AU620472B2 - Process for the continuous preparation of catalysts for low-pressure polymerisation of olefins - Google Patents
Process for the continuous preparation of catalysts for low-pressure polymerisation of olefins Download PDFInfo
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- AU620472B2 AU620472B2 AU45479/89A AU4547989A AU620472B2 AU 620472 B2 AU620472 B2 AU 620472B2 AU 45479/89 A AU45479/89 A AU 45479/89A AU 4547989 A AU4547989 A AU 4547989A AU 620472 B2 AU620472 B2 AU 620472B2
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- 239000003054 catalyst Substances 0.000 title claims abstract description 25
- 238000000034 method Methods 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title claims description 12
- 150000001336 alkenes Chemical class 0.000 title description 4
- 239000004711 α-olefin Substances 0.000 claims abstract description 10
- 239000010936 titanium Substances 0.000 claims description 40
- 150000001875 compounds Chemical class 0.000 claims description 35
- 150000001399 aluminium compounds Chemical class 0.000 claims description 14
- 239000004411 aluminium Substances 0.000 claims description 11
- 229910052782 aluminium Inorganic materials 0.000 claims description 11
- 239000000203 mixture Substances 0.000 claims description 9
- 125000004432 carbon atom Chemical group C* 0.000 claims description 8
- 150000002430 hydrocarbons Chemical group 0.000 claims description 8
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 7
- 239000005977 Ethylene Substances 0.000 claims description 7
- 238000006243 chemical reaction Methods 0.000 claims description 7
- 125000000217 alkyl group Chemical group 0.000 claims description 6
- 229940077746 antacid containing aluminium compound Drugs 0.000 claims description 6
- 239000007795 chemical reaction product Substances 0.000 claims description 5
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 claims description 4
- 239000000460 chlorine Substances 0.000 claims description 4
- 239000000725 suspension Substances 0.000 claims description 4
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 3
- 150000001648 bromium Chemical class 0.000 claims description 3
- 229910052794 bromium Inorganic materials 0.000 claims description 3
- 229910052801 chlorine Inorganic materials 0.000 claims description 3
- 150000003609 titanium compounds Chemical class 0.000 claims description 3
- 235000009917 Crataegus X brevipes Nutrition 0.000 claims 1
- 235000013204 Crataegus X haemacarpa Nutrition 0.000 claims 1
- 235000009685 Crataegus X maligna Nutrition 0.000 claims 1
- 235000009444 Crataegus X rubrocarnea Nutrition 0.000 claims 1
- 235000009486 Crataegus bullatus Nutrition 0.000 claims 1
- 235000017181 Crataegus chrysocarpa Nutrition 0.000 claims 1
- 235000009682 Crataegus limnophila Nutrition 0.000 claims 1
- 235000004423 Crataegus monogyna Nutrition 0.000 claims 1
- 240000000171 Crataegus monogyna Species 0.000 claims 1
- 235000002313 Crataegus paludosa Nutrition 0.000 claims 1
- 235000009840 Crataegus x incaedua Nutrition 0.000 claims 1
- 239000007792 gaseous phase Substances 0.000 claims 1
- 239000002245 particle Substances 0.000 description 26
- 229920000642 polymer Polymers 0.000 description 14
- 239000000243 solution Substances 0.000 description 14
- 238000009826 distribution Methods 0.000 description 11
- 229910052719 titanium Inorganic materials 0.000 description 8
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 7
- -1 aluminium alkyl halides Chemical class 0.000 description 7
- 229930195733 hydrocarbon Natural products 0.000 description 6
- 239000012190 activator Substances 0.000 description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 150000002902 organometallic compounds Chemical class 0.000 description 5
- ONJXMLOOLFUVAT-UHFFFAOYSA-N C(=CC(C)=C)[AlH2] Chemical compound C(=CC(C)=C)[AlH2] ONJXMLOOLFUVAT-UHFFFAOYSA-N 0.000 description 4
