AU600353B2 - Preparation of homopolymers and copolymers of propene using a ziegler-natta catalyst system - Google Patents
Preparation of homopolymers and copolymers of propene using a ziegler-natta catalyst system Download PDFInfo
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- AU600353B2 AU600353B2 AU15087/88A AU1508788A AU600353B2 AU 600353 B2 AU600353 B2 AU 600353B2 AU 15087/88 A AU15087/88 A AU 15087/88A AU 1508788 A AU1508788 A AU 1508788A AU 600353 B2 AU600353 B2 AU 600353B2
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- Prior art keywords
- titanium
- catalyst system
- component
- preparation
- propene
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- QQONPFPTGQHPMA-UHFFFAOYSA-N Propene Chemical compound CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 title description 20
- 238000002360 preparation method Methods 0.000 title description 14
- 239000011954 Ziegler–Natta catalyst Substances 0.000 title description 5
- 229920001519 homopolymer Polymers 0.000 title description 5
- 229920001577 copolymer Polymers 0.000 title description 4
- 238000000034 method Methods 0.000 claims description 27
- 239000003054 catalyst Substances 0.000 claims description 23
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 10
- 229910000077 silane Inorganic materials 0.000 claims description 10
- 125000004432 carbon atom Chemical group C* 0.000 claims description 8
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- -1 ethylphenyl Chemical group 0.000 claims description 4
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 31
- 239000010936 titanium Substances 0.000 description 31
- 229910052719 titanium Inorganic materials 0.000 description 31
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 20
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 16
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical class CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 14
- 238000006116 polymerization reaction Methods 0.000 description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 13
- 150000002901 organomagnesium compounds Chemical class 0.000 description 12
- 229910052782 aluminium Inorganic materials 0.000 description 11
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 11
- 239000011777 magnesium Substances 0.000 description 11
- 239000000741 silica gel Substances 0.000 description 11
- 229910002027 silica gel Inorganic materials 0.000 description 11
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 10
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 10
- 239000000460 chlorine Substances 0.000 description 10
- 229910052801 chlorine Inorganic materials 0.000 description 10
- 229910052749 magnesium Inorganic materials 0.000 description 10
- 229920000642 polymer Polymers 0.000 description 10
- 239000007790 solid phase Substances 0.000 description 10
- 229930195733 hydrocarbon Natural products 0.000 description 8
- 150000002430 hydrocarbons Chemical class 0.000 description 8
- 150000003021 phthalic acid derivatives Chemical class 0.000 description 8
- 239000004215 Carbon black (E152) Substances 0.000 description 7
- 238000002156 mixing Methods 0.000 description 7
- 239000002245 particle Substances 0.000 description 7
- 229910052799 carbon Inorganic materials 0.000 description 6
- 239000012320 chlorinating reagent Substances 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 239000000203 mixture Substances 0.000 description 5
- 239000000178 monomer Substances 0.000 description 5
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 4
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 239000007791 liquid phase Substances 0.000 description 4
- 239000012071 phase Substances 0.000 description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 3
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 3
- LCKIEQZJEYYRIY-UHFFFAOYSA-N Titanium ion Chemical compound [Ti+4] LCKIEQZJEYYRIY-UHFFFAOYSA-N 0.000 description 3
- 150000001335 aliphatic alkanes Chemical class 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 229910052736 halogen Inorganic materials 0.000 description 3
- 150000002367 halogens Chemical class 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- XNGIFLGASWRNHJ-UHFFFAOYSA-L phthalate(2-) Chemical compound [O-]C(=O)C1=CC=CC=C1C([O-])=O XNGIFLGASWRNHJ-UHFFFAOYSA-L 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 239000010703 silicon Substances 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 2
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 2
