CA2011880A1 - Process for the preparation of a syndiotactic polyolefin - Google Patents
Process for the preparation of a syndiotactic polyolefinInfo
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- CA2011880A1 CA2011880A1 CA002011880A CA2011880A CA2011880A1 CA 2011880 A1 CA2011880 A1 CA 2011880A1 CA 002011880 A CA002011880 A CA 002011880A CA 2011880 A CA2011880 A CA 2011880A CA 2011880 A1 CA2011880 A1 CA 2011880A1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F110/04—Monomers containing three or four carbon atoms
- C08F110/06—Propene
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F17/00—Metallocenes
-
- 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
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- 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 a syndiotactic polyolefin A syndiotactic polyolefin is obtained in a high yield by polymerization or copolymerization of an olefin of the formula Ra-CH=CH-Rb in the presence of a catalyst consist-ing of a metallocene of the formula I
Process for the preparation of a syndiotactic polyolefin A syndiotactic polyolefin is obtained in a high yield by polymerization or copolymerization of an olefin of the formula Ra-CH=CH-Rb in the presence of a catalyst consist-ing of a metallocene of the formula I
Description
2~0~8~
HOECHST AgTIENGESELLSCHAFT }~OE 89/F 084 Dr.DA/b8 Description Pro~es~ for the preparation of a syndiotactic pol~olefin The invention relates to a novel proce~s which can be employed on a large industrial ~cale for the preparation of a syndiotactic polyolefin.
Syndiotactic polyolefins, in particular syndiotactic polypropylene, are known per fie. However, it has not yet been possible to prepare such poly~er~ in an adequate yield under polymerization conditions which are of interest industrially. ~hus, it is known that ~yndiotac-tic polypropylene can be prepared by polymerization of propylene at -78C in the presence of a catalyst sy~tem consisting of VCl4, anisole, heptane and diisobutylalumi-num chloride (compare B. Lotz et al., Nacsomolecules 21, (1988), 23~5). However, the syndiotactic index (~ 76.9%) and the yield (= 0.16%) are too low.
It is furthermore known that a ~yndiotactic polypropylene having a narrow molecular weigh* distribution can be obtained in a ~ignificantly improved yield with the aid of a catalyst consi~ting of i~opropylene(cyclopentadi-enyl)(l-fluorenyl~-zirconium dichloride or isopropylene-(cyclopentadienyl)(l-fluorenyl)-hafnium dichloride and a methylaluminoxane at a temperature of 25 to 70C (compare J.A. ~wen et al., J. Am. Chem. Soc., 110 (1988), 6255).
Nevertheless, the molecular weight of the polymer which can be schie~ed by means of the zirconium compound is still too low. The ~yndiotactic indices which can be achieved are moreover ~till in need of improvement.
HOECHST AgTIENGESELLSCHAFT }~OE 89/F 084 Dr.DA/b8 Description Pro~es~ for the preparation of a syndiotactic pol~olefin The invention relates to a novel proce~s which can be employed on a large industrial ~cale for the preparation of a syndiotactic polyolefin.
Syndiotactic polyolefins, in particular syndiotactic polypropylene, are known per fie. However, it has not yet been possible to prepare such poly~er~ in an adequate yield under polymerization conditions which are of interest industrially. ~hus, it is known that ~yndiotac-tic polypropylene can be prepared by polymerization of propylene at -78C in the presence of a catalyst sy~tem consisting of VCl4, anisole, heptane and diisobutylalumi-num chloride (compare B. Lotz et al., Nacsomolecules 21, (1988), 23~5). However, the syndiotactic index (~ 76.9%) and the yield (= 0.16%) are too low.
It is furthermore known that a ~yndiotactic polypropylene having a narrow molecular weigh* distribution can be obtained in a ~ignificantly improved yield with the aid of a catalyst consi~ting of i~opropylene(cyclopentadi-enyl)(l-fluorenyl~-zirconium dichloride or isopropylene-(cyclopentadienyl)(l-fluorenyl)-hafnium dichloride and a methylaluminoxane at a temperature of 25 to 70C (compare J.A. ~wen et al., J. Am. Chem. Soc., 110 (1988), 6255).