- 239000004698 Polyethylene Substances 0.000 description 4
- 239000002270 dispersing agent Substances 0.000 description 4
- 239000000376 reactant Substances 0.000 description 4
- 239000004215 Carbon black (E152) Substances 0.000 description 3
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 3
- 239000011261 inert gas Substances 0.000 description 3
- 239000012442 inert solvent Substances 0.000 description 3
- 229920000573 polyethylene Polymers 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 description 3
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 2
- 229910010061 TiC13 Inorganic materials 0.000 description 2
- 229910010066 TiC14 Inorganic materials 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 150000001993 dienes Chemical class 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 230000000737 periodic effect Effects 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 229910003074 TiCl4 Inorganic materials 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000001649 bromium compounds Chemical class 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 239000002283 diesel fuel Substances 0.000 description 1
- YNLAOSYQHBDIKW-UHFFFAOYSA-M diethylaluminium chloride Chemical compound CC[Al](Cl)CC YNLAOSYQHBDIKW-UHFFFAOYSA-M 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- MGDOJPNDRJNJBK-UHFFFAOYSA-N ethylaluminum Chemical compound [Al].C[CH2] MGDOJPNDRJNJBK-UHFFFAOYSA-N 0.000 description 1
- UAIZDWNSWGTKFZ-UHFFFAOYSA-L ethylaluminum(2+);dichloride Chemical compound CC[Al](Cl)Cl UAIZDWNSWGTKFZ-UHFFFAOYSA-L 0.000 description 1
- 230000007717 exclusion Effects 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 238000000265 homogenisation Methods 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
- 238000001746 injection moulding Methods 0.000 description 1
- 235000017932 juta Nutrition 0.000 description 1
- 239000012280 lithium aluminium hydride Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 150000002899 organoaluminium compounds Chemical class 0.000 description 1
- 125000002370 organoaluminium group Chemical group 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- AQSJGOWTSHOLKH-UHFFFAOYSA-N phosphite(3-) Chemical group [O-]P([O-])[O-] AQSJGOWTSHOLKH-UHFFFAOYSA-N 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- UIIBXLJGQPHPIJ-UHFFFAOYSA-N propan-2-yl hypochlorite;titanium Chemical compound [Ti].CC(C)OCl UIIBXLJGQPHPIJ-UHFFFAOYSA-N 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000003464 sulfur compounds Chemical class 0.000 description 1
- LLZRNZOLAXHGLL-UHFFFAOYSA-J titanic acid Chemical compound O[Ti](O)(O)O LLZRNZOLAXHGLL-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
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 238000010626 work up procedure Methods 0.000 description 1
- 239000008096 xylene Substances 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
- C08F2/00—Processes of polymerisation
-
- 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)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Catalysts (AREA)
Abstract
The invention relates to a process for continuously preparing catalysts for the low-pressure polymerisation of alpha-olefins in a homogeniser.
Description
Tc: THE COMMISSIONER OF PATENTS.
WATERMARK PATENT TRADEMARK ATTORNEYS iI I111 Pr COMMONWEALTH OF AUSTRALI0 7om PATENTS ACT 1952-69
COMPLETE
SPECIFICATION
(ORIGINAL)
Class Int. Class Application Number: Lodged: b Q o 4 6 4 0 Complete Specification Lodged: 0 S Accepted: Published: Priority Related Art 0 0 QZ 0 or 0 04< 0 Name of Applicant HOECHST (S'449 *«06 r AKTIENGESELLSCHAFT Address of Applicant: 50 Bruningstrasse, D-6230 Frankfurt/Main 80, Federal Republic of Germany 0 00 o Actual Inventor Address for Service ERNST PROTT, WOLFGANG PAYER, JUTA WALTER, WINFRIED MATERNE and MHER
ONALLAH
WATERMARK PATENT TRADEMARK ATTORNEYS.