- WSSSPWUEQFSQQG-UHFFFAOYSA-N 4-methyl-1-pentene Chemical compound CC(C)CC=C WSSSPWUEQFSQQG-UHFFFAOYSA-N 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 239000002879 Lewis base Substances 0.000 description 2
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical class OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- 229910052796 boron Inorganic materials 0.000 description 2
- 229910052681 coesite Inorganic materials 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 229910052906 cristobalite Inorganic materials 0.000 description 2
- AAMBIAPMLISIDH-UHFFFAOYSA-N dimethoxy-bis(2-methylphenyl)silane Chemical compound C=1C=CC=C(C)C=1[Si](OC)(OC)C1=CC=CC=C1C AAMBIAPMLISIDH-UHFFFAOYSA-N 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 150000007527 lewis bases Chemical class 0.000 description 2
- KXDANLFHGCWFRQ-UHFFFAOYSA-N magnesium;butane;octane Chemical compound [Mg+2].CCC[CH2-].CCCCCCC[CH2-] KXDANLFHGCWFRQ-UHFFFAOYSA-N 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical class CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- 125000002734 organomagnesium group Chemical group 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 229910052682 stishovite Inorganic materials 0.000 description 2
- 229910052905 tridymite Inorganic materials 0.000 description 2
- KPZGRMZPZLOPBS-UHFFFAOYSA-N 1,3-dichloro-2,2-bis(chloromethyl)propane Chemical compound ClCC(CCl)(CCl)CCl KPZGRMZPZLOPBS-UHFFFAOYSA-N 0.000 description 1
- AFFLGGQVNFXPEV-UHFFFAOYSA-N 1-decene Chemical compound CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical class CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 1
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 229910000323 aluminium silicate Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- FYXKZNLBZKRYSS-UHFFFAOYSA-N benzene-1,2-dicarbonyl chloride Chemical compound ClC(=O)C1=CC=CC=C1C(Cl)=O FYXKZNLBZKRYSS-UHFFFAOYSA-N 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- 125000004106 butoxy group Chemical group [*]OC([H])([H])C([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 1
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 229960002380 dibutyl phthalate Drugs 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 239000000499 gel Substances 0.000 description 1
- 230000002140 halogenating effect Effects 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- 229910052809 inorganic oxide Inorganic materials 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 150000002681 magnesium compounds Chemical class 0.000 description 1
- KJJBSBKRXUVBMX-UHFFFAOYSA-N magnesium;butane Chemical compound [Mg+2].CCC[CH2-].CCC[CH2-] KJJBSBKRXUVBMX-UHFFFAOYSA-N 0.000 description 1
- RVOYYLUVELMWJF-UHFFFAOYSA-N magnesium;hexane Chemical compound [Mg+2].CCCCC[CH2-].CCCCC[CH2-] RVOYYLUVELMWJF-UHFFFAOYSA-N 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 230000000877 morphologic effect Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- PARWUHTVGZSQPD-UHFFFAOYSA-N phenylsilane Chemical compound [SiH3]C1=CC=CC=C1 PARWUHTVGZSQPD-UHFFFAOYSA-N 0.000 description 1
- 125000005498 phthalate group Chemical class 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000010557 suspension polymerization reaction Methods 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- WBYKGOGDEZGLDO-UHFFFAOYSA-N triethoxy-(2-methylphenyl)silane Chemical compound CCO[Si](OCC)(OCC)C1=CC=CC=C1C WBYKGOGDEZGLDO-UHFFFAOYSA-N 0.000 description 1
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 description 1
- 239000003643 water by type 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
- C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F10/04—Monomers containing three or four carbon atoms
- C08F10/06—Propene
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Description
COMMONWEALTH OF AUSTRAL 6 0~0 3 5 3 M PATENTS ACT 1952.69 COMPLETE SPECIFICATION (OR IGINAL) Class Int. Class Application Number: Lodged: Complete Specification Lodged: Accepted: Published: Priority: Related Art: IThis document contaiins the amenclineilts rjrdjde i 6~eaijoa at is correct for p rin ti ng J, Nime of Applicant: BASF AKTEINGE SELLS CHAFT Address of Applicant: of 6700 Ludwigshafen., Federal Repulic of Germany Actual Inventor: JUERGEN KERTH, RALF ZOLK, RAINER ALEXANDER WERNER and GUENTHER SCHWEIER.
Address for Service: EDWD. WATERS SONSY 50 QUEEN STREET, MELBOURNE, AUSTRALIA, 3000.
Complete Specification for the invention entitled: "PREPARATION OF HOMOPOLYVERS AND COPOLYMERS OF PROPENE USING A ZIEGLER-NATTA CATALYST SYSTEM" The following statement is a full description of this invqntion, including the best method of performing it. known to US I1.
