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
- Publication number
- 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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- Canada
- Prior art keywords
- catalyst
- compound
- aluminium
- group
- metal
- Prior art date
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- Expired
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- 238000000034 method Methods 0.000 title claims abstract description 22
- 239000003054 catalyst Substances 0.000 claims abstract description 57
- 150000001875 compounds Chemical class 0.000 claims abstract description 19
- 150000002736 metal compounds Chemical class 0.000 claims abstract description 13
- 229910001385 heavy metal Inorganic materials 0.000 claims abstract description 12
- 229910052751 metal Inorganic materials 0.000 claims abstract description 7
- 239000002184 metal Substances 0.000 claims abstract description 7
- 150000001399 aluminium compounds Chemical class 0.000 claims abstract description 6
- 230000000737 periodic effect Effects 0.000 claims abstract description 6
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical group [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 claims abstract description 4
- 150000001450 anions Chemical class 0.000 claims abstract description 3
- 125000005843 halogen group Chemical group 0.000 claims abstract description 3
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract 2
- 239000010936 titanium Substances 0.000 claims description 21
- KLZUFWVZNOTSEM-UHFFFAOYSA-K Aluminium flouride Chemical compound F[Al](F)F KLZUFWVZNOTSEM-UHFFFAOYSA-K 0.000 claims description 20
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 11
- 229910052719 titanium Inorganic materials 0.000 claims description 11
- 239000004411 aluminium Substances 0.000 claims description 9
- 229910052782 aluminium Inorganic materials 0.000 claims description 9
- 229910052720 vanadium Inorganic materials 0.000 claims description 7
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 6
- 150000004820 halides Chemical class 0.000 claims description 5
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical group [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 3
- QAOWNCQODCNURD-UHFFFAOYSA-L sulfate group Chemical group S(=O)(=O)([O-])[O-] QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 3
- 229910021653 sulphate ion Inorganic materials 0.000 claims description 3
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 2
- 125000005234 alkyl aluminium group Chemical group 0.000 claims description 2
- 229910052804 chromium Inorganic materials 0.000 claims description 2
- 239000011651 chromium Substances 0.000 claims description 2
- 150000001336 alkenes Chemical class 0.000 claims 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical group F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 claims 1
- 229920000642 polymer Polymers 0.000 abstract description 22
- 239000000155 melt Substances 0.000 abstract description 12
- 229920001577 copolymer Polymers 0.000 abstract description 2
- 229920001519 homopolymer Polymers 0.000 abstract description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 21
- 239000005977 Ethylene Substances 0.000 description 21
- -1 aluminium halides Chemical class 0.000 description 20
- 239000004698 Polyethylene Substances 0.000 description 18
- 229920000573 polyethylene Polymers 0.000 description 18
- 230000000052 comparative effect Effects 0.000 description 15
- 230000000694 effects Effects 0.000 description 11
- 229910010066 TiC14 Inorganic materials 0.000 description 9
- 230000003197 catalytic effect Effects 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- 229920006395 saturated elastomer Polymers 0.000 description 6
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 239000000047 product Substances 0.000 description 5
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 4
- 125000000217 alkyl group Chemical group 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 239000001307 helium Substances 0.000 description 4
- 229910052734 helium Inorganic materials 0.000 description 4
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- NJXPYZHXZZCTNI-UHFFFAOYSA-N 3-aminobenzonitrile Chemical compound NC1=CC=CC(C#N)=C1 NJXPYZHXZZCTNI-UHFFFAOYSA-N 0.000 description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 3
- 150000001398 aluminium Chemical class 0.000 description 3
- IMNFDUFMRHMDMM-UHFFFAOYSA-N anhydrous n-heptane Natural products CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 3
- 229910052681 coesite Inorganic materials 0.000 description 3
- 229910052906 cristobalite Inorganic materials 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- 235000012239 silicon dioxide Nutrition 0.000 description 3
- 229910052682 stishovite Inorganic materials 0.000 description 3
- 229910052723 transition metal Inorganic materials 0.000 description 3
- 150000003624 transition metals Chemical class 0.000 description 3
- 229910052905 tridymite Inorganic materials 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- 229910002651 NO3 Inorganic materials 0.000 description 2
- 150000004703 alkoxides Chemical class 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- AFABGHUZZDYHJO-UHFFFAOYSA-N dimethyl butane Natural products CCCC(C)C AFABGHUZZDYHJO-UHFFFAOYSA-N 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 235000012245 magnesium oxide Nutrition 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910019440 Mg(OH) Inorganic materials 0.000 description 1
- 229910017974 NH40H Inorganic materials 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 229910010061 TiC13 Inorganic materials 0.000 description 1
- 229910021552 Vanadium(IV) chloride Inorganic materials 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 229910000091 aluminium hydride Inorganic materials 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 229910000323 aluminium silicate Inorganic materials 0.000 description 1
- AVKUERGKIZMTKX-NJBDSQKTSA-N ampicillin Chemical compound C1([C@@H](N)C(=O)N[C@H]2[C@H]3SC([C@@H](N3C2=O)C(O)=O)(C)C)=CC=CC=C1 AVKUERGKIZMTKX-NJBDSQKTSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 238000000071 blow moulding Methods 0.000 description 1
- YNLAOSYQHBDIKW-UHFFFAOYSA-M diethylaluminium chloride Chemical compound CC[Al](Cl)CC YNLAOSYQHBDIKW-UHFFFAOYSA-M 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000007792 gaseous phase Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 230000026030 halogenation Effects 0.000 description 1
- 238000005658 halogenation reaction Methods 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 150000004678 hydrides Chemical class 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000012442 inert solvent Substances 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- UBZYKBZMAMTNKW-UHFFFAOYSA-J titanium tetrabromide Chemical compound Br[Ti](Br)(Br)Br UBZYKBZMAMTNKW-UHFFFAOYSA-J 0.000 description 1
- MCULRUJILOGHCJ-UHFFFAOYSA-N triisobutylaluminium Chemical compound CC(C)C[Al](CC(C)C)CC(C)C MCULRUJILOGHCJ-UHFFFAOYSA-N 0.000 description 1
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical compound C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 description 1
- JTJFQBNJBPPZRI-UHFFFAOYSA-J vanadium tetrachloride Chemical compound Cl[V](Cl)(Cl)Cl JTJFQBNJBPPZRI-UHFFFAOYSA-J 0.000 description 1
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
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
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
~s~
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.
~S4~C~
,.
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.
`~
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.
~S4~C~
,.
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.
`~
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 |
|---|---|---|---|
| IT1915177A IT1074699B (en) | 1977-01-11 | 1977-01-11 | HIGH ACTIVITY CATALYSTS FOR THE POLYMERIZATION OF ALFA-OLEFINE |
| IT19151A/77 | 1977-01-11 |
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 |
|---|---|
| IT1074699B (en) | 1985-04-20 |
| AR217262A1 (en) | 1980-03-14 |
| GB1588643A (en) | 1981-04-29 |
| MX5181E (en) | 1983-04-21 |
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