290 Burwood Road, Hawthorn, Victoria, Australia Complete Specification for the invention entitled: PROCESS FOR THE CONTINUOUS PREPARATION OF CATALYSTS FOR LOW-PRESSURE POLYMERISATION OF OLEFINS The following statement is a full description of this invention, including the best method of performing it known to To: THE COMMISSIONER OF PATENTS COMMONWEALTH OF AUSTRALIA Process for the continuous preparation of catalysts for lowpressure polymerisation of olefins The invention relates to a process for the preparation of catalysts for low-pressure polymerisation of alpha-olefins.
o" Procedures for polymerising alpha-olefins using the Ziegler low- 00 0 o pressure process are known. Compounds of the elements of the o 000 .oo fourth to sixth subgroups of the Periodic System mixed with o 00 0. o organometallic compounds of the first to third groups of the 0.
o000 Periodic System are used as catalysts. Of the compounds of the elements of the fourth to sixth subgroups, titanium compounds have gained the greatest significance. Aluminium alkyls and 0000 0 0 S000 aluminium alkyl halides are used most frequently as 0 .o 0 organometallic compounds of the first to third groups.
0 0 S.In most cases the Ziegler catalysts are prepared by reduction of Ti(IV) compounds, such as titanium tetrachloride or titanic acid 0 0o ester, with organoaluminium compounds. This leads to Ti(III) compounds which are often isolated, suspended in a suitable -i medium and mixed with the activator required for polymerisation.
The catalysts are normally prepared discontinuously in agitator vessels. Generallyr the organometallic compound dissolved in an inert solvent, e.g. a hydrocarbon or a hydrocarbon mixture, is taken and a solution of the compound of the subgroup element is stirred in. According to a process described in the DE 15 95 666 i titanium ester in cyclohexane is added to a solution of ethyl aluminium sesquichloride in n-heptane, the mixture is left to after-react with stirring at 20"C for 6 hours, the titanium isopropoxychloride precipitate formed is washed out and used for polymerisation. Correspondingly, when TiC14 is used as a compound of the subgroup element, TiC13 is the product of the reaction S with the organometallic compound. It is isolated, re-suspended o** 0:00 and mixed with the activator required for polymerisation.
ooo The average particle size and the particle size distribution of the catalytically active compound obtained in this manner, which are also decisive for the particle size and particle size 0 00 00 distribution of the polymer, can be controlled by varying the S concentrations of the reactants present in solution, the type of 0 reducing agent, the reaction temperature and the selection of the o inert solvent. Another possible way to influence the particle spectrum is to add electron donors to the organometallic compound used as a reducing agent. It leads to fine-grained polymers, which also exhibit a narrow particle size distribution. According to the DE 19 26 940 Al water or alcohols can be used as electron donors and secondary phosphites according to the DE 19 26 941 Al.
The average size and size distribution of the polymer particles are important properties for the use of polymers. Thus, for example, relatively small particle sizes are required for processing high-molecular polyethylene which takes place bythe I 2 4cold-moulding of powder with subsequent melt sintering or by extrusion. Coarse-grained material which has no fine particles is, however, preferred for the extrusion or injection moulding of low-molecular polyethylene powders.
Therefore, although there are a number of possibilities for controlling the particle size and particle size distribution as 00 described above, the preparation of polymerisation catalysts in a000 agitator vessels does not always lead to satisfactory results.
a For example, depending on the further processing of the polymers, it is not always possible to use electron donors as additives.
The degree to which the particle morphology (which has a decisive influence on the polymer properties, such as bulk density and 0 particle size distribution) can be influenced by changing the 0 0 0 concentrations of the reactants in the solutions destined for the 0"'44: reaction is also limited. As the concentration of the starting components decreases, the reactors become bigger and bigger or, if the reactor volume does not change, the batches get smaller 0004 -o and smaller so that storing supplies of the catalyst becomes a problem. Moreover, when the reaction takes place in agitator vessels, uniform formation of the catalyst particles cannot be ensured owing to the continually changing concentration ratios caused by the addition of the reactants and the different residence periods of the reaction product in the reaction mixture. This leads to unsatisfactory catalyst activity.
l Therefore the task consisted in developing a process for preparing catalysts for low-pressure polymerisation of alphaolefins which can not only be performed continuously but also avoids the disadvantages described above.
The invention consists in a process for the continuous preparation of catalysts consisting of a Ti(III) compound and an o organic aluminium compound for low-pressure polymerisation of 00o0 0 alpha-olefins. It is characterised in that a Ti(III) compound is 0 00 0 used which is obtained by the reduction of a Ti(IV) compound with an organic aluminium compound in a homogenizer.
