CA1268594A - Process for the preparation of optically active polyolefins - Google Patents
Process for the preparation of optically active polyolefinsInfo
- Publication number
- CA1268594A CA1268594A CA000503755A CA503755A CA1268594A CA 1268594 A CA1268594 A CA 1268594A CA 000503755 A CA000503755 A CA 000503755A CA 503755 A CA503755 A CA 503755A CA 1268594 A CA1268594 A CA 1268594A
- Authority
- CA
- Canada
- Prior art keywords
- optically active
- transition metal
- aluminoxane
- metal compound
- poly
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- 238000000034 method Methods 0.000 title claims abstract description 19
- 230000008569 process Effects 0.000 title claims abstract description 16
- 229920000098 polyolefin Polymers 0.000 title claims abstract description 11
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 239000003054 catalyst Substances 0.000 claims abstract description 17
- 150000003623 transition metal compounds Chemical class 0.000 claims abstract description 12
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 6
- 150000001875 compounds Chemical class 0.000 claims abstract description 6
- 150000001336 alkenes Chemical class 0.000 claims abstract description 4
- 125000000008 (C1-C10) alkyl group Chemical group 0.000 claims abstract description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 3
- 230000000379 polymerizing effect Effects 0.000 claims abstract description 3
- -1 hydrocarbon radical Chemical class 0.000 claims description 23
- 238000006116 polymerization reaction Methods 0.000 claims description 15
- 239000004215 Carbon black (E152) Substances 0.000 claims description 6
- 229930195733 hydrocarbon Natural products 0.000 claims description 6
- CPOFMOWDMVWCLF-UHFFFAOYSA-N methyl(oxo)alumane Chemical compound C[Al]=O CPOFMOWDMVWCLF-UHFFFAOYSA-N 0.000 claims description 6
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 5
- 229910052719 titanium Inorganic materials 0.000 claims description 5
- 239000010936 titanium Substances 0.000 claims description 5
- 229910052723 transition metal Inorganic materials 0.000 claims description 5
- 150000003624 transition metals Chemical class 0.000 claims description 5
- 239000000178 monomer Substances 0.000 claims description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- 125000004122 cyclic group Chemical group 0.000 claims description 2
- ZSWFCLXCOIISFI-UHFFFAOYSA-N endo-cyclopentadiene Natural products C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 claims description 2
- QUPDWYMUPZLYJZ-UHFFFAOYSA-N ethyl Chemical group C[CH2] QUPDWYMUPZLYJZ-UHFFFAOYSA-N 0.000 claims description 2
- 229910052736 halogen Inorganic materials 0.000 claims description 2
- 150000002367 halogens Chemical class 0.000 claims description 2
- 125000003454 indenyl group Chemical group C1(C=CC2=CC=CC=C12)* 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- 150000003755 zirconium compounds Chemical class 0.000 claims description 2
- YBYIRNPNPLQARY-UHFFFAOYSA-N 1H-indene Natural products C1=CC=C2CC=CC2=C1 YBYIRNPNPLQARY-UHFFFAOYSA-N 0.000 claims 1
- 239000004743 Polypropylene Substances 0.000 description 13
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- 229920001155 polypropylene Polymers 0.000 description 10
- QQONPFPTGQHPMA-UHFFFAOYSA-N Propene Chemical compound CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 9
- 229920000642 polymer Polymers 0.000 description 7
- 229910052726 zirconium Inorganic materials 0.000 description 7
- NNBZCPXTIHJBJL-UHFFFAOYSA-N decalin Chemical compound C1CCCC2CCCCC21 NNBZCPXTIHJBJL-UHFFFAOYSA-N 0.000 description 6
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 4
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 4
- 235000010210 aluminium Nutrition 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 229940095050 propylene Drugs 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 230000003287 optical effect Effects 0.000 description 3
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000006384 oligomerization reaction Methods 0.000 description 2
- 229920001083 polybutene Polymers 0.000 description 2
- SYTBZMRGLBWNTM-SNVBAGLBSA-N (R)-flurbiprofen Chemical compound FC1=CC([C@H](C(O)=O)C)=CC=C1C1=CC=CC=C1 SYTBZMRGLBWNTM-SNVBAGLBSA-N 0.000 description 1
- HBAQYPYDRFILMT-UHFFFAOYSA-N 8-[3-(1-cyclopropylpyrazol-4-yl)-1H-pyrazolo[4,3-d]pyrimidin-5-yl]-3-methyl-3,8-diazabicyclo[3.2.1]octan-2-one Chemical class C1(CC1)N1N=CC(=C1)C1=NNC2=C1N=C(N=C2)N1C2C(N(CC1CC2)C)=O HBAQYPYDRFILMT-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical group CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical compound [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- 229910000329 aluminium sulfate Inorganic materials 0.000 description 1