-h7 II -I i la= O.Z. 0050/39143 Preparation of homopolymers and copolymers of propene using a ZiegLer-Natta catalyst system The present invention relates to a process for the preparation of homopolymers of propene and copolyfiers of propene with minor amounts of other C 2
-C
12 -c-monoolefins, in particular C2-C6-o-monoolefins, by polymerization, in particulir by dry-phase polymerization, of the monomer or monomers at from 20 to 160 0 C, in particular from 50 to 120 0 C, and under from 1 to 100, in particular from 20 to 70, bar using a Ziegler-Natta catalyst system consisting of a titanium component which is based on a finely divi- S ded, shape-imparting silica gel and, in addition to titanium, contains magnesium, chlorine and a benzenecarboxylic acid derivative, t"i. 15 an aluminum comporn:- of the formula 0 R 3 I where R is alkyl of not more than 3, in particular not more than 4, carbon atoms, and a silane component of the formula RA Si(OR2')4 n, where R is a saturated aliphatic and/or aromatic hydrocarbon radical of not more than 16, preferably not more than 10, carbon atoms, R2 is alkyl of not i more than 15, preferably not more than 8, in particu- S Lar not more than 4, carbon atoms and n is from 0 to 3, preferably from 0 to 2, in particular 1, with the provisos that the atomic ratio of titanium from the titanium component to aluminum from the aluminum component is from 1 10 to 1 800, in particular from 1 20 to 1 200, and the molar ratio of aluminum component to silane component is from 1 0.03 to 1 0.8, in particular from 1 0.05 to 1 Polymerization processes of this type are known; their special feature compared with other similar processes 2 is the specific embodiment of the catalyst system, and the processes disclosed in Australian Patent Application Nos.
54527/80, 73971/81, 73972/81, 73973/81, 44679/85 and 52761/86 and in British Patents 2,101,609 and 2,101,611 may be mentioned as prototypes for the present case.
The specific embodiments of the catalyst systems are employed in order to achieve certain purposes, such as the following: !i The catalyst system should be easy to prepare and i 10 give a high yield of polymer which must contain a very large I isotactic fraction. The catalyst system should moreover produce polymers having special morphological properties, for example uniform particle size and/or a smaller fraction of very fine particles and/or a high bulk density. In addition to these parameters which are important for !i controlling the polymerization systems, working up the Ki polymers and/or processing them, a low halogen content in I the polymer is also important, particularly with regard to ii' corrosion problems; this can be achieved by increasing the polymer yield and/or by means of a catalyst system which I contains very little halogen.
In the prior art, some of these purposes can be J achieved only by very expensive methods or if other 2 purposes are neglected: 25 For example,Australian Patent Application Nos.
73971/81, 73972/81 and 73973/81 describe a catalyst system o consisting of active MgCI Ticd 4 and a phthalic acid derivative. With silica gel as the shape-imparting carrier, the productivity of the catalyst system is, however, no "a 30 longer satisfactory; furthermore, the chlorine content of othe polymers is comparatively high.
Australian Patent Appliction Nos. 54527/80 and 44679/85 and British Patents, 2,101,609 and 2,101,611 describe catalyst systems whose titanium component is obtained by treating a solid, inorganic oxide with an organic magnesium compound, a Lewis base and titanium 3 0050/39143 tetrachloride, it being necessary in addition to use a haLogenating agent which is not titanium tetrachloride and/or an organic compounJ of the metals boron, aluminum, silicon or tin or a boron trihalide or a halogen-containing alcohol. In spite of an expensive and tedious preparation procedure, the productivity of the corresponding catalyst system is unsatisfactory.
Er opean La pe Application 5 describes a catalyst system whose titanium component is obtained by treating Si02 with an organic Mg compound, an alcohol, a Lewis base and TiCL 4 In the case of this catalyst system too, the productivity is low.
The known processes are thus unsatisfactory, particularly with regard to good productivity and a low 15 chlorine content in the polymers, in combination with high isotacticity and good morphology.
S, It is an object of the present invention to provide a titanium component which, compared with the prior art processes, has good productivity and is also capable of giving polymers having a Low chlorine content, high isotacticity and good morphology.
W, e have found that this object is achieved by a catalyst system which contains a titanium component (1) Sprepared in a particular manner from a special carrier obtained in a defined manner from (la) a certain finely divided silica gel, (Ib) a certain organomagnesium i l't compound and (Ic) a certain gaseous chlorinating agent, I and (II) a certain alkanol, (III) titanium tetrachLoride and (IV) a specially selected phthalic acid derivative.