The new process makes it possible not only to prepare the Ti(III) 0 00 component of the polymerisation catalyst continuously but also to 0 0 0 prepare it with reproducible particle size and particle size odistribution.
000000 0 0 According to the invention the reduction of the Ti(IV) compound 0080 takes place in a homogenizer as a reactor. Solutions of the starting materials Ti(IV) compound and organic aluminium s compound are added to the homogenizer separately. The reduction product, the Ti(III) compound, is precipitated as an insoluble solid and is subjected to the mechanical action of the homogenizer as soon as it is formed. This procedure ensures that the size of the Ti(III) particles can be controlled and limited.
This mechanical treatment is supported by reducing the residence period of the reaction product in the reactor. It leads to a more -k i 6 uniform particle size distribution and more uniform crystal growth.
In the sense of the present invention a homogenizer is understood to be an apparatus in which the energy required for homogenization is introduced into a small volume. Owing to the locally high energy input distinctive shearing stress fields ?0 0o occur in which particles of controlled dimensions are produced.
0 0Of Examples of such homogenizers are mixing pumps and jet mixers.
0 8t .a Centrifugal homogenizers with rotor-stator systems have proved particularly useful. In these homogenizers the solid particles are subjected to intensive impact and friction loading with cavitation. The material is discharged from the machine directly o o 0 after the treatment.
0 0 0 0 0 The Ti(IV) compound is reacted with the organic aluminium St compound in an inert solvent at temperatures of -20 to 50 0
C,
preferably 0 to 20"C. The concentration of the reactants in the 8O84 starting solutions is 50 to 3000, in particular 100 to 1500 mmoles/litre. Solutions of the same or different concentrations can be used. Per mole of titanium compound 0.3 to 2.0, preferably 0.4 to 1.0 moles of aluminium compound are used.
Suitable Ti(IV) compounds are chlorides and bromides as well as compounds of the general formula Ti(OR)4_nX n where n is 1 to 3, R stands for the same or different hydrocarbon groupsr in 3L1s particular alkyl groups with 1 to 18, preferably 2 to 8 carbon 4s Ti(OC 2
H
5 )Cl 3 Ti(OC 5
H
7 )C1 3 Ti(Oi-C 4
H
9 )C1 3 are mentioned by way of example.
Organic aluminium compounds, which can be used according to the invention for the reduction of Ti(IV) compounds, correspond to go the general formula A1R 3 n Xn with n equal to O0 1 or 2; R stands o for the same or different alkyl groups with 1 to 12, in 0 0 0 particular 2 to 6 carbon atoms; X denotes chlorine or bromium.
4 Examples of such compounds are triethylaluminium, o O triisobutylaluminium, diethylaluminium chloride and ethylaluminium dichloride. Other suitable compounds are polymeric aluminium organyls which are obtained by the reaction of lithium aluminium hydride or aluminium trialkyls or aluminium dialkyl a a 0 9 e hydrides, whose alkyl groups each have 1 to 16 carbon atoms, with
C
4 to C 20 diolefins, in particular C 4 to C 1 2 diolefins.
S Preference is given to the reaction products of Al(i-C 4
H
9 3 or Al(i-C 4
H)
2 H with isoprene ("isoprenylaluminium"). The aluminium compounds can be used in pure form or also as a mixture of two or more compounds. Inert hydrocarbons are used as solvents for the STi(IV) compounds and the organic aluminium compounds. Preference is given to saturated, aliphatic hydrocarbons or mixtures of hydrocarbons with 6 to 14 carbon atoms in the molecule.
The dispersion of the Ti(III) compound leaving the homogenizer can be used for olefin polymerisation as soon as the activator has been added. Normally, however, the Ti(III) compound is isolated and washed with an inert dispersant.
8 It is expedient to activate the Ti catalyst with the same organic aluminium compounds which have been used for the reduction of the Ti(IV) compound. As in the reduction the aluminium compounds can be used in pure form or as mixtures, aluminium isoprenyl is preferably used as an activator.
0 4 00 1 °o The organoaluminium activator is used in concentrations of 0.1 to o eo, 0"s 5.0 mmoles, preferably 1 to 3 mmoles/l of dilutant or reactor o volume whilst the Ti component is used in concentrations of 0.05 OF QQ 00oo to 0.5 mmoles/l of dilutant or reactor volume.