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 125000000058 cyclopentadienyl group Chemical group C1(=CC=CC1)* 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 150000002430 hydrocarbons Chemical group 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- WCYWZMWISLQXQU-UHFFFAOYSA-N methyl Chemical compound [CH3] WCYWZMWISLQXQU-UHFFFAOYSA-N 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 150000003609 titanium compounds Chemical class 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
- PXXNTAGJWPJAGM-UHFFFAOYSA-N vertaline Natural products C1C2C=3C=C(OC)C(OC)=CC=3OC(C=C3)=CC=C3CCC(=O)OC1CC1N2CCCC1 PXXNTAGJWPJAGM-UHFFFAOYSA-N 0.000 description 1
- 229910052845 zircon Inorganic materials 0.000 description 1
- GFQYVLUOOAAOGM-UHFFFAOYSA-N zirconium(iv) silicate Chemical compound [Zr+4].[O-][Si]([O-])([O-])[O-] GFQYVLUOOAAOGM-UHFFFAOYSA-N 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F4/00—Polymerisation catalysts
- C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
- C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
- C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
- C08F4/62—Refractory metals or compounds thereof
- C08F4/64—Titanium, zirconium, hafnium or compounds thereof
- C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
- C08F4/65912—Component covered by group C08F4/64 containing a transition metal-carbon bond in combination with an organoaluminium compound
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F4/00—Polymerisation catalysts
- C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
- C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
- C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
- C08F4/62—Refractory metals or compounds thereof
- C08F4/64—Titanium, zirconium, hafnium or compounds thereof
- C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
- C08F4/6592—Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring
- C08F4/65922—Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring containing at least two cyclopentadienyl rings, fused or not
- C08F4/65927—Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring containing at least two cyclopentadienyl rings, fused or not two cyclopentadienyl rings being mutually bridged
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S526/00—Synthetic resins or natural rubbers -- part of the class 520 series
- Y10S526/943—Polymerization with metallocene catalysts
Abstract
Abstract of the disclosure:
Process for the preparation of optically active polyolefins by polymerizing olefins of the formula CH2=CHR
in which R = C1-C10-alkyl in the presence of an optic-ally active catalyst system composed of an optically active transition metal compound containing only one enantiomer (R- or S-form) of a stereorigid, chiral transition metal compound and an aluminum-containing compound of the aluminoxane type.
Process for the preparation of optically active polyolefins by polymerizing olefins of the formula CH2=CHR
in which R = C1-C10-alkyl in the presence of an optic-ally active catalyst system composed of an optically active transition metal compound containing only one enantiomer (R- or S-form) of a stereorigid, chiral transition metal compound and an aluminum-containing compound of the aluminoxane type.
Description
HOECHST AKTIENGESELLSCHAFT HOE 85/F 044 Dr.DA/mk Process for the preparation of optically active polyolefins The present invention relates to a process for the prepara-t;on of optically active polyolefins by polymerizing propyl-ene and higher 1-olefins using new Ziegler catalyst systems.
The invention relates, in particular, to a process for the preparation of optically active polypropylene, wherein the polymerizat;on is carried out in the presence of a catalyst system composed of an optically active enantiomer of a stereorigid, chiral transition metal compound and an alu-minum alkyl compound containing oxygen.
As is known, isotactic polypropylene is prepared with theaid of so-called supported catalyst systems. These are mixed catalysts in which, for example, a titanium compound and, in order to increase the isotacticity, an electron donor are deposited onto a magnesium halide, and in which aluminum alkyls are employed as activators. Catalysts of this type are described, for example, in German Offen-legungsschrift 2,230,672 and in European Patent 7,061.