The present invention accordingly relates to a process for the preparation of homopolymers of propene and copolyners of propene with minor amounts of other
C
2
-C
12 -a-monoolefins, in particular C 2
-C
6 -ci-monoolefins, by polymerization, in particular by dry-phase poLymerization of the mom'n er or monomers at from 20 to 160 0 C, in particuLar from 0 to 1200C, under from 1 to 100, in particular from 20 to 70, bar using a Ziegterr i I 1 I *i
II
a' I II 4 O.Z. 0050/39143 Natta catalyst system consisting of a titanium component which is based on a finely divided, shape-imparting siLica gel and, in addition to titanium, contains magnesium, chlorine and a benzenecarboxylic acid derivative, an aluminum component of the formula
AIR
3 where R is alkyL of not more than 8, in particular not more than 4, carbon atoms, and a silane component of the formula Rn Si(OR2)4_n where R 1 is a saturated aliphatic and/or aromatic hydrocarbon radical of not more than 16, preferabLy not more than 10, carbon atoms, R 2 is alkyL of not more than 15, preferably not more than 8, in particular not more than 4, carbon atoms and n is from 0 to 3, preferably from 0 to 2, in particular 1, with the provisos that the atomic ratio of titanium from the titanium component to aluminum from the aluminum component is from 1 10 to 1 800, in particular from 1 20 to 1 200, and the molar ratio of aluminum component to silane component is from 1 0.03 to 1 0.8, in particular from 1 0.05 to 1 In the novel process, the titanium component (1) used is one which is obtained by a method in which first in a first stage a carrier is prepared from (la) a finely divided silica gel which has a particle diameter of from 1 to 1,000 pm, in particular from to 400 pm, a pore volume of from 0.3 to 3, in particular from 1 to 2.5, cm /g and 'o surface area of from 100 to 1,000, in particular from 200 to 40Q, m2 /g and is of the formula SiO2 a A1203, where a is from 0 to 2, in part-iular from 0 to 0.5, (Ib) an organomagnesium compound of the formula MgR 3 R where R 3 and R 4 are each C 2
C
10 -alkyL, preferably C 4
-C
8 -alkyl, and (Ic) a gaseous 5 O.Z. 0050/39143 chlorinating agent of the formula CLZ, where Z is CL or H, preferably H, by a method in which first in a first substage, in a liquid inert hydrocarbon, in particuLar an alkane, with constant thorough mixing at room temperature, the finely divided silica gel (la) and the organomagnesium compound (Ib) are combined, from 1 to in particular from 1.5 to 4, molar parts of the organomagnesium compound (Ib) being used per 10 molar parts of silicon of the silica gel and the substances combined are kept at from 20 to 1400C, in particular from to 900C, for from 0.5 to 5, in particular from 1 to 2, hours, then in a second substage, with constant thorough mix-
S.
t ing at from -20 to +80°C, in particular 0 to +200C, the I 1k 15 gaseous chlorinating agent (Ic) is passed into the product obtained from the first substage, from 2 to 40, in particular from 10 to 20, molar parts of the chlorinating Itt agent (Ic) being used per molar part of the organomagnesium compound the entire mixture is left at a temperature in the stated range for from 0.5 to 5 hours, in particular from 0.5 to 1 hour, and the resulting solidphase product, ie. the carrier is isolated with removal of the liquid phase, thereafter in a second stage, a solid-phase intermediate is prepared from the carrier obtained in the first stage, (II) a C 2
-C
6 -alkanol, in particular ethanoL, (III) titanium tetrachloride and (IV) a phthalic acid derivative of the formula 44
SCO-X
where X and Y togethr form oxygen or X and Y are each chlorine or C 1
-C
10 -alkoxy, preferably C 2
-C
8 -alkoxy, in particular butoxy, by a method in which first in a first substage, in a liquid inert hydrocarbon, in particular an alkane, and with constant thorough mixing at room temperature, the carrier and the alkanol 4~ f ii ii 6 o.Z. 0050/39143 (II) are combined, from 1 to 5, in particular from to 3.5, molar parts of the alkanol (II) being used per molar part of magnesium of the carrier and the substances combined are kept at from 20 to 140 0 C, in particu- 5 lar from 70 to 900C, for from 0.5 to 5, in particular from 1 to 2, hours, then in a second substage, with constant thorough mixing at room temperature, the titanium tetrachLoride (III) is introduced into the reaction mixture resulting from the first substage, from 2 to 20, in particular from 4 to 8, molar parts of the titanium tetrachloride (III) being used per molar part of magnesium of the carrier the substances combined are kept at from 10 to 150 0 C, in particular from 90 to 120°C, for from 0.5 to 5, in particular from 1 to 2, hours, and the resulting solid-phase intermediate is isolated with removal of the liquid phase, with the proviso that the phthalic acid derivative (IV) is introduced in the course of one or both of the substages and from 0.01 to 1, preferably from 0.1 to 0.4, in particular from 0.25 to 0.30, molar part of the phthalic acid derivative (IV) being used per molar part of magnesium of the carrier then in a third stage, the solid-phase intermediate obtained from the second stage is subjected to a singlestage or multi-stage or continuous extraction with titanium tetrachloride or a mixture of titanium tetrachloride and ethylbenzene, containing not less than 10, in particular not less than 20, by weight of titanium tetrachloride, at from 100 to 150 0 C, in particular from 115 to 1350C, in the course of from 0.2 to 5, in particular from to 3, hours, a total of from 10 to 1,000, preferably from 20 to 800, in particular from 150 to 300, parts by weight of the extracting agent being used per 10 parts by weight of the solid-phase intermediate obtained from the secon stage, and finally in a fourth stage, the solid-phase product formed in the third stage is washed with a liquid inert hydrocarbon, $1 I -7 O.Z. 0050/39143 in particular an alkane, until the hydrocarbon takes up virtually no more titanium tetrachloride, and the titanium component is obtained in this manner.