Polymerisation can be performed in solutions, in suspension or in 0000 00 t S"o discontinuously, at temperatures of 20 to 250OC, preferably 60 to o 100 0 C. The pressures are below 2.0 MPa, preferably about 0.15 to 0.8 MPa.
0 The standard inert dilutants used for Ziegler low-pressure processes, such as aliphatic or cycloaliphatic hydrocarbons, are suitable for solution and suspension polymerisation; examples are butaner pentaner hexaner cyclohexane. Furthermore, aromatic hydrocarbons, such as benzener xylene, can also be used as well as petrol or hydrogenated diesel oil fractions which have been carefully freed from oxygen, sulfur compounds and moisture.
Finally, aromatic or aliphatic halogenated hydrocarbons can also be used.
K
u i" CL C C CC C 4 4 4C Cr
ECCC
I~
9 With suspension polymerisation the only work-up needed is that the solid has to be separated from the dispersant in an inert gas atmosphere and dried. Under the exclusion of air and moisture the dispersant can be reused for polymerisation without any further intermediate treatment.
Ethylene or mixtures of ethylene with up to 10 by weight, in particular up to 5 by weight of alpha-olefins having 3 to 16 carbon atoms are used as monomers. The ethylene is preferably copolymerised with alpha-olefins of the formula R-CH=CH 2 where R stands for a branched or unbranched hydrocarbon group, in particular a straight-chain or branched, substituted or unsubstituted alkyl group with 1 to 8 carbon atoms. Propylene, butene-(l), pentene-(l), 4-methylpentene-(l1 are examples of such alpha-olefins.
The molecular weights of the polymers can be adjusted in the known manner with molecular weight regulators, preferably hydrogen.
C I4 C CC C L Cl1 CCCI 4' 1444CC Ct C The claimed process makes it possible to influence the particle structure, i.e. particle size and particle distribution of the polymers, by varying the conditions under which reduction of the Ti(IV) compound takes place in the homogenizer. The decisive variables are, et alia, the concentrations of the starting solutions, the residence time of the reaction product in the 1 '1 I i i i jl reactor as well as the conditions in the homogenizer. In the case of a centrifugal homogenizer they are, for example, the number of revolutions and the design of the rotor and stator.
The invention is explained in greater detail in the following examples. Naturally it is not intended to restrict it to the special embodiments described here.
0 00 00 0 oo ,r, Prenaration of the catalyst The .titanium component of the polymerisation catalyst is prepared 4000 o-ro ooo" continuously under the conditions listed in the table by reduction of TiCl4 with isoprenylaluminium or a mixture of isoprenylaluminium and triethylaluminium in a centrifugal 0 0 0 "0 homogenizer. To this end the starting substances dissolved in 0 petrol are pumped into the homogenizer through separate feed lines and at a certain speed. The resultant TiC13 dispersion is 054G collected and used for polymerisation without any intermediate treatment.
0 Pol yme risation 2 litres of petrol are placed in an inert gas atmosphere in a 3litre steel autoclave preheated to 70°C. 0.1 mmoles of titanium component prepared as described above and 4 mmoles of isoprenylaluminium are added, the mixture is stirred at 70°C for minutes and ethylene is introduced with stirring at 75 0 C, the pressure being maintained at 0.4 MPa. The ethylene feed is discontinued after 2 hours. The polyethylene formed is filtered Soff from the dispersant and dried.
I__
-11 0 00 00 0 009 0 0 6 O9 9 a 00 000 0 a 0 00 Q 0o o 0 0 Examples 1 to 4 The examples 1 to 4 describe the influence of the concentration of the starting solutions during preparation of the titanium component on the particle structure of the polymer prepared with it. Increasing titanium and aluminium concentrations lead to an increase in the bulk density and to a finer particle size distribution.
Examples 1, 5 and 6 A reduction of the residence period of the titanium- component in the reactor leads to improved catalyst activity, a decrease in the bulk density of the polymer and a coarser particle distribution.
