comparative example 1.
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The yield is 750 g of polyethylene/g catalyst/h/atmosphere of ethylene.
The specific activity of the catalyst component is 28,6 kg of polyethylene/g Ti/h/atmosphere of ethylene.
The polymer has a melt index of 2.0 g/10 minutes.
5 g of ~-hexagonal A1~3 are treated with 75 cc of pure liquid VOC13 and refluxed at a temperature of 127C
for one hour with strong agitation. This solid reaction product is separated, washed firstly with VOC13 and then with anhydrous n-heptane until free chloride in the wash solvent completely disappears. It is then dried.
The catalyst component thus prepared has a vanadium content of 1.3~ by weight with respect to the support.
Polymerisation is carried out as described in comparative example 1.
The yield is 210 g of polyethylene/g catalyst/h/atmosphere o~ ethylene.
The specific activity of the catalyst component is 16.15 kg of polyethylene/g vanadium/h/atmosphere of ethylene.
The polymer has a melt index of 0.2 g/10 minutes.
5 g of ~-hexagonal AlF3 are treated in a fluidised bed with helium saturated with water, at a temperature of 300C for 4 hours.
The compound thus obtained is treated with VOC13 to prepare the catalyst component, using the same me-thod as described in comparative example 5. The catalyst component thus prepared has a vanadium content of 2.7% by weight with respect to the support.
,, Polymerisation is carried out as described in comparative example 1.
The yield is 760 9 of polyethylene/g catalyst/h/atmosphere of ethylene.
The specific activity of the catalyst component is 28.1 kg of polyethylene/g vanadium/h/atmosphere of ethylene.
The polymer has a melt index of 1.4 9/lO minutes.
5 g of A12~SO4)3 are treated in a fluidised bed with nitrogen containing water vapour, at a temperature of 200C for 6 hours.
The compound thus obtained is treated with TiC14 to prepare the catalyst component r using the same method as described in comparative example 1. The catalyst component thus prepared has a titanium content of 0.55~ by weight with respect to the support.
Polymerisation is carried out as described in comparative example 1, The yield is 139 9 of polyethylene/g catalyst/h/atmosphere of ethylene.
The specific activity of the catalyst component is 25.3 kg of polyethylene/g Ti/h/atmosphere of ethylene.
The polymer has a melt index of 0.5 9/10 minutes.
`~
An object o~ the present invention is to provide supports particularly suitable for the production of catalysts for the low pressure polymerisation and copolymerisation of ~-olefines. In such processes, the catalytic system generally consists of a Ziegler catalyst, for example a halogen of a transition metal and an organic metal compound.
The transition metal may notably be fixed onto a support such as A1203, aluminium silicates, SiO2, MgO, MgC03 or Mg(OH)2-Said low pressure polymerisation processes may also be executed in the presence of catalytic complexes of the TiC13. 1/3 AlC13 type, as described in British patent 1,268,415, and in U.S.A. patent 3,639,377.
Processes of this type have the advantage of easy control of the average molecular weight of the product polymers. However, they have a considerable drawback in that the polymers generally require washing with alcoholic solutions to separate them from the harmful residues of the catalytic system.
Halogenation of the supports, for example A1203, SiO2, MgO or SiO2.A1203, lead to a considerable increase in the activity of the catalyst system, such that it i5 possible to avoid the costly final wash of the polymer (see for example, British patents 1,31~,78~, and 1,315,770).
Such catalysts however do not allow easy control of the average molecular weight of the polymer, and the products are therefore often difficult to work, having, in general, very high average molecular weights and melt indices approximately equal to zero (measured by the ASTM
D 1238 method, with a weight of 2.16 Kg).
We have now discovered a process for the polymerisation and copolymerisation of ~-olefines, which combines the advantages of both the aforementioned types of catalyst, .e.:
a) high catalytic activity in polymerisation such that it is possible to dispense with any washing of the polymers obtained;
b) easy control of the average molecular weights of the polymers.