We have found that the novel process can be carried out particularly successfully if the catalyst system used contains a silane component which is of the formula RI SI(OR2) _n where R is phenyl or CI-C4-alkyLphenyl, especially methyl- or ethylphenyl, R 2 is alkyl of not more than 4 carbon atoms, especially methyl or ethyl, and n is 1 or 2.
Regarding the process according to the invention, the following may be noted specifically: Provided that the defining feature is taken into account, the polymerization process as such can be carried out in virtually any relevant conventional technological embodiments, for example as a batchwise, periodic or, in particular, continuous process eg. a suspension polymerization process or, in particular, dry-phase polymerization process. The stated technological embodiments, ie. the technological versions of the polymerization of a-monoolefins by the Ziegler-Natta method, are well known from the literature and in practice, so that no further discussion is required here.
For the sake of completeness, it may be mentioned that, in the novel process, it is also possible to regulate the molecular weights of the polymers by the relevant conventional measures, for Ixample by means of regulators, in particular hydrogen.
Regarding the composition of the novel catalyst system, the following may be stated specifically; the finely divided silica gel (la) to be used for the preparation of the titanium component is in general an aluminosilicate or, in particular, a silica; it is important that it has the required properties. We have r 8 O.Z. 0050/39143 found that the commercial silica gels which meet the stated specification and are conventionaLLy used for carriers are very suitable.
The organomagnesium compound (Ib) likewise to be used may be, for example, dibutylmagnesium, dihexylmagnesium or, in particular, butyloctyLmagnesium.
The gaseous chlorinating agent (Ic) also to be used should be very dry and pure; it consists of chlorine or, in particular, hydrogen chloride.
The liquid inert hydrocarbon which serves as an assistant can be a hydrocarbon of the type usually combined with titanium components for catalyst systems of the Ziegler-Natta type without damage to the catalyst system or its titanium component. Examples of suitable hydrocarbons are pentanes, hexanes, heptanes, gasolines and cyclohexane.
The alkanols (I1I to be used for the preparation of the titanium component can be commercial ones; they should advantageously have very high purities. ExampLes of highly suitable alkanols are ethanol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, isobutyl 6lcohol and tert-butyl alcohol; ethanol is particularly suitable.
The titanium tetrachloride (III) likewise to be used for the preparation of the titanium component (1) should be one conventionally used in Ziegler-Natta catalyst systems; the ethylbenzene which may be used as a mixture with the titanium tetrachloride should be very pure and dry.
Furthermore, the phthalic acid derivative (IV) to be used, which is defined in detail above, can be a commercial one; it should advantageously have high purity. We have found that dibutyl phthalate is very particularly suitable for the purpose of the present invention; however, other dialkyl phthalates and phthalic anhydride and phthaloyl dichloride are also suitable.
The hydrocarbon to be used for the preparation
F
1 9 O.Z. 00'0/39143 of the titanium component in stage can likewise be a conventional one; it should advanta have a reLatively high purity.
The preparation of the titaniup ,.mponent is simple and can be carried out by the skilled worker without explanations. Regarding stages and all that need be stated is that the isolation of the particular resulting solid is advantageously carried out by filtration under suction.
Suitable aluminum components of the stated formula are the reLevant conventionaL ones of this formuLa; they are sufficiently well known from the literature and in practice that no further discussion is required.
An example of an outstanding member is triethylauminum.
The silane component which completes the catalyst system is, in particular, a trialkyoxy(alkyl)phenylsilane or a dialkoxydi(akyl)phenylsiane of the stated formula. TriethoxytoLuyLsilane is an outstanding member; other examples are triethoxyethylphenysiLane, dimethoxyditoLuylsilane and diethoxyditoluyLs iLane.
The novel process permits the preparation of homopolymers and copolymers, for exampe of the binary or ternary type, including block copolymers, of propene with minor amounts of other C2-C12-ta-monooLefins in an advantageous manner, ca-monooLefins which are particu- Lary suitabLe comonomers to be polymerized being ethene, but-1-ene, 4-methyLpent-1-ene and hex-1-ene; however, n-oct-i-ee, n-dec-i-ene and n-dodec-l-(ne are, for example, also suitable.