Examples 1 to 7 and 8 to The influence of the rotor speed during preparation of the titanium component from starting solutions of different concentrations is shown. As the number of revolutions per time unit increases, the bulk densi' 'f the polymer increases and particle spectrum is widened.
Examples 11 to 13 Preparation of the Ti(III) component under cooling leads to an increase in the bulk density of the polymer with high catalyst activity.
L n I L I~ i 12 Examples 14 to 16 As in the examples 1 to 4, the influence of the concentration of the starting solution during the preparation of the Ti(III) component on the catalyst properties is investigated; in addition, the reaction takes place under cooling. A further increase in the bulk density of the polymer is achieved.
C 0 a O 0 00, In the following table the numbers 1 to 6 under the heading u "screen distribution" have the following meaning: 0 O 0.0 1 1000 m 4 125 um 2 500 um 5 63 im 3 250 um 6 63 um 0o a Example 17 (comparison) a 00 i In a 2-litre flask a solution of 450 mmoles of isoprenylaluminium and 50 mmoles of triethylaluminium in 0.6 litres of petrol are cooled to 0°C in an inert gas atmonphere. With stirring 1 mole of TiC14 is added at 0 C and then heated to room temperature. The titanium component formed is activated as described above and used for polymerisation. The activity of the resultant catalyst is only about one fifth of the activity of the catalysts prepared according to the claimed process.
I
I 1 1 t o 0 004 666 0 0 06 04 6 0 00 6 0 4, 6 6 00 44 4 0 00 0 600 0 6 6 0 0 Ct' 4 460 0 *06 604 6 0 0 Table
II
Preparation of the titanium component I Polymer
II
I Example I Ti IIPRA I TEA I rpm IThroughlTemp. I Yield I Bulk I Screen distributionI I I I I I I put I I mmolTi/ densitytl 1 I 2 i 3 I 4 I 5 1 6 1 Immol/l1 I ll/min I C I g I kg PE I g/ I I I I I I I I I I I I I I I I I I I L I I 100 I 250 I 500 11000 1 7 8 9 1I 12 13 14 16 Tr 1001 1001 1001 1001I 1001 500 1 500 1 5001 45 112.
225 450 45 45 45 45 45 225 225 225 500 500 500 250 500 750 5000 5000 5000 5000 5000 5000 5000 5000 7500 1000 5000 16000 1000 1000 1000 1000 1000 1000 0.2 1 0.5 1 1.0 1
RT
RT
RT
0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 110001 110001 11000 1 1 500 1 11000 1 115001 traces 0.2 1 0.2 I 0.2 1 0.2 1 0.2 1 0.2 1
RT
RT
RT
RT
RT
0 -20 -35 -30 -30 -30 290 1 420 1 450 1 335 1 370 1 290 1 1701 290 1 3501 565 1 4501 300 1 450 1 4101 450 1 445 1 4401 335 1 0.34 0.23 0.22 0.30 0.27 0.34 0.59 0.34 0.30 0.18 0.22 0.33 0.22 0.24 0.22 185 I 130 I 95 I 130 165 240 245 235 130 190 245 260 Tr I Tr I Trl 1I
TI
iI TrlI
II
Trl TrI Trl TrI 21 275 10.5 1 285 ITr 295 Tr I 11 11 Tr I Tr 1 21 21 11I 11 11 20 1 5 1 10 1 41 31 67 1 501 731 55 1 47 1 201 671 121 TO 281 621 81 11 41 551 401 11 61 531 381 1I 151 631 221 TrI 201 671 121 Tr! 251 611 101 Tr Tr Tr Tr 11 13.51 121 TrI 381 21 151 21 401 11 451 11 '.51 Tr 41 11 51 2! 21 Tr 31 TO 201 Tr 281 6515 54 1 401 66 1 25 1 291 671 241 721 61 781 0.22 0.23 0.30 250 1 275 1 310 1 Tr TrlI Comparative example 17: 1.4 1 308 1 1 6 40 47.5 4.51
I
Claims (4)
1. A process for the continuous preparation of catalysts consisting of a Ti(III) compound and an organic aluminium compound for low-pressure polymerisation of alpha- olefins, characterised in that a Ti(III) compound is used which is obtained by reducing a Ti(IV) compound with an organic aluminium compound in a homogenizer.