These active catalyst systems are characterized by a high degree of isotacticity. The active centers of the catalyst fixed on the support are in this case arranged in a chiral manner by the firmly fixed ligands.
In the known isotactic polypropylenes equal proportions of both enantiomers (racemates) are present.
Soluble Ziegler catalysts are also known. Thus processes for the preparation of polyolefins which are carried out us;ng bis-(cyclopentadienyl)-z;rcon;um alkyl or bis-(cyclo-pentadienyl)-zirconium halogen compounds in comb;nat;on with ol;gomer;c aluminumoxanes are described, for example, in German Offenlegungsschrift 3,007,725 and German Offen-legungsschrift 3,127,133. Although these soluble catalyst systems display a very high activity in the polymerization ~.~
of ethylene and propylene, in the case of propylene poly-merization ~he product contains predominant proportions of atactic material. Isotactic polypropylene is only obtained by using cata~ysts having sterically large radicals on the transition metal or by us;ng stereorigid, ch;ral zircon;um compounds in combination with methyl aluminoxane (J.A. ~wen, J. Am. Chem. Soc. 106 t1984) 6355; European Published Specification No. 12~,3b8~.
It has now been found that polymers which are optically active and exhibit a high degree of isotacticity are obtained when propylene and other higher 1-olefins are poly-merized in the presence of a catalyst system composed of a) an optically active transition metal compound which is composed only of one enantiomer (R- or S-form) of a stereorigid and chiral transition metal compound of the 4th to 6th sub-group, preferably a titanium or zirconium compound, and which corresponds to the general formula R1Me(2A)R2R3, and b) an aluminum-containing compound of the aluminoxane type of the general formulae Al20R4(Al(R )~)n for a linear aluminoxane, and (Al(R5~-O)n+2 for a cycl;c aluminoxane, n being 4 to 20 and R5 being methyl or ethyl.
In addition, the catalyst systems are exceptionally active.
The optically active, stereorig;d, chiral transition metal compound of the catalyst system to be employed in the pro-cess according to the invention comprises ~-linked, unsym-metrical, mononuclear or polynuclear compounds which are 5~4 ~ 3 -bridged by hydrocarbon chains and preferably contain titan-ium or zirconium as the transition metal and correspond to the following general structural formula R1 R2 _ Me - R3 In this formula Me denotes a transition metal of the 4th to 6th sub-group, such as titanium, zirconium, vanadium, chromium, molybdenum or tungsten~ preferably titanium or zirconium and especiaLly zirconium;
A denotes a mononuclear or polynuclear, unsymmetrical hydrocarbon radical, preferably an indenyl group or a substituted cyclopentadienyl group, especially 4,5,6,7-tetrahydro-1-indenyl;
R1 denotes a C1 to C4 hydrocarbon radical, preferably a C2~l4 hydrocarbon radical; and R2 and R3 denote halogen, preferably chlorine, or a C
to C6-alkyl radical, R2 and R3 being identical or different.
The R- or S-forms of ethylene-bis-(4,5,6,7-tetrahydro-1-indenyl)-zirconium d;chloride or of ethylene-bis-(4~5,6,7-tetrahydro-1-indenyl)--titanium dichloride, particularly those of ethylene-bis-(4,5,6,7-tetrahydro-1-indenyl)-zirconium dichloride, are preferred.
The optically active transition metal compounds are employed in a particular case as the pure R-form or S-form. They are prepared by known processes which are described, for example, in the Journal of OrganometalLic Chemistry, Z32 t1982) 233-247.
Aluminoxanes of the general formulae Al20R4(Al(R )~)n for a linear aluminoxane and (Al(R5)-0-)n+2 for a cyclic aluminoxane, in which n is an integer from 4 to 20 and R5 is a methyl or ethyl radical, preferably a methyl radical, are used as the organoaluminum catalyst component. The preparation of compounds of this type is known. It is important that the aluminoxane should have a degree of polymerization of at least 6; preferably it is over 10.
Monomers employed in the preparation of homopolymers are olefins of the formula CH2=CHR in which R is C1 to C10-alkyl. It is preferable to use propene or 1-butene.