EXAMPLE 1 Preparation of the titanium component (1) The procedure is as follows: first in a first stage a carrier is prepared 4rom (1a) a finely divided silica gel which has a particle diameter of from 20 to 45 pm, a pore volume of 1.75 c 3 /g and a surface area of 320 m 2 /g and is of the forniuLa Sio, (ib) butyloctylmagnesium and (1c) hydrogen chLoridc, by 4 46 0 O.Z. 0050/39143 a method in which first in a first substage, in n-heptane and with constant thorough mixing by means of stirring at room temperature, the finely divided silica geL (Ia) and the organomagnesium compound (Ib) are combined, 2.5 molar parts of the organomagnesium compound (Ib) being used per 10 molar parts of silicon of the silica gel and the substances combined are kept at 900C for 1.5 hours, then in a second substage, with constant thorough mixing by means of stirring at 10 0 C, gaseous chlorinating agent (Ic) is passed into the product obtained from the first substage, 10 molar parts of the chlorinating agent (Ic) being used per mclar part of the organomagnesium com- I O' pound the entire mixture is left at a temperature 0 in the stated range for 0.5 hour and the resulting solid- 4* phase !rodu t, ie. the carrier is isolated with re- S; vi moval of the Liquid phase, thereafter in a second stage, a solid-stage intermediate is prepared from (I the carrier obtained in the first stage, (11) ethanol, (III) titanium tetrachloride and (IV) di-nbutyl phthalate, by a method in which first in a first substage, in n-heptane and with constant thorough mixing by means of stirring at room temperature, the carrier and the ethanol (II) are combined, 3 molar parts of the etharlol (II) being used per molar part of magnesium of the carrier and the substances tombined are kept at 80°C for 1.5 hours, then in a second substage, with constant thorough mixing by means of stirring at room temperature, the titanium tetrachlorid (III) is introduced into the reaction mixture resulting from the first substage,, 6 molar parts of the titanium tetrachloride (III) being used per molar part of magnesium of the carrier after which the di-n-butyl phthalate is introduced, 0.30 molar part of the phthalate (1V) being used per molar part of magnesium of the carrier the substances combined are kept at 120°C for 2 hours with stirring, and the resulting I- i 11 O.Z. 0050/39143 solid-phase intermediate is isolated with removal of the Liquid phase by filtration under suction, then in a third stage, the solid-phase intermediate obtained in the second stage is subjected to a continuous extraction with titanium t\trachlorid at 125 0 C in the course of 2 hours, 140 parts by weig't of the titanium tetrachloride being used per 10 parts by weight of the solid-phase intermediate obtained in the second stage, after which the resulting solid-stage intermediate is isolated by filtration, and finally in a fourth stage, the solid-phase product obtained in the third stage is washed with n-heptane until che nheptane takes up virtually no more titanium tetrachloride, and the titaniumn component (1 is obtained in this man- S 15 ner; it contains 3.5% by weight of titanium, 6.0% by i weight of magnesium and 23% by weight of chlorine.
Polymerization A steel autoclave, having a volume of 10 L and equipped with a stirrer, is charged with 50 g of poly- 'i 20 propene powder, 10 millimoles of triethylaluminum (in the form of a 1 olar solution in n-heptane) as aluminum component 1 millimole of trietn.oxyphenylsilane (in the form of a 1 molar solution in n-hep'ane), as silane component 5 liters of hydrogen and finally 100 mg (q 0.07 millimole of titanium) nf the titanium component described above, at 30 0 C. The reactor temperature is brought to 70 0 C in the course of 10 minutes, r and the reactor pressure is brought to 28 bir in this time by forcing in gaseous propene.
30 The actual polymerization is carrieo out with constant stirring at 70 0 C and under 28 bar in the course of 2 hours, monomer consumed during this procedure being continuously replaced with fresh monomer.
The productivity of the catalyst component the heptane-soluble fraction (as a measure of the isotacticity) and the particle size distribution of the resulting polymer are summarized in the Table below.
i ^l -uri;i.t-iu.
12 O.Z. 0050/39143 EXAMPLE 2 The procedure described in Example 1 is followed, with the sole exception that the same molar amount of dimethoxyditoluyLsiLane is used as silane component The result of the polymerization carried out in this manner is likewise shown in the Table below.
COMPARATIVE EXPERIMENT Preparation of the titanium component \a\ The procedure described in Example 1 of Frp n No. S2lC uc -SZ4a;ea Application a 0X9-7~-7 is followed.