The catalyst support used in this process, which before use is reacted with a Ziegler catalyst, consists of an aluminium compound of the formula (I).
lK (3K _ n) nH (I) where:
X is a halogen atom or an inorganic oxygenated anion such as a sulphate or nitrate);
m is the valency of the individual group X;
K is the number of aluminium atoms;
n is an integer from 0.01 to 3, and preferably from 0.05 to 3.
This support may be obtained from the corresponding nonhydroxylated aluminium compound by subjecting it to partial hydrolysis by the method described in detail below.
It may be mentioned that the best results are obtained starting from aluminium halides, in particular AlF3.
Aluminium fluoride exists in three different allotropic forms: ~-rhombic, ~-hexagonal and ~-tetragonal.
All three forms are very suitable for the preparation of highly active supports. However, particularly good ~' ~
results have been obtained from the ~-hexagonal form.
The catalytic hydroxylated support is formed by treating an aluminium hydride or an oxygenated inorganic salt of aluminium (such as sulphate or nitrate) with any compound able to partially hydrolyse it and thus introduce hydroxyl groups therein. Water or aqueous ammonia are preferred ~or this purpose, but other organic or inorganic substances, either pure or in solution, have been found to give good results.
The reaction between the aluminium compound of formula AlX3 and the compound which is to introduce hydroxyl groups therein may be carried out in a fixed or fluidised bed.
In general, an inert gas is added. Examples include-nitrogen; helium; argon; and air~ These gasses may be completely or only partially saturated with the hydrolysing compound. The critical conditions of the partial hydrolysis reaction of the compound AlX3 are the temperature and duration of treatment. By varying these, the value of n varies in the following manner: as the temperature and duration of treatment increase, n tends to decrease until it reaches zero.
In the operating conditions of the invention the zero value is never reached.
The treatment temperature may vary from 100 to 800C, and preferably from 200 to 600C.
The duration of treatment may vary from l to 24 hours and preferably from 4 to 12 hours.
The present invention provides a method for preparing a wide range of catalytic supports for which the specific activity of the final catalytic system, expressed as kg of obtained polymer/g transition metal/hour/atmosphere of olefine, varies as the value of n varies. A simultaneous variation in the properties of the product polymer (such as specific density, crystallinity, average molecular weight and melt index) occurs enabling the preparation of a wide variety of polymers having, for example, a specific density which varies from 0.93 to 0.97 and a melt index which can reach 20 lmeasured by the ASTM D 1238 method, with a weight of 2.16 kg).
The catalytic system according to the present invention is prepared by reacting the hydroxylated aluminium support with a compound of a heavy metal of Group IV to Group VI of the Periodic Table, and subsequently activating the catalyst component thus formed by treating it with an organic metal compound of a metal of Group I to Group III of the Periodic Table.
Heavy metal compounds which are shown to be par~icularly suitable are halides, oxyhalides and alkoxyhalides.
Preferred heavy metals are titanium, vanadium and chromium.
Suitable compounds are, therefore: TiC14, TiBr4, VCl4, VOC13, V0Br3, CrO2C12, Ti(O_c2H5)3cl and Ti(O-isoC4Hg)2Cl2. However, best results are obtained with TiC14.
The conditions required for the reaction between the hydroxylated aluminium support and the heavy metal compound are not critical, and they may vary over a wide range. The reaction temperature may vary from 0 to 300C, and the duration of the reaction from l to 4 hours. The heavy metal compound may be used in its pure ~.~
state or in mixture with an anhydrous organic solvent.
It is pxeferable to use an excess of heavy metal compound with respect to the hydroxylated aluminium support.
Examples of organic metal compounds which may be used include: metal alkyls, halides or hydrides of metal alkyls; and Grignard compounds.
Examples of the relative metals are: aluminium; Zn;
Mg; Na; and Li. Thus, examples of suitable compounds are:
trimethylaluminium; monochlorodiethylaluminium; aluminium diisobutylhydride; (C2H5)MgBr; and ethylaluminiumsesquichloride.
However, best results are generally obtained with aluminium alkyls or halides of alkyl aluminium. In particular triethylaluminium and triisobutylaluminium are excellent.
The quantity of organic metal compound to be used is not critical. Preferably however, the compound should be present in molar excess with respect to the heavy metal contained in the support.