The polymerization can be carried out in solvents, in the liquid monomers or in the gas phase. When polymerization is carried out in solvents, it is advantageous to use 20 aluminoxane concentrations of 10 4 to 10 1 mole per liter and to use the aluminum and transition metal components in a molar ratio of 10:1 to 108:1.
The polymerization is carried out at temperatures within the range from -80 to 100C, but preferably at -40 to 25 80C, the range between -20 and 60C being particularly preferred.
The average molecular weight of the polymers formed can be controlled in a manner known per se by adding hydrogen and/
or by varying the temperature. The molecular weight is adjusted to higher values at low temperatures and to lower values at higher temperatures.
35~
The polyolefins obtained by the process according to the invention, especially polypropylenes and polybutenes, are distinguished by optical activity. The polyoLefin is found to have an optical rotation if the polymer is dis-solved in decahydronaphthalene by means of an ultrasonicbath and is examined in a commercially available polarimeter (Perkin Elmer 241~. Values of the rotat;on C~]T between 50 and 200 are found, depending on the amount of polymer and the aging time, [~]~ being defined as the measured value of ~x1ûO/mpv.
The measured value of ~ denotes the angle of rotation measured; mp V denotes grams of polymer per 100 cm3 of decahydronaphthalene.
No analogous optically active polypropylenes or polybutyl-enes have hitherto been described. It is extremely surpris-ing that it has been possible to prepare polymers of this type at all. Like known polyolefins, the polyolefins according to the invention can be processed by thermoplas-tic means, for example to give shaped articles such as fibers and films.
The optically active polypropylene according to the inven-tion is distinguished by having a melting point which is 7 to 10C higher than that of an optically inactive product which has been prepared under identical conditions using the racemate o-f the chiral transition metal compound.
The polyolefins obtained by the process according to the invention are also distinguished by having a very high degree of isotacticity, the fraction soluble in heptane being less than 1%. 99% by weight or more of the poly-propylene obtained by the process according to the inventionis isotactic polypropylene.
i85~
Example 1 a) Preparation of methyl aluminoxane 44.3 9 of Al2(S04)3 . 16 H20 (0.056 mole, corresponding to 1 mole of HzO) were suspended in 250 ml of toluene, 50 ml of tr;methylalum;num (0.52 mole) were added, and the mixture was allowed to react at 20C. After a reaction time of 30 hours approx. 0.9 moLe of methane had been evolved. The solution was then freed from sol;d aLuminum sulfate by filtration. Removal of the toluene gave 19.7 9 of methyl aluminoxane. The yield was 63% of theory. The average molecular weight, determined cryoscopically in benzene, was 1,170.
The average degree of oligomerization was approx. 16.
b) Preparation of optically active R-(rotation ~ 270) -ethylene-bis-(4,5,6,7-tetrahydroindenyl)-zirconium di-chloride The preparation was carried out analogously to the method described in the Journal of Organometallic Chemistry, 232 (1982), 233-247 on pages 245-247 for ethylene-bis-(4,5,6,7-tetrahydroindenyl)-titanium dichloride.
c) Polymerization A 1 liter glass autoclave which had been cleansed by heating and flushed several times w;th argon was charged, while thermostatically controlled at -10C, with 330 ml of absolute toluene, 360 mg of methyl aluminoxane having an average degree of oligomerization of 16 and 1.2x10 6 mole of R-ethylene-bis-(4,5,6,7-tetrahydroindenyl)-zirconium di-chloride. 70 ml of propene were rapidly condensed into this solution, the mixture becoming cloudy after a few minutes.
After a polymerization t;me of 2 hours the temperature was raised to 18C and the polymerization was continued for a _ 7 _ further 13 hours. The pressure was approx. 2.5 bar. The polymerization was then terminated by blowing off the excess monomer and add;ng ethanol Residues Gf catalyst were removed by stirring with HCl solution, and the polymer was then filtered off with suction and dried at 40C to constant weight~ The yield of optically active, pulverulent, iso-tactic polypropylene was 33.5 9; the activity was thus 1,860 kg of PP/mole of Zrxh, at an Mn of 45,000.
The rotation was determined by suspending 20 mg of the poly-mer in 2 ml of decalin and then dissolving it substantially by means of an ultrasonic bath. After the solution had been transferred into a 10 cm cell, a rotation of -90 was determined in an automatically compensating polarimeter using the Na D l ine.