2. A process according to claim 1, characterised in that a centrifugal homogenizer is used as a homogenizer.
3. A process according to claim 1 or 2, characterised in that the reaction of the Ti(IV) compound with the organic aluminium compound takes place at temperatures of -20 to 50°C, preferably 0 to 200C.
4. A process according to one or more of the claims 1 to 3, characterised in 'hat the concentration of the Ti(IV) compound and the organic aluminium compound in the starting solutions is 50 to 3000, in particular 100 to 1500 mmoles/litre. A process according to one or more of the claims 1 to 4, characterised in that 0.3 to 2.0, preferably 0.4 to 1.0 moles of organic aluminium compound are used per mole of titanium compound. 4: 1 (1 4: 4 #14:4 4: 4:4 4: 4 4 4:44: 44:44 .4:4 4:4:: I4: AU004547989.WPC S,e i stirred in. According to a process described in the DE 15 95 666 6) A process according to one or more of the claims 1 to characterised in that the Ti(IV) compound is TiCl 4 TiBr 4 or compounds with the general formula Ti(OR) 4-nXn n being 1 to 3, R being the same or different hydrocarbon groups, in particular alkyl groups with 1 to 18, preferably 2 to 8 carbon atoms and X denoting chlorine or bromium. EI 0 7) A process according to one or more of the claims 1 to 6, characterised in that the organic aluminium compounds are "9 polymeric aluminium organyls or compounds of the general o. formula AIR X n being 0, 1 or 2r R standing for the same 3-n n or different alkyl groups with 1 to 12, in particular 2 to 6 carbon atoms and X denoting chlorine or bromium. o e °co 8) A process according to claim 7, characterised in that the reaction products of Al(i-C 4 H 9 3 or Al(i-C 4 H 9 2 H with isoprene o 9 o, are used as polymeric aluminium organyls. D 68 O4 s 9) The use of the catalysts according to one or more of the claims 1 to 8 for polymerising ethylene or mixtures of ethylene and up to 10 by weight of an alpha-olefin with 3 to 16 carbon atoms in solution, suspension or in the gaseous phase at temperatures of 20 to 250°C and pressures of 0.15 to MPa. DATED this 23rd dav of November 1989. HOECHST AKTIENGESELLSCHAFT WATERMARK PATENT TRADEMARK ATTORNEYS 290 BURWOOD ROAD HAWTHORN. VIC. 3122.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE3839813 | 1988-11-25 | ||
| DE3839813A DE3839813A1 (en) | 1988-11-25 | 1988-11-25 | METHOD FOR THE CONTINUOUS PRODUCTION OF CATALYSTS FOR THE LOW PRESSURE POLYMERIZATION OF OLEFINS |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| AU4547989A AU4547989A (en) | 1990-05-31 |
| AU620472B2 true AU620472B2 (en) | 1992-02-20 |
Family
ID=6367877
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| AU45479/89A Ceased AU620472B2 (en) | 1988-11-25 | 1989-11-24 | Process for the continuous preparation of catalysts for low-pressure polymerisation of olefins |
Country Status (10)
| Country | Link |
|---|---|
| EP (1) | EP0370372B1 (en) |
| JP (1) | JPH02189306A (en) |
| KR (1) | KR920007041B1 (en) |
| AT (1) | ATE102958T1 (en) |
| AU (1) | AU620472B2 (en) |
| BR (1) | BR8905954A (en) |
| CA (1) | CA2003625A1 (en) |
| DE (2) | DE3839813A1 (en) |
| ES (1) | ES2052866T3 (en) |
| ZA (1) | ZA898800B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| AU649489B2 (en) * | 1990-11-08 | 1994-05-26 | Solvay Polyolefins Europe - Belgium (Societe Anonyme) | Catalytic solid usable for the stereospecific polymerisation of alpha-olefins, process for preparing it and process for polymerising alpha-olefins in its presence |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE4434294C2 (en) * | 1994-09-19 | 1999-04-29 | Hartmann & Braun Gmbh & Co Kg | Method for controlling a non-linear, technical process |