The catalytic system according to the present invention is applicable to homo or copolymerisation of ~-olefines r for example ethylene, propylene, butene.1, pentene.l, he~ene.l and 4-methyl-pentane.l.
It is particularly advantageous when used for the preparation of homo or copolymers of ethylene. The homo or copolymerisation of olefines may be carried out by any of the usual methods, either in the gaseous phase or in solution. In this second case, inert solvents are used, for example, aliphatic or cyclo-aliphatic hydrocarbons.
The average molecular weight of the polymer to be \, ,~ . . .
obtained may be controlled either b~ the choice of the hydroxylated support, prepared in accordance with the invention, or by the addition of one or more molecular weight regulators, such as hydrogen, alcohols, CO2, Zn alkyls or Cd alkyls.
The density of the product polymers may be controlled by adding to the polymerisation reaction mixture an alkoxide of a ~etal from Group IV or V of the Periodic Table. Alkoxides of titanium or vanadium, for example Ti (i-butoxy)4 are preferred.
As the melt index of the homo and coplymers obtained by the present invention can vary over a very wide range, these polymers are suitable for many types of operation, such as extrusion or blow moulding.
Some examples are given hereinafter for purposes of illustration. In no case are they to be considered as limiting the invention. All melt index measurements were made in accordance with the ASTM D 1238 method, with a weight of 2.16 Kg.
5 g of ~-rhombic AlF3 are treated with 75 cc of pure li~uid TiC14 and heated under reflux and strong a~itation for one hour at a temperature of 136C. The solid reaction product is separated, washed firstly with TiC14 and then ~ith anhydrous n-heptane until free chloride has completely disappeared from the wash solvent. It is then dried.
The catalyst component thus prepared has a titanium content of 1.5% by weight with respect to the support.
Polymerisation is then carried out in the following manner:
0.2 g of the catalyst component are added to a solution of l g of triethylaluminium in 1500 cc of anhydrous n-heptane. The entire mlxture is then transferred under anhydrous nitrogen into a 51.steel autoclave provided with a bladed stirrer having a stirring speed variable from 500 to 2000 r.p.m. The autoclave is heated to a temperature of 90C and kept at this temperature during polymerisation (l hour).
The pressure is raised to 4 Kg/cm2 with hydrogen and then to 14 Kg/cm with ethylene. During polymerisationr the partial pressure of the ethylene is kept constant by continuously adding new ethylene. After one hour the autoclave is degassed and the product discharged. The yield is 180 g of polyethylene/g catalyst/h/atmosphere of ethylene.
The specific activity of the catalyst component in terms of the quantity of titanium contained in it is 12.0 kg of polyethylene/g Ti/h/atmosphere of ethylene.
The polymer has a melt index of 0.00 y/lO minutes.
E~AMPI,E l 5 g of ~-rhombic AlF3 are treated in a fluidised bed with nitrogen saturated with lNl aqueous ammonia at a temperature of 200C for 4 hours.
The compound thus obtained is treated with TiC14 to prepare the catalyst component, using the same method as ~escribed in comparative example l. The catalyst component thus prepared has a titanium content of 1. 8% by weight with respect to the support.
Polymerisation is carried out as described in comparative example l.
The yield is 610 g of polyethylene/g catalyst/h/atmosphere of ethylene.
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,.
The specific activity of the catalyst component is 33.88 kg of polyethylene/g Ti/h/atmosphere of ethylene.
The polymer has a melt index of 4.0 g/10 minutes.
5 g of ~-hexagonal AlF3 are treated with TiC14 to prepare the catalyst component using the same method as described in comparative example 1. The catalyst component thus prepared has a titanium content of 0.45% by weight with respect to the support.
Polymerisation is carried out as described in comparative example 1.
The yield is 67 g of polyethylene/g catalyst/h/atmosphere of ethylene.
The specific activity of the catalyst component is 14.88 kg of polyethylene/g Ti/h/atmosphere of e-thylene.
The polymer has a melt index of 0.1 g/10 minutes.