Nevertheless, the molecular weight of the polymer which can be schie~ed by means of the zirconium compound is still too low. The ~yndiotactic indices which can be achieved are moreover ~till in need of improvement.
3~ Althoughthenarrowmolecularweightdi~tributionsaresuit-able for in~ectionmolding and precision in~ectionmolding, a medium to broad molecular weight di~tribution would be advantageous for dee~ drawing, extrusion, hollow body blow molding, plate casting and the production of films.
.~Y~ L'8`~
It i8 known that the polymerization of ethylene in the presence of two or more metallocene cataly~ts simultane-ously can produce polyethylene having a broad molecular weight distribution (compare EP 128,045). However, because several catalyst systems are used, the polymer is of poor homogeneity. The catalyst~ described moreover produce only atactic polymer, which is of only minor interest industrially, on polymerization of l-olefins.
The object was to discover a process which produces a highly syndiotactic polyolefin of very high molecular weight and broad molecular weight distribution.
It has been found that the ob~ect can be achieved by u~ing special hafnocene cataly~t.
The invention thus relates to a process for the prepara-tion of a ~yndiotactic polyolefin by polymerization or copolymerization of an olefin of the formula R~CH=CHR~, in which R- ~nd Rb are identical or different and denote a hydrogen atom or an alkyl radical having 1 to 28 carbon atoms, or R~ and *, with the atoms ~oining them, can form a ring, at a temperature of -60 to 200C under a pressure of 0.5 to 100 bar in solution, in ~uspension or in the ga~ phase in the presence of a cataly~t which consists of a metallocene as the transition metal component and an aluminoxane of the formula II
R9 ~ R9 ~ / 9 (II) for the linear type and/or of the formula III
r~s 1 t Al-O ~ (III) l2 for the cyclic type, in which, in the formulae II and 2~
III, R~ denotes a Cl-C~-alkyl grou~ or a C6-C1O-aryl group or benzyl and n iB an integer from 2 to 50, which com-prises carrying out the polymerization in the presence of a catalyst, the tran~ition m~tal component of which i~ a compound of the formula I
/ ~ ~ 1 (I) R5 Hf I \R2 ~ 4 ::
in which R1 and R2 are identical or differen~ ~nd denote a hydrogen atom, a halogen atom, a Cl-C1O-alkyl group, a Cl-C,O-alkoxy group, a C6-C1O-aryl group, a C6-C,O-aryloxy group, a C2-C,0-alkenyl group, a C,-C40-arylalkyl group, a C,-C40-alkylaryl group or a C8-C40-arylalkenyl group, R3 and R4 are different and denote a mono- or polynuclear hydrocarbon radical, which can form a sandwich structure with the hafnium, R~ is Ml - I 1 - Xl -, - Ml - CR2 -, - 1; -, l6 R6 R6 _ O _ Ml _, - C - C -, - BR~, = AlRb, -Ge-, -Sn-, -O-, -S-, G 80 ~ ~ S2 1 = NR6 ~
c CO, - pR6 or c P(O)RB, in which RB, R7 and R~ are identi-cal or different and danote a hydrogen atom, a halogen ntom, a C1-Cl0-alkyl group, a Cl-C10-fluoroalkyl group, a C6-C~0-fluoroaryl group, a C6-C10-aryl group, a C1-C10-alkoxy group, a C2-C10-alkenyl group, a C,-C~0-arylalkyl group, a CB-C40-arylalkenyl group or a C~-C~0-alkylaryl group, or RB
and R7 or RB and RB, in each case with the atoms ~oining them, form a ring, and is ~ilicon, germanium or tin.
~0~18~
.~Y~ L'8`~
It i8 known that the polymerization of ethylene in the presence of two or more metallocene cataly~ts simultane-ously can produce polyethylene having a broad molecular weight distribution (compare EP 128,045). However, because several catalyst systems are used, the polymer is of poor homogeneity. The catalyst~ described moreover produce only atactic polymer, which is of only minor interest industrially, on polymerization of l-olefins.
The object was to discover a process which produces a highly syndiotactic polyolefin of very high molecular weight and broad molecular weight distribution.
It has been found that the ob~ect can be achieved by u~ing special hafnocene cataly~t.