Example 2 The procedure was as in Example 1, but polymerization was carried out at a temperature of 10C. 24.5 9 of optically active polypropylene were obtained after a polymerization time of 16 hours. The activity was 1,280 kg of PP/mole of Zrxh. The rotation was -150~
Example 3 The procedure was as in Example 1, but only 270 mg of methyl aluminoxane in 250 ml of toluene were initially taken.
2x10 6 mole of the R-zirconium compound and 48 9 of 1-butene were metered in. Polymerization was carried out for 15 hours at a temperature of 15C.
The yield of optically active, crystalline polybutene was 0.2 9. Calculation gives an activity of 6.8 kg of PE~/mole of Zrxh. The optical rotation of the polybutadiene was determined as + 100.
The invention relates, in particular, to a process for the preparation of optically active polypropylene, wherein the polymerizat;on is carried out in the presence of a catalyst system composed of an optically active enantiomer of a stereorigid, chiral transition metal compound and an alu-minum alkyl compound containing oxygen.
As is known, isotactic polypropylene is prepared with theaid of so-called supported catalyst systems. These are mixed catalysts in which, for example, a titanium compound and, in order to increase the isotacticity, an electron donor are deposited onto a magnesium halide, and in which aluminum alkyls are employed as activators. Catalysts of this type are described, for example, in German Offen-legungsschrift 2,230,672 and in European Patent 7,061.
These active catalyst systems are characterized by a high degree of isotacticity. The active centers of the catalyst fixed on the support are in this case arranged in a chiral manner by the firmly fixed ligands.
In the known isotactic polypropylenes equal proportions of both enantiomers (racemates) are present.
Soluble Ziegler catalysts are also known. Thus processes for the preparation of polyolefins which are carried out us;ng bis-(cyclopentadienyl)-z;rcon;um alkyl or bis-(cyclo-pentadienyl)-zirconium halogen compounds in comb;nat;on with ol;gomer;c aluminumoxanes are described, for example, in German Offenlegungsschrift 3,007,725 and German Offen-legungsschrift 3,127,133. Although these soluble catalyst systems display a very high activity in the polymerization ~.~
of ethylene and propylene, in the case of propylene poly-merization ~he product contains predominant proportions of atactic material. Isotactic polypropylene is only obtained by using cata~ysts having sterically large radicals on the transition metal or by us;ng stereorigid, ch;ral zircon;um compounds in combination with methyl aluminoxane (J.A. ~wen, J. Am. Chem. Soc. 106 t1984) 6355; European Published Specification No. 12~,3b8~.
It has now been found that polymers which are optically active and exhibit a high degree of isotacticity are obtained when propylene and other higher 1-olefins are poly-merized in the presence of a catalyst system composed of a) an optically active transition metal compound which is composed only of one enantiomer (R- or S-form) of a stereorigid and chiral transition metal compound of the 4th to 6th sub-group, preferably a titanium or zirconium compound, and which corresponds to the general formula R1Me(2A)R2R3, and b) an aluminum-containing compound of the aluminoxane type of the general formulae Al20R4(Al(R )~)n for a linear aluminoxane, and (Al(R5~-O)n+2 for a cycl;c aluminoxane, n being 4 to 20 and R5 being methyl or ethyl.
In addition, the catalyst systems are exceptionally active.
The optically active, stereorig;d, chiral transition metal compound of the catalyst system to be employed in the pro-cess according to the invention comprises ~-linked, unsym-metrical, mononuclear or polynuclear compounds which are 5~4 ~ 3 -bridged by hydrocarbon chains and preferably contain titan-ium or zirconium as the transition metal and correspond to the following general structural formula R1 R2 _ Me - R3 In this formula Me denotes a transition metal of the 4th to 6th sub-group, such as titanium, zirconium, vanadium, chromium, molybdenum or tungsten~ preferably titanium or zirconium and especiaLly zirconium;
A denotes a mononuclear or polynuclear, unsymmetrical hydrocarbon radical, preferably an indenyl group or a substituted cyclopentadienyl group, especially 4,5,6,7-tetrahydro-1-indenyl;
R1 denotes a C1 to C4 hydrocarbon radical, preferably a C2~l4 hydrocarbon radical; and R2 and R3 denote halogen, preferably chlorine, or a C
to C6-alkyl radical, R2 and R3 being identical or different.