| US6770718B2 (en) | 2000-12-15 | 2004-08-03 | Basell Poliolefine Italia S.P.A. | Continuous process for the preparation of solid catalyst components for the polymerization of α-olefins |
| DE102014212747A1 (en) * | 2014-07-01 | 2016-01-07 | Siemens Aktiengesellschaft | Interactive assistance system and method for computer-aided control optimization for a technical system |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| AU484234B2 (en) * | 1972-10-06 | 1975-02-27 | Shell Internationale Research Maatschappij Bv | Titanium trichloride composition |
| AU460459B2 (en) * | 1971-09-24 | 1975-04-24 | Hoechst Aktiengesellschaft | Process forthe polymerization ofd-olefins |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR73574E (en) * | 1958-05-09 | 1960-08-22 | Exxon Research Engineering Co | Polymerization of olefins and new catalysts for the latter |
| NL125865C (en) * | 1963-08-08 | |||
| DE1595666C3 (en) | 1966-08-09 | 1982-06-16 | Hoechst Ag, 6000 Frankfurt | Process for the polymerization of ethylene or its mixtures with higher alpha-olefins |
| DE1926940A1 (en) | 1969-05-27 | 1970-12-03 | Hoechst Ag | Catalyst for low pressure polymerisation - of alpha olefins |
| DE1926941A1 (en) | 1969-05-27 | 1970-12-03 | Hoechst Ag | Titanium catalyst for polymerisation of alp - ha olefins |
-
1988
- 1988-11-25 DE DE3839813A patent/DE3839813A1/en not_active Withdrawn
-
1989
- 1989-10-24 KR KR1019890015298A patent/KR920007041B1/en not_active Expired
- 1989-11-15 ES ES89121117T patent/ES2052866T3/en not_active Expired - Lifetime
- 1989-11-15 AT AT89121117T patent/ATE102958T1/en not_active IP Right Cessation
- 1989-11-15 EP EP89121117A patent/EP0370372B1/en not_active Expired - Lifetime
- 1989-11-15 DE DE89121117T patent/DE58907231D1/en not_active Expired - Fee Related
- 1989-11-17 ZA ZA898800A patent/ZA898800B/en unknown
- 1989-11-22 CA CA002003625A patent/CA2003625A1/en not_active Abandoned
- 1989-11-24 JP JP1303421A patent/JPH02189306A/en active Pending
- 1989-11-24 AU AU45479/89A patent/AU620472B2/en not_active Ceased
- 1989-11-27 BR BR898905954A patent/BR8905954A/en not_active Application Discontinuation
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| AU460459B2 (en) * | 1971-09-24 | 1975-04-24 | Hoechst Aktiengesellschaft | Process forthe polymerization ofd-olefins |
| AU484234B2 (en) * | 1972-10-06 | 1975-02-27 | Shell Internationale Research Maatschappij Bv | Titanium trichloride composition |
| AU481545B2 (en) * | 1974-07-18 | 1976-01-22 | The Dow Chemical Company | Process for manufacture of high bulk density powders of olefin polymers |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| AU649489B2 (en) * | 1990-11-08 | 1994-05-26 | Solvay Polyolefins Europe - Belgium (Societe Anonyme) | Catalytic solid usable for the stereospecific polymerisation of alpha-olefins, process for preparing it and process for polymerising alpha-olefins in its presence |
Also Published As
| Publication number | Publication date |
|---|---|
| KR900007873A (en) | 1990-06-02 |
| ZA898800B (en) | 1990-08-29 |
| AU4547989A (en) | 1990-05-31 |
| JPH02189306A (en) | 1990-07-25 |
| DE58907231D1 (en) | 1994-04-21 |
| DE3839813A1 (en) | 1990-05-31 |
| KR920007041B1 (en) | 1992-08-24 |
| CA2003625A1 (en) | 1990-05-25 |
| ATE102958T1 (en) | 1994-04-15 |
| ES2052866T3 (en) | 1994-07-16 |
| BR8905954A (en) | 1990-06-19 |
| EP0370372A3 (en) | 1991-10-16 |
| EP0370372B1 (en) | 1994-03-16 |
| EP0370372A2 (en) | 1990-05-30 |
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