The invention thus relates to a process for the prepara-tion of a ~yndiotactic polyolefin by polymerization or copolymerization of an olefin of the formula R~CH=CHR~, in which R- ~nd Rb are identical or different and denote a hydrogen atom or an alkyl radical having 1 to 28 carbon atoms, or R~ and *, with the atoms ~oining them, can form a ring, at a temperature of -60 to 200C under a pressure of 0.5 to 100 bar in solution, in ~uspension or in the ga~ phase in the presence of a cataly~t which consists of a metallocene as the transition metal component and an aluminoxane of the formula II
R9 ~ R9 ~ / 9 (II) for the linear type and/or of the formula III
r~s 1 t Al-O ~ (III) l2 for the cyclic type, in which, in the formulae II and 2~
III, R~ denotes a Cl-C~-alkyl grou~ or a C6-C1O-aryl group or benzyl and n iB an integer from 2 to 50, which com-prises carrying out the polymerization in the presence of a catalyst, the tran~ition m~tal component of which i~ a compound of the formula I
/ ~ ~ 1 (I) R5 Hf I \R2 ~ 4 ::
in which R1 and R2 are identical or differen~ ~nd denote a hydrogen atom, a halogen atom, a Cl-C1O-alkyl group, a Cl-C,O-alkoxy group, a C6-C1O-aryl group, a C6-C,O-aryloxy group, a C2-C,0-alkenyl group, a C,-C40-arylalkyl group, a C,-C40-alkylaryl group or a C8-C40-arylalkenyl group, R3 and R4 are different and denote a mono- or polynuclear hydrocarbon radical, which can form a sandwich structure with the hafnium, R~ is Ml - I 1 - Xl -, - Ml - CR2 -, - 1; -, l6 R6 R6 _ O _ Ml _, - C - C -, - BR~, = AlRb, -Ge-, -Sn-, -O-, -S-, G 80 ~ ~ S2 1 = NR6 ~
c CO, - pR6 or c P(O)RB, in which RB, R7 and R~ are identi-cal or different and danote a hydrogen atom, a halogen ntom, a C1-Cl0-alkyl group, a Cl-C10-fluoroalkyl group, a C6-C~0-fluoroaryl group, a C6-C10-aryl group, a C1-C10-alkoxy group, a C2-C10-alkenyl group, a C,-C~0-arylalkyl group, a CB-C40-arylalkenyl group or a C~-C~0-alkylaryl group, or RB
and R7 or RB and RB, in each case with the atoms ~oining them, form a ring, and is ~ilicon, germanium or tin.
~0~18~
~he catalyst to be u6ed for the process according to the invention consi~ts of an aluminoxane and a metallocene of the formula I
~ R3 R5 Hf \ ~I) wherein Rl and R2 are identical or different and denote a hydrogen atom, a C~-C10-, preferably Cl-C3-alkyl group, a Cl-C10-, preferably Cl-C3-alkoxy group, a C6-C10-, prefer-ably C6-C8-aryl group, a C6-C10-, preferably CB-C~-aryloxy group, a C2-C10-, preferably C2-C4-alkenyl group, a C7-C40-1~ preferably C7-C10-arylalkyl group, a C7-C~o-~ preferably C7-Cl2-alkylaryl group, a CB-C40-~ preferably Ct-C12-arylalk-enyl group or a halogen ~tom, preferably ~hlorine.
R3 and R4 are different and denote a mono- or polynuclear hydrocarbon radical, which can form a ~andwich 6tructure with the hafnium. R3 and R4 are preferably fluorenyl and cyclopentadienyl, it al60 being pos~ible for the fluor-enyl or cyclopentadienyl base structures additionally to carry sub~ituent~.