The R- or S-forms of ethylene-bis-(4,5,6,7-tetrahydro-1-indenyl)-zirconium d;chloride or of ethylene-bis-(4~5,6,7-tetrahydro-1-indenyl)--titanium dichloride, particularly those of ethylene-bis-(4,5,6,7-tetrahydro-1-indenyl)-zirconium dichloride, are preferred.
The optically active transition metal compounds are employed in a particular case as the pure R-form or S-form. They are prepared by known processes which are described, for example, in the Journal of OrganometalLic Chemistry, Z32 t1982) 233-247.
Aluminoxanes of the general formulae Al20R4(Al(R )~)n for a linear aluminoxane and (Al(R5)-0-)n+2 for a cyclic aluminoxane, in which n is an integer from 4 to 20 and R5 is a methyl or ethyl radical, preferably a methyl radical, are used as the organoaluminum catalyst component. The preparation of compounds of this type is known. It is important that the aluminoxane should have a degree of polymerization of at least 6; preferably it is over 10.
Monomers employed in the preparation of homopolymers are olefins of the formula CH2=CHR in which R is C1 to C10-alkyl. It is preferable to use propene or 1-butene.
The polymerization can be carried out in solvents, in the liquid monomers or in the gas phase. When polymerization is carried out in solvents, it is advantageous to use 20 aluminoxane concentrations of 10 4 to 10 1 mole per liter and to use the aluminum and transition metal components in a molar ratio of 10:1 to 108:1.
The polymerization is carried out at temperatures within the range from -80 to 100C, but preferably at -40 to 25 80C, the range between -20 and 60C being particularly preferred.
The average molecular weight of the polymers formed can be controlled in a manner known per se by adding hydrogen and/
or by varying the temperature. The molecular weight is adjusted to higher values at low temperatures and to lower values at higher temperatures.
35~
The polyolefins obtained by the process according to the invention, especially polypropylenes and polybutenes, are distinguished by optical activity. The polyoLefin is found to have an optical rotation if the polymer is dis-solved in decahydronaphthalene by means of an ultrasonicbath and is examined in a commercially available polarimeter (Perkin Elmer 241~. Values of the rotat;on C~]T between 50 and 200 are found, depending on the amount of polymer and the aging time, [~]~ being defined as the measured value of ~x1ûO/mpv.
The measured value of ~ denotes the angle of rotation measured; mp V denotes grams of polymer per 100 cm3 of decahydronaphthalene.
No analogous optically active polypropylenes or polybutyl-enes have hitherto been described. It is extremely surpris-ing that it has been possible to prepare polymers of this type at all. Like known polyolefins, the polyolefins according to the invention can be processed by thermoplas-tic means, for example to give shaped articles such as fibers and films.
The optically active polypropylene according to the inven-tion is distinguished by having a melting point which is 7 to 10C higher than that of an optically inactive product which has been prepared under identical conditions using the racemate o-f the chiral transition metal compound.
The polyolefins obtained by the process according to the invention are also distinguished by having a very high degree of isotacticity, the fraction soluble in heptane being less than 1%. 99% by weight or more of the poly-propylene obtained by the process according to the inventionis isotactic polypropylene.
i85~
Example 1 a) Preparation of methyl aluminoxane 44.3 9 of Al2(S04)3 . 16 H20 (0.056 mole, corresponding to 1 mole of HzO) were suspended in 250 ml of toluene, 50 ml of tr;methylalum;num (0.52 mole) were added, and the mixture was allowed to react at 20C. After a reaction time of 30 hours approx. 0.9 moLe of methane had been evolved. The solution was then freed from sol;d aLuminum sulfate by filtration. Removal of the toluene gave 19.7 9 of methyl aluminoxane. The yield was 63% of theory. The average molecular weight, determined cryoscopically in benzene, was 1,170.