5 g of ~-hexagonal AlF3 are treated in a fluidised bed with helium saturated with water, at a temperature of 500C for 4 hours.
The compound thus obtained is treated with TiCl~ to prepare the catalyst component, using the same method as described in comparative example 1. The catalyst component thus prepared has a titanium content of 0.65~ by weight with respect to the support.
Polymerisation is carried out as described in comparative example 1.
The yield is 193 g of polyethylene/g catalyst/h/atmosphere of ethylene.
The specific activity of the catalyst component is 29.7 kg of polyethylene/g Ti/h/atmosphere of ethylene.
~r The polymer has a melt index of 2.6 g/10 minutes.
5 g of ~-hexagonal AlF3 are treated in a fluidised bed with helium saturated with water, at a temperature of 300C for 4 hours.
The compound thus obtained ls treated with TiC14 to prepare the catalyst component, using the same method as described in comparative example 1. The catalyst component thus prepared shows a titanium content of 0.9%
by weight with respect to the support.
Polymerisation is carried out as described in comparative example 1, except that instead of using aluminium triethyl, an equal quantity (1 g) of aluminium triisobutyl is used.
The yield is 315 g of polyethylene/g catalyst/h/atmosphere of ethylene.
The specific activity of the catalyst component is 35.0 kg of polyethylene/g Ti/h/atmosphere of ethylene.
The polymer has a melt index of 1~5 9/10 minutes.
5 9 of ~-hexagonal AlF3 are treated in a fluidised bed with nitrogen saturated with an aqueous solution containing 3 g equivalent/litre of NH40H, at a temperature o 200C for 4 hours.
The compound thus obtained is treated with TiC14 to prepare the catalyst component, using the same method as described in comparative example 1. The catalyst thus prepared has a titanium content of 2.5~ by weight with respect to the support.
Polymerisation is carried out as described in comparative example 1.
.~ , ~59~
The yield is 750 g of polyethylene/g catalyst/h/atmosphere of ethylene.
The specific activity of the catalyst component is 28,6 kg of polyethylene/g Ti/h/atmosphere of ethylene.
The polymer has a melt index of 2.0 g/10 minutes.
5 g of ~-hexagonal A1~3 are treated with 75 cc of pure liquid VOC13 and refluxed at a temperature of 127C
for one hour with strong agitation. This solid reaction product is separated, washed firstly with VOC13 and then with anhydrous n-heptane until free chloride in the wash solvent completely disappears. It is then dried.
The catalyst component thus prepared has a vanadium content of 1.3~ by weight with respect to the support.
Polymerisation is carried out as described in comparative example 1.
The yield is 210 g of polyethylene/g catalyst/h/atmosphere o~ ethylene.
The specific activity of the catalyst component is 16.15 kg of polyethylene/g vanadium/h/atmosphere of ethylene.
The polymer has a melt index of 0.2 g/10 minutes.
5 g of ~-hexagonal AlF3 are treated in a fluidised bed with helium saturated with water, at a temperature of 300C for 4 hours.
The compound thus obtained is treated with VOC13 to prepare the catalyst component, using the same me-thod as described in comparative example 5. The catalyst component thus prepared has a vanadium content of 2.7% by weight with respect to the support.
,, Polymerisation is carried out as described in comparative example 1.
The yield is 760 9 of polyethylene/g catalyst/h/atmosphere of ethylene.
The specific activity of the catalyst component is 28.1 kg of polyethylene/g vanadium/h/atmosphere of ethylene.
The polymer has a melt index of 1.4 9/lO minutes.
5 g of A12~SO4)3 are treated in a fluidised bed with nitrogen containing water vapour, at a temperature of 200C for 6 hours.
The compound thus obtained is treated with TiC14 to prepare the catalyst component r using the same method as described in comparative example 1. The catalyst component thus prepared has a titanium content of 0.55~ by weight with respect to the support.
Polymerisation is carried out as described in comparative example 1, The yield is 139 9 of polyethylene/g catalyst/h/atmosphere of ethylene.
The specific activity of the catalyst component is 25.3 kg of polyethylene/g Ti/h/atmosphere of ethylene.