R5 i~ a single- or multi-membered bridge which link~ the radicals R3 and R4 and denotes Ml ~1 -, - Ml - CR2 -, - C -, _ o _ ~ C - C - ,-R7 R7 ~7 - BR6, z AlR6, -Ge-, -Sn-, -O-, -S-, = SO, = SO2, = NR6, = CO, = PR5 or = P(o)R6, in which R~, R7 and R~ are identi-cal or different and denote a hydrogen atGm, a halogen 20~1~8~
atom, preferably chlorine, a C1-C~O-, preferably Cl-C3-alkyl group, in particular a methyl group, a Cl-C10-fluoroalkyl group, preferably a CF3 group, a C6-C1O-fluoro-aryl group, preferably a pentafluorophenyl group, a C6-C10-, preferably C6-C6-aryl group, a Cl-C~O-, preferably Cl-C4-alkoxy group, in particular a methoxy group, a Cz-C1o-, preferably C2-C4-alkenyl group, a C,-C~O-, preferably C,-C10-arylalkyl group, a C8-C~O-, preferably C8-C~-arylalk-enyl group or a C7-c~o-~ preferably C,-C~-alkylaryl group, or R6 and R' or R6 and R8, in each ca~e together with the ato~s ~oining them, form a ring.
M~ is ~ilicon, germanium or tin, preferably 6ilicon or germanium.
Rs i6 preferably =CR6R', =SiR6R', =GeR6R', -O-, -S-, =SO, =pR6 or =P(o)R6.
The metallocenes described akove can be prepared in accordance with the following general equation:
H2R3~ButylL1 -~HR3L1 5~ X-R5-X
H2R4~ButylL1-i~HR4LlJ
HR3-RS-R4H 2 ButvlLi~
LiR3-R5-R4Li Hf C14_~
tR
2~8~
(X = Cl, ~r, J, O-Tosyl) or H2R3~ButylLi ~HR3Li R6 R7 ~ R4H
\C a HR3L1 R6R7c R4 b H20 1 ~ R3H
2 8utylL1 6R7C lLi2 ~ H~C14 C ~
~R4 ~l ~c ~r R2Li, .
201~8g~
Metallocene~whicharepreferablyemployedare(arylalkyli-dene)(fluorenyl)(cyclopentadienyl)-hafniumdichlorideand (diarylmethylene)(fluorenyl)(cyclopentadienyl)-hafnium dichloride. (Methyl(phenyl)methylene)(fluorenyl)(cyclo-pentadienyl)-hafnium dichloride and (diphenylmethylene)-(fluorenyl)(cyclopentadienyl)-hafnium dichloride are particularly preferred here.
The cocataly~t is an aluminoxane of the formula II
--Al- O _EA1- Ol~Al ( I I ) ~0 for the linear type and/or of the formula III
_ rAl~O (III) ~ n~2 for the cyclic typs. In these formulae, the radicals R~
denote a Cl-C6-alkyl group, pxeferably methyl, ethyl, isobutyl, butyl or neopentyl, or a C~-C1O-aryl ~roup, preferably phenyl or benzyl. Methyl iB particularly preferred. n is an integer from 2 to 50, preferably 5 to ~0. However, the exact structure of the sluminoxane i8 not known.
~he aluminoxane can be prepared in variou~ ways.
One possibility is careful addition of water to a dilute ~olution of an aluminum trialkyl by introducing in each ca~e small portion~ of the ~olution of the nluminum trialkyl, preferably aluminum trimethyl, and the water into an initially introduced relatively l~rge amount of an inert solvent and waiting for the evolution of gas to end between each addition.
In another process, finely powdered copper sulfate penta-20~ ~8~
hydrate i8 suspended in toluene in a gla6s ~lask, and aluminum trialkyl i8 added under an inert ga6 at about -20C in an amount such that about 1 mole of CuSO4 5H20 i~
available for every 4 Al atoms. After 810w hydrolysi~, alkane being split off, the reaction mixture i8 left at room temperature for 24 to 48 hour6, during wh~ch it must be cooled, if appropriate, 80 that the temperature does not rise above 30~C. The ~luminoxane di6solved in the toluene i6 then filtered off from the copper sulfate and the solution i~ concentrated in vacuo. It is assumed that in this preparation process the low molecular weight aluminoxanes undergo condenæation to higher oligomer6, aluminum trialkyl being split off.
Aluminoxane6 are furthermore obtained by a procedure in which aluminum trialkyl, preferably aluminum trLmethyl, dis601ved in an inert aliphatic or aromatic solvent, preferably heptane or toluene, i6 reacted with aluminum ~alt6 containing water of cry6tallization, preferably aluminum sulfate, at a temperature of -20 to 100C. The volume ratio here between solvent and the aluminum 81kyl used i6 1:1 to 50:1 - preferably 5:1 - and the reaction time, which can be controlled by the ~plitting off of the alkane, i6 1 to 200 hours - preferably 10 to 40 hour6.