The resulting titanium component contains 3.6% by weight of titanium, 4.4% by weight of magnesium and 16% by weight of chlorine.
Polymerization This is carried out as described in Example 1, but using, instead of the titanium component described there, the same molar amount of the titanium component defined above.
The polymerization result achieved is once again shown in the Table below.
i* It o 0~ 0 00 S 0~
S
ExampLe 1 Exampte 2 Compa rative Experiment Productivity Heptane-soLubLe (g of PP/g ofi cat.) fractions (%by wt.) 10,900 4,9 13,100 2-0 3,500 4.0 ParticLe size distribution (mm) /0-25 0.25-0,5 0.5-1 1-2 2 (ppm) ChLorine content of product 4-1 3-6 3-0 10.6 11.-1 ,29-8, 30.8 34.5 12.2 21 17.5 46
I
I
14 O.Z. 0050/39143 As shown in the Table, the cataLyst component from the Comparative Experiment has a substantiaLLy Lower productivity and stereospecificity than the cataLyst components from the Examples according to the invention.
Moreover, the particLe size distributi o i- hi-fr-Ttod a g-e-o-f--und-esriraB- y Lar ge particLes.
ii
Claims (2)
- 2. A process as claimed in claim 1, wherein a cata- lyst system is used whose silane component is of the formula RA Si(OR2)4n where R I is phenyl or C 1 -C 4 -alkylphenyl, R 2 is alkyl of not more than 4 carbon atoms and n is i or 2.
- 3. A process as claimed in cLaim 2, wherein a cata- lyst system is used whose silane component is of the formula Rr Si(OR 2 )4.n where R is methyl- or ethylphenyl, R 2 is methyl or ethyl 18 0.Z. 0050/39143 and n is 1 or 2. DATED this 21st day of April, 1988 BASF AKTIENGE SELLS CHAFT EDWD, W-ATERS SONS PATENT ATTORNEYS QUEEN STREET, MELBOURNE, VIC. 3000 It 4 II I I. 4 I I ~4 44 44 I I~ I Il I $4
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE3713943 | 1987-04-25 | ||
| DE19873713943 DE3713943A1 (en) | 1987-04-25 | 1987-04-25 | METHOD FOR PRODUCING HOMO AND COPOLYMERISATES OF PROPEN BY MEANS OF A ZIEGLER-NATTA CATALYST SYSTEM |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| AU1508788A AU1508788A (en) | 1988-10-27 |
| AU600353B2 true AU600353B2 (en) | 1990-08-09 |
Family
ID=6326327
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| AU15087/88A Ceased AU600353B2 (en) | 1987-04-25 | 1988-04-26 | Preparation of homopolymers and copolymers of propene using a ziegler-natta catalyst system |
Country Status (8)
| Country | Link |
|---|---|
| EP (1) | EP0288845B1 (en) |
| JP (1) | JP2594311B2 (en) |
| AR (1) | AR245149A1 (en) |
| AT (1) | ATE62697T1 (en) |
| AU (1) | AU600353B2 (en) |
| CA (1) | CA1304883C (en) |
| DE (2) | DE3713943A1 (en) |
| ES (1) | ES2021782B3 (en) |
Families Citing this family (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3730022A1 (en) * | 1987-09-08 | 1989-03-16 | Basf Ag | METHOD FOR PRODUCING HOMO AND COPOLYMERISATS OF PROPEN BY MEANS OF A ZIEGLER-NATTA CATALYST SYSTEM |
| DE3829519A1 (en) * | 1988-08-31 | 1990-03-01 | Basf Ag | METHOD FOR PRODUCING HOMO AND COPOLYMERISATS OF PROPEN BY MEANS OF A ZIEGLER-NATTA CATALYST SYSTEM |
| DE3830195A1 (en) * | 1988-09-06 | 1990-03-15 | Basf Ag | Process for the preparation of homopolymers and copolymers of propene by means of a Ziegler-Natta catalyst system |
| FI90083C (en) * | 1990-12-20 | 1993-12-27 | Neste Oy | FOER OLEFINPOLYMERISATION AVSETT STEREOSPECIFIKT KATALYSATORSYSTEM |
| US5773537A (en) * | 1992-05-19 | 1998-06-30 | Basf Aktiengesellschaft | Ziegler-natta catalyst systems containing specific organosilicon compounds |
| US6184328B1 (en) | 1994-09-07 | 2001-02-06 | Showa Denko Kabushiki Kaisha | Propylene-based polymer, method for its production, composition thereof, catalyst component for polymerization, and method for its production |
| CN1100069C (en) * | 1994-05-12 | 2003-01-29 | 昭和电工株式会社 | Propylene polymer and its preparation method |