The polymer has a melt index of 0.5 9/10 minutes.
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Claims (11)
1. A catalyst for the homo- or copolymerisation of olefines in accordance with the low pressure Ziegler method, said catalyst comprising a compound of a Group IV, V or VI
heavy metal (Periodic Table of Mendeleev), and an organic metal compound of a metal of Group I, II or III of the Periodic Table of Mendeleev, supported on an aluminium compound as represented by the formula (I) I
where:
X is a halogen atom or an inorganic oxygenated anion m is the valency of the individual group X
K is the number of aluminium atoms n is a number varying from 0.01 to 3.
heavy metal (Periodic Table of Mendeleev), and an organic metal compound of a metal of Group I, II or III of the Periodic Table of Mendeleev, supported on an aluminium compound as represented by the formula (I) I
where:
X is a halogen atom or an inorganic oxygenated anion m is the valency of the individual group X
K is the number of aluminium atoms n is a number varying from 0.01 to 3.
2. A catalyst as claimed in claim 1 wherein n is a number from 0.05 to 3.
3. A catalyst as claimed in claim 1 wherein X is a fluoride atom, the aluminium fluoride being in any of its allotropic forms .alpha.-rhombic, .beta.-hexagonal and .gamma.-tetragonal.
4. A catalyst as claimed in claim 1 wherein X is a sulphate or nitrate anion.
5. A catalyst as claimed in claim 1, 2 or 3, wherein said Group IV, V or VI heavy metal is titanium, vanadium or chromium.
6. A catalyst as claimed in claim 1, 2 or 3, wherein said compound of a Group IV, V or VI heavy metal is a halide, oxyhalide or alkoxyhalide.
7. A catalyst as claimed in claim 1, 2 or 3, wherein said Group IV compound is titanium tetrachloride.
8. A catalyst as claimed in claim 1, 2 or 3, wherein said organic metal compound is an aluminium alkyl or a halide of alkyl aluminium.
9. A catalyst as claimed in claim 1, 2 or 3, wherein the organic metal compound is aluminium triethyl or triisobutyl.
10. A process for producing a catalyst as defined in claim 1 which comprises reacting a Group IV, V or VI heavy metal with an aluminium compound of formula (I) and reacting the product obtained with an organic metal compound of a metal of Group I, II or III.
11. A process for the homo- or copolymerisation of olefins containing 2 to 10 carbon atoms in the molecule which com-prises reacting the olefins in the presence of a catalyst as defined in claim 1.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| IT19151A/77 | 1977-01-11 | ||
| IT1915177A IT1074699B (en) | 1977-01-11 | 1977-01-11 | HIGH ACTIVITY CATALYSTS FOR THE POLYMERIZATION OF ALFA-OLEFINE |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1105440A true CA1105440A (en) | 1981-07-21 |
Family
ID=11155297
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA288,180A Expired CA1105440A (en) | 1977-01-11 | 1977-10-05 | PROCESS FOR THE LOW PRESSURE POLYMERISATION AND COPOLYMERISATION OF .alpha.-OLEFINS |
Country Status (5)
| Country | Link |
|---|---|
| AR (1) | AR217262A1 (en) |
| CA (1) | CA1105440A (en) |
| GB (1) | GB1588643A (en) |
| IT (1) | IT1074699B (en) |
| MX (1) | MX5181E (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5064796A (en) * | 1991-01-07 | 1991-11-12 | Exxon Chemical Patents Inc. | Support adjuvant for improved vanadium polymerization catalyst |
-
1977
- 1977-01-11 IT IT1915177A patent/IT1074699B/en active
- 1977-10-03 AR AR26942477A patent/AR217262A1/en active
- 1977-10-05 CA CA288,180A patent/CA1105440A/en not_active Expired
- 1977-10-06 MX MX645877U patent/MX5181E/en unknown
- 1977-10-10 GB GB4205477A patent/GB1588643A/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| MX5181E (en) | 1983-04-21 |
| IT1074699B (en) | 1985-04-20 |
| AR217262A1 (en) | 1980-03-14 |
| GB1588643A (en) | 1981-04-29 |
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