Of the aluminum ~alts containing water of crystalliza-tion, tho6e which have a high content of water of cry8-tallization are u~ed in particular. Aluminum sulfAte hydrate is particularly preferred, above all the com-pound6 Al2(SO4)3-16H20 and Al2~SO~)3 18H20, with the parti-cularly high water of cry6tallization content of 16 and 18 mole~ of H20/mole of Al2(SO4)3 re6pectively.
Another variant for the preparation of aluminoxanes compri6es di6solving aluminum trialkyl, preferably aluminum trimethyl, in heptane or toluene in the suspend-ing sgent which ha6 been initially introduced into the polymerization ve~sel, preferably in the liquid monomer, and then reacting the aluminum compound with water.
In addition to the proces~e6 described above for the preparation of aluminoxanes, there are others which can be used. Regardless of the nature of the preparation, all the aluminoxane ~olutions have the common feature of a varying content of unreacted aluminum trialkyl which is in free form or as an adduct. This content has an influ-ence on the catalytic activity which ha6 not yet been clarified precisely and differs according to the metal-locene compound employed.
It is possible for the metallocene to be preactivated before use in the polymerization reaction with an alumin-oxane of the formula (II) and/or (III). The polymeriza-tion ac~ivity is in this way increased significantly and the grain morphology is improved.
The preactivation of the transition metal compound is carried out in solution. Preferably, in thi6 procedure, the metallocene is dissolved in a solution of the alumin-oxane in an inert hydrocarbon. An aliphatic or aromatic hydrocarbon is suitable as the inert hydrocarbon. Toluene is preferably used.
The concentration of the aluminoxane in the solution i8 in the range from about 1% by weight up to the ~atura~ion limit, preferably 5 to 30% by weight, in each case based on the total solution. The metallocene can be employed in the sam6 concentration, but it is preferably employed in an amount of 10-~ - 1 mole per mole of aluminoxane. The preactivation time i8 5 minutes to 60 hours, preferably S to 60 minutes. The reaction i~ carried out at a tem-perature of -78 to 100C, preferably 0 to 70~C.
A significantly longer preactivation is possible, but this usually has neither an activity-increasing nor an activity-reducing effect, although it may be entirely appropriate for storage purposes.
The polymerization is carried out in a known manner in 201~8801 solution, in suspension or in the gas phase, continuously or discontinuously, in one or more stage~ at a tempera-ture of -60 to 200C, preferably -30 to lOO-C, in parti-cular 0 to 80C.
The total pressure in the polymerization ~ystem i8 0.5 to 100 bar. The polymerization in the pressure range of 5 to 60 bar, which is of particular interest industrially, is preferred. Monomers of boiling points higher than the polymerization temperature are preferably polymerized under normal pressure.
In this reaction, the metallocene compound is u~ed in a concentration, based on the transition metal, of 10-3 to 10-', preferably 10-4 to 10-6 mol of transition metal per dm3 of solvent or per dm3 of reactor volume. The aluminox-ane is used in a concentration of 10-5 to 10~1 ~ol, prefer-ably 10-5 to 10-2 mol per dm3 of ~olvent or per dm3 of reactor volume. In principle, however, higher concentra-tions are also possible.
If the polymerization is carried out as su~pen~ion or ~olution polymerization, an inert ~ol~ent which iB
customary for the Ziegler low pressure process i~ u~ed.
For example, the polymerization is carried out in an aliphatic or cycloaliphatic hydrocarbon; examples of these which may be mentioned are butane, pentane, hexane, heptane, isooctane, cyclohexane and methylcyclohexane.
A benzihe or hydrogenated diesel oil fraction can furthermore be u~ed. Toluene can also ba used. The poly-merization is preferably carried out in ~he liquid monomer.
Olefins of the formula R-CH = CH*, in which R- and Rb are identical or different and denote a hydrogen atom or an alkyl radical having 1 to 28 carbon atoM~, it also being possible for R- and Rb to be bonded as a ring, are poly-merized or copolymerized. Examples of ~uch olefins are .