The average degree of oligomerization was approx. 16.
b) Preparation of optically active R-(rotation ~ 270) -ethylene-bis-(4,5,6,7-tetrahydroindenyl)-zirconium di-chloride The preparation was carried out analogously to the method described in the Journal of Organometallic Chemistry, 232 (1982), 233-247 on pages 245-247 for ethylene-bis-(4,5,6,7-tetrahydroindenyl)-titanium dichloride.
c) Polymerization A 1 liter glass autoclave which had been cleansed by heating and flushed several times w;th argon was charged, while thermostatically controlled at -10C, with 330 ml of absolute toluene, 360 mg of methyl aluminoxane having an average degree of oligomerization of 16 and 1.2x10 6 mole of R-ethylene-bis-(4,5,6,7-tetrahydroindenyl)-zirconium di-chloride. 70 ml of propene were rapidly condensed into this solution, the mixture becoming cloudy after a few minutes.
After a polymerization t;me of 2 hours the temperature was raised to 18C and the polymerization was continued for a _ 7 _ further 13 hours. The pressure was approx. 2.5 bar. The polymerization was then terminated by blowing off the excess monomer and add;ng ethanol Residues Gf catalyst were removed by stirring with HCl solution, and the polymer was then filtered off with suction and dried at 40C to constant weight~ The yield of optically active, pulverulent, iso-tactic polypropylene was 33.5 9; the activity was thus 1,860 kg of PP/mole of Zrxh, at an Mn of 45,000.
The rotation was determined by suspending 20 mg of the poly-mer in 2 ml of decalin and then dissolving it substantially by means of an ultrasonic bath. After the solution had been transferred into a 10 cm cell, a rotation of -90 was determined in an automatically compensating polarimeter using the Na D l ine.
Example 2 The procedure was as in Example 1, but polymerization was carried out at a temperature of 10C. 24.5 9 of optically active polypropylene were obtained after a polymerization time of 16 hours. The activity was 1,280 kg of PP/mole of Zrxh. The rotation was -150~
Example 3 The procedure was as in Example 1, but only 270 mg of methyl aluminoxane in 250 ml of toluene were initially taken.
2x10 6 mole of the R-zirconium compound and 48 9 of 1-butene were metered in. Polymerization was carried out for 15 hours at a temperature of 15C.
The yield of optically active, crystalline polybutene was 0.2 9. Calculation gives an activity of 6.8 kg of PE~/mole of Zrxh. The optical rotation of the polybutadiene was determined as + 100.
Claims (5)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A process for the preparation of optically active poly-olefins by polymerizing olefins of the formula CH2=CHR
in which R = C1-C10-alkyl in solvents, liquid monomers or the gas phase at temperatures between -50 and 100°C
by means of a soluble transition metal compound and an aluminoxane, which comprises carrying out the poly-merization in the presence of an optically active cata-lyst system composed of the following components a) an optically active transition metal compound con-taining only one enantiomer (R- or S-form) of a stereorigid, chiral transition metal compound of the formula in which R1 is a C1 to C4 hydrocarbon radical, Me is a transition metal of the 4th to 6th sub-group and A is a mononuclear or polynuclear, unsymmetrical hydrocarbon radical and R2 and R3 are halogen or a C1 to C6 alkyl radical, it being possible for R2 and R3 to be identical or different, and b) an aluminum-containing compound of the aluminoxane type of the formulae Al2OR?(Al(R5)-O)n for a linear aluminoxane and (Al(R5)-O)n=2 for a cyclic aluminoxane, in which n is a number from 4 to 20 and R5 is a methyl or ethyl radical.
in which R = C1-C10-alkyl in solvents, liquid monomers or the gas phase at temperatures between -50 and 100°C
by means of a soluble transition metal compound and an aluminoxane, which comprises carrying out the poly-merization in the presence of an optically active cata-lyst system composed of the following components a) an optically active transition metal compound con-taining only one enantiomer (R- or S-form) of a stereorigid, chiral transition metal compound of the formula in which R1 is a C1 to C4 hydrocarbon radical, Me is a transition metal of the 4th to 6th sub-group and A is a mononuclear or polynuclear, unsymmetrical hydrocarbon radical and R2 and R3 are halogen or a C1 to C6 alkyl radical, it being possible for R2 and R3 to be identical or different, and b) an aluminum-containing compound of the aluminoxane type of the formulae Al2OR?(Al(R5)-O)n for a linear aluminoxane and (Al(R5)-O)n=2 for a cyclic aluminoxane, in which n is a number from 4 to 20 and R5 is a methyl or ethyl radical.