| EP2113520B1 (en) | 2001-11-01 | 2015-10-07 | Idemitsu Kosan Co., Ltd. | Solid catalyst component for olefin polymerization, catalyst for olefin polymerization and process for producing olefin polymer |
| KR100989997B1 (en) | 2002-05-24 | 2010-10-26 | 이데미쓰 고산 가부시키가이샤 | Magnesium Compounds, Solid Catalyst Components for Olefin Polymerization, Catalysts for Olefin Polymerization and Polyolefin Production Process |
| US7737069B2 (en) | 2004-04-23 | 2010-06-15 | Idemitsu Kosan Co., Ltd. | Magnesium compound, catalyst for olefin polymerization and method for producing olefin polymer |
| US20070219326A1 (en) | 2004-08-03 | 2007-09-20 | Idemitsu Kosan Co., Ltd. | Magnesium Compound, Solid Catalyst Component, Olefin Polymerization Catalyst, and Method for Producing Olefin Polymer |
| CN101014558A (en) | 2004-08-24 | 2007-08-08 | 出光兴产株式会社 | Magnesium compound, solid catalyst component, olefin polymerization catalyst, and method for producing polyolefin |
| US7329626B2 (en) | 2004-09-07 | 2008-02-12 | Lummus Novolen Technology Gmbh | Ziegler-Natta catalyst, preparation, and use for the polymerization of alkenes |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| AU7766287A (en) * | 1986-08-30 | 1988-03-03 | Basf Aktiengesellschaft | Catalyst containing ti, mg, al and si |
| AU7777987A (en) * | 1986-09-03 | 1988-03-10 | Basf Aktiengesellschaft | Titanium, magnesium, aluminium and silicone catalyst |
| AU1436988A (en) * | 1987-04-08 | 1988-10-13 | Basf Aktiengesellschaft | Preparation of homo- and copolymers of propene using a ziegler-natta catalyst system |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3062482D1 (en) * | 1979-01-10 | 1983-05-05 | Ici Plc | Olefine polymerisation catalyst and the production and use thereof |
| IT1209255B (en) * | 1980-08-13 | 1989-07-16 | Montedison Spa | CATALYSTS FOR THE POLYMERIZATION OF OLEFINE. |
| US4565796A (en) * | 1984-08-06 | 1986-01-21 | Exxon Research & Engineering Co. | Polymerization catalyst, production and use |
-
1987
- 1987-04-25 DE DE19873713943 patent/DE3713943A1/en not_active Withdrawn
-
1988
- 1988-04-16 ES ES88106087T patent/ES2021782B3/en not_active Expired - Lifetime
- 1988-04-16 EP EP88106087A patent/EP0288845B1/en not_active Expired - Lifetime
- 1988-04-16 DE DE8888106087T patent/DE3862417D1/en not_active Expired - Lifetime
- 1988-04-16 AT AT88106087T patent/ATE62697T1/en not_active IP Right Cessation
- 1988-04-19 CA CA000564511A patent/CA1304883C/en not_active Expired - Lifetime
- 1988-04-22 AR AR88310633A patent/AR245149A1/en active
- 1988-04-22 JP JP63098495A patent/JP2594311B2/en not_active Expired - Fee Related
- 1988-04-26 AU AU15087/88A patent/AU600353B2/en not_active Ceased
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| AU7766287A (en) * | 1986-08-30 | 1988-03-03 | Basf Aktiengesellschaft | Catalyst containing ti, mg, al and si |
| AU7777987A (en) * | 1986-09-03 | 1988-03-10 | Basf Aktiengesellschaft | Titanium, magnesium, aluminium and silicone catalyst |
| AU1436988A (en) * | 1987-04-08 | 1988-10-13 | Basf Aktiengesellschaft | Preparation of homo- and copolymers of propene using a ziegler-natta catalyst system |
Also Published As
| Publication number | Publication date |
|---|---|
| CA1304883C (en) | 1992-07-07 |
| JPS63280707A (en) | 1988-11-17 |
| DE3862417D1 (en) | 1991-05-23 |
| ES2021782B3 (en) | 1991-11-16 |
| AR245149A1 (en) | 1993-12-30 |
| EP0288845A3 (en) | 1989-03-22 |
| EP0288845B1 (en) | 1991-04-17 |
| DE3713943A1 (en) | 1988-11-03 |
| JP2594311B2 (en) | 1997-03-26 |
| EP0288845A2 (en) | 1988-11-02 |
| ATE62697T1 (en) | 1991-05-15 |
| AU1508788A (en) | 1988-10-27 |
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