2~
ethylene, propylene, l-butene, l-hexene, 4-methyl-1-pentene, l-octene, norbornene or norbornad$ene. Propyl-ene, l-butene and 4-methyl-1-pentene are preferred.
The molecular weight of the polymer can be regulated in a known manner. For example, the molecular weight can be regulated with excess trialkylaluminum, preferably tri-methylaluminum present in the aluminoxane 801ution.
Hydrogen i~ preferably used.
The polymeriz~tion can be of any desired duration, since the catalyst sy~tem to be used according to the invention exhibits only a slight time-dependent decrease in poly-merization activity.
If the polymerization time i8 relatively long, the high molecular weight content in the polymer increases sig-nificantly. A longer residence time in the polymerization~ystem i~ therefore advi~able~n order to achieve high average molecular weights. In order to achieve high mole-cular weights, it i6 advantageous to maintain a high polymerization temperature, ~ince, in contrast to known processe~, 8~ the polymerization temperature increa~es in the polymerization ~y~tem to be used according to the invention, a higher molecular weight ha~ also simultane-ously been found. Furthermore, a hi~her metallocene activity is al~o simultaneously achieved at a higher polymerization temperature. This means that lower resi-dual ash contents are obtained in the polymer.
The molecular weight distribution is broad to bimodal at a higher polymerization temperature, and is narrow and monomodal at a lower temperature.
The polymers prepared accord.ing to the invention moreover generally exhibit a very high syndiotactic index of more than 90~; in this, the process according to the invention is significantly superior to the kn~wn processes.
2 ~
The followin~ example~ are intended to illustrate the invention. In these examples VN - viscosity number in cm3/g k~ - weight-average molecular weight in g/mol N~ = n~ er-average molecular weight in g/mol N~/M~ = molecular weight distribution The molecular weight was determined by gel permeation chromatography~
SI - syndiotactic index, determined by l3C-NMR
I0 spectroscopy n~ = average ~yndiotactic block length (l+ ~F) All the following working operations of metallocene ~ynthesis were carried out under an inert gas atmosphere using absolute colvent~.
~ample 1 (Phenyl(methyl)methylene)(9-fluorenyl)(cyclopentadienyl)-hafnium dichloride Ph ~ ~ ~ Cl ~ C ~ Hf A ~olution of 67.8 mmol of lithium-fluorene in 50 cm3 of tetrahydrofuran was added to a solution of 11.4 g (67.8 mmol) of 6-methyl-6-phenylfulvene in 40 cm3 of tetrahydrofuran at room temperature. After the mixture had been ~tirred at room temperature for 2 hour~, 60 cm3 of water were added. The ~ub~tance which precipitated out wa~ filtered off with ~uction, washed with diethyl ether and dried under an oil pump vacuum. 19.1 g (84.2%) of 1-cyclopentadienyl-l-(9-fluorenyl)-ethylbenzene were 2`~
_ 13 -obtained (correct elemental analyses; ~H-NMR spectrum).
10.0 g (19.9 mmol) of the compound were dis~olved in 60 cm3 of tetrahydrofuran and 26 cm3 (65 mmol) of a 2.5 molar hexane ~olution of n-butyllithium were added at 0C. After the mixture had been stirred for 15 minutes, the solvent was ~tripped off in vacuo. The dark red residue which remained was washed several times with hexane and drie~ under an oil pump vacuum. 15.6 g of the red dilithium ~alt were obtained as the tetrahydrofur~n adduct which contained about 30% of tetrahydrofuran. A
su~pension of 4.78 q (14.9 mmol) of HfCl~ in 70 cm3 of CH2CH2 was reacted with~14.9 mmol of the dilithium salt and the reaction product wa~ worked up. Cry~tallization at -35-C gave 2.6 g (30~) of the hafnocene dichloride compound as orange crystal~.
Correct elemental analy~is.
1 H-NMR 8pectrum (100 MHz, CDC13)s 7.17 - 8.20 (m, 11 H, Flu-H,Ph-H), 6.87 (m, 1, Ph-H), 6.12 - 6.42 (m,3, Ph-H,CpH), 5.82, 5.67 (2xdd,2xl,Cp-H), 2.52 (s,3,CH3).
~ample 2 Diphenylmethylene(9-fluorenyl)(cyclopentadienyl)-hafnium dichloride Ph ~ ~ ~ Cl ~ C Hf~
Ph ~ Cl 12.3 cm3 (30.7 mmol) of a 2.5 molar hexane solution of n-butyllithium were ~lowly added to a solution of 5.10 g(30.7 mmol) of fluorene in 60 cm3 of tetrahydrofur~n at room temperature. After 40 minutes, 7.07 q (30.7 mmol) of diphenylfulvene were added to the orange solution and the m~xture was ~t~rred overnight. 60 cm3 of water were added to the dark red ~olution, whereupon the ~olution became yellow-colored, and the mixture was extracted with ether.
The ether phase was dried over MgS04 and concentrated and the residue was left to crystallize at -35C. 5.1 g (42%) of l-cyclopentadienyl-l-(9-fluorenyl)-diphenylmethane were obtained as a beige powder. 1.25 g (3.15mmol) of 1-cyclo-pentadienyl-l-(9-fluorenyl)-diphenylmethane were reacted with 6.3 mmol of butyllithium analogously to Example 1.
The dilithium salt was reacted with 1.0 g (3.15 mmol) of HfCl4 analogously to Example 1. Filtration of the orange reaction mixture over a G4 frit and extraction of the filtrate with lO0 cm3 of toluene gave 0.70 g (34~) of the hafnocene dichloride complex ~s ~ yellow-orange powder.
Correct elemental analysis. The mass spectrum gave M+ - 644.
1 H-NNR spectrum ~100 NHz,CDCl3): 6.85 - 8.25 (m,16,Flu-H,Ph-H), 6.37 (m,2,Ph-H), 6.31 (t,2,Cp-H), 5.75 (t,2,Cp-I5 M).
8xample 3 A dry 16 dm3 reactor was flushed with nitrogen and filledwith 10 dm3 of liquid propylene. ~0 cm3 of a toluene-~olution of methylaluminoxane (corresponding ~o 40 mmol of Al, average degree of oligomeri~ation of the methyl-aluminoxsne n = 20) were then added and the mixture wa~
stirred for 15 minutes.
In parallel to thi~, 53.0 mg (O.082 mmol) of diphenyl-methylene(fluorenyl)(cyclopentedienyl)-hafnium dichloride were di~solved in 15 cm3 of a toluene Qolution of methyl-aluminoxane (20 mmol of Al). After 15 minutes, the ~olution was introduced into the reactor and the polymer-ization temperature was brought to 60C. Polymerization was carried out for 5 hours. 3.20 kg of polypropylene, corre~ponding to a metallocene activity of 12.0 kg of polypropylene/g of metallocene x hour, were obtained.
VN = 1254 cm3/g; M~ = 2.34-10~, N~ = 580,000, ~/M~ = 4.0, bimodal molecular weight di~tribution; SI = 96.9~, n.~ =
39.4; melt fl~w index 230/5 s 0.1 dg/minute.
2 ~ 8 ~
~aJple ~
The procedure was analogous to Example 3, but 64.4 mg (O.10 mmol) of diphenylmethylenetfluorenyl)(cyclopentadi-enyl)-hafnium dichloride were employed, the polymeriza-tion temperature wa6 50~C and the polymerization time was 1 hour. 0.34 kg of polypropylene, corresponding to a metallocene activity of 5.3 kg of polypropylene/g of metallocene x hour, was obtained.
VN = 978 cm3/g; N~ = 2.01-106, ~ = 0.61-106, X~/M~ z 3.3, bimodal molecular weiqht distribution; SI = 97.0%, n~m =
40.0; melt flow index 230/5 s 0.1 dg/minute.
B~ample 5 The process wa~ analogous to Example 3, but 126.4 mg (0.196 mmol) of diphenylmethylene(fluorenyl)(cyclopenta-dienyl)-hafnium dichloride were employed, the polymeriza-tion temperature was 30~C and the polymerization time was 2 hours. 0.35 kg of polypropylene, corresponding to a metallocene activity of 1.4 kg of polypropylene/g of metallocene x hour, were obtained.
VN - 487 c~3/g; M~ = 672,500, ~ = 196,500, N~/M~ - 3.4, monomodal molecular weight distribution; SI - 97.5%, n,~
- 48.0; melt flow index 230/5 z 0.1 dg/~inute.
ExaMples 3 to 5 ~how that a high polymerization tempera-ture must be used to achieve a high molecular weight. At the same time, at the higher polymerization temperature the polymerization activity of the metallocens catalyst system i~ advantageously higher.
~ample 6 The procedure was analogous to ~xample 3, but 66.6 mg (0.114 mmol) of (phenyl(methyl)methylene)(fluorenyl)-(cyclopentadienyl)-hafnium dichloride were employed.
1.89 kg of polypropylene, corresponding to a metallocene activity of 5.7 kg of polypropylene/g of metallocene x 2~ 8~
hour, were obtained.
VN = 603 cm3/g; M~ = 806,000, N~ - 175,000, ~/N~ - 4.6, the molecular weight distribution was bimodal; SI =
96.4%, n~m = 38.0; melt flow index 230/5 s 0.1 dg/minute.
~xample 7 The procedure wa~ ~nalogous to Example 3, but 63.9 mg (O.11 mmol) of (phenyl(methyl)methylene)(fluorenyl)-(cyclopentadienyl)-h~fnium dichloride were employed, ~he polymerization temper~ture was 50C and the polymeriza-tion time was 1 hour. 0~17 kg of polypropylene, corre~-ponding to a metallocene activity of 2.7 kg of polypro-pylene/g of me~allocene x hour, was obtained.
VN = 380 cm3/g; M~ = 434,000, ~ = 116,000, N~/M~ ~ 3.7, the molecular weight distribution was bimodal; SI -96.1%, n,~ - 37.0; melt flow index 230/5 = 0.24 dg/
minute.
~ample 8 The procedure was analogous to Example 3, but 110.3 mg (O.19 mmol) of (phenyl(methyl)methylene)(fluorenyl)-(cyclopentadienyl)-hafnium dichloride were employed and the polymerization temperature was 40C. 0.65 kg of polypropylene, corresponding to a metallocene activity of 1.2 kg of polypropylene/g of metsllocene x hour, was obtained~
VN = 576 cm3/g; M~ = 837,500, M~ = 131,500, M~M~ = 6.4;
the molecular weight distribution was bimodal; SI =
97.1%, n.~ = 40.0; melt flow index 230/5 < 0.1 dg/
minute.
~aople 9 The procedure wa~ analogous to ~xample 3, but 151.1 mg (0.26 mmol) of (phenyl(methyl)methylene)(fluorenyl)-(cyclopentadienyl)-hafnium dichloride were employed and the polymerization tempersture was 30C. 0.35 kg of 20~8~
polypropylene, corresponding to a metallocene activity of O.5 kg of polypropylene/g of metallocene x hour, was obtained. VN = 251 cm3/g; N~ ~ 280,500, ~ = 108,500, ~/N~
= 2.6; the molecul~r weight distribution was monomodal;
SI - 97.5~, n.~ c 49.4; melt flow index 230/5 = 1.1 dg/
minute.
The ex2mple6 ~how that a high polymerization temperature must be used to achieve the maximum possible molecular weight. At the eame time, the activity of the metallocene catalyst i8 higher at a h gher polymerization temperature than at a lower polyme~ization temperature. Example B
show6 that instead of a high polymeri~ation temperature, a long polymerization time also leads to a high molecular weight.
~ample 10 A dry 16 dm3 reactor wa~ flushed ~ith nitrogen and filled with 1.6 Ndm3 (corre6ponding to 0.1 bar) of hydrogen and with 10 dm3 of liquid propylene. 30 cm3 of a toluene solution of methylaluminumoxane (corresponding to 40 mmol of Al, average degree of oligomerization of the methyl-aluminumoxane n=20) were then added and the mixture wa~
stirred for 15 minutes.
In parallel with this, 55.7 mg (0.087 mmol) of diphenyl-methylene(fluorenyl)(cyclopentadienyl)-hafnium dichloride were dissolved in 15 cm3 of a toluene 301ution of methyl-aluminoxane (20 mmol of Al