2. The process as claimed in claim 1, wherein the transi-tion metal compound used is an optically active titanium or zirconium compound.
3. The process as claimed in claim 1, wherein the unsym-metrical hydrocarbon radicals A are indenyl or substitu-ted cyclopentadienyl radicals.
4. The process as claimed in claim 1, wherein the poly-merization is carried out in the presence of a catalyst composed of S-ethylene-bis-(4,5,6,7-tetrahydroindenyl)-zirconium dichloride or R-ethylene-bis-(4,5,6,7-tetra-hydroindenyl)-zirconium dichloride and methyl aluminox-ane.
5. An optically active polyolefin which can be obtained by the process as claimed in claim 1.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19853508887 DE3508887A1 (en) | 1985-03-13 | 1985-03-13 | METHOD FOR PRODUCING OPTICALLY ACTIVE POLYOLEFINES |
| DEP3508887.7 | 1985-03-13 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1268594A true CA1268594A (en) | 1990-05-01 |
Family
ID=6265013
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000503755A Expired - Fee Related CA1268594A (en) | 1985-03-13 | 1986-03-11 | Process for the preparation of optically active polyolefins |
Country Status (5)
| Country | Link |
|---|---|
| US (1) | US4933403A (en) |
| EP (1) | EP0197319B1 (en) |
| JP (1) | JPS61264010A (en) |
| CA (1) | CA1268594A (en) |
| DE (2) | DE3508887A1 (en) |
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| DE3808268A1 (en) * | 1988-03-12 | 1989-09-21 | Hoechst Ag | METHOD FOR PRODUCING A 1-OLEFIN POLYMER |
| DE3808267A1 (en) * | 1988-03-12 | 1989-09-21 | Hoechst Ag | METHOD FOR PRODUCING 1-OLEFIN POLYMERS |
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| US3197452A (en) * | 1955-11-30 | 1965-07-27 | Montedison Spa | Method for preparing prevailingly to substantially isotactic crude polymerizates of butene-1 |
| NL247349A (en) * | 1959-01-15 | |||
| NL160286C (en) * | 1971-06-25 | |||
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| DE3007725A1 (en) * | 1980-02-29 | 1981-09-17 | Hansjörg Prof. Dr. 2000 Hamburg Sinn | METHOD FOR PRODUCING POLYETHYLENE, POLYPROPYLENE AND COPOLYMERS |
| DE3127133A1 (en) * | 1981-07-09 | 1983-01-27 | Hoechst Ag, 6000 Frankfurt | METHOD FOR PRODUCING POLYOLEFINS AND THEIR COPOLYMERISATS |
| ZA844157B (en) * | 1983-06-06 | 1986-01-29 | Exxon Research Engineering Co | Process and catalyst for polyolefin density and molecular weight control |
| US4522982A (en) * | 1983-06-06 | 1985-06-11 | Exxon Research & Engineering Co. | Isotactic-stereoblock polymers of alpha-olefins and process for producing the same |
| DE3443087A1 (en) * | 1984-11-27 | 1986-05-28 | Hoechst Ag, 6230 Frankfurt | METHOD FOR PRODUCING POLYOLEFINES |
-
1985
- 1985-03-13 DE DE19853508887 patent/DE3508887A1/en not_active Withdrawn
-
1986
- 1986-03-07 DE DE8686103086T patent/DE3666439D1/en not_active Expired
- 1986-03-07 EP EP86103086A patent/EP0197319B1/en not_active Expired
- 1986-03-11 CA CA000503755A patent/CA1268594A/en not_active Expired - Fee Related
- 1986-03-11 US US06/838,678 patent/US4933403A/en not_active Expired - Lifetime
- 1986-03-12 JP JP61052756A patent/JPS61264010A/en active Pending
Also Published As
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| EP0197319A3 (en) | 1987-09-30 |
| DE3666439D1 (en) | 1989-11-23 |
| EP0197319B1 (en) | 1989-10-18 |
| JPS61264010A (en) | 1986-11-21 |
| DE3508887A1 (en) | 1986-09-25 |
| EP0197319A2 (en) | 1986-10-15 |
| US4933403A (en) | 1990-06-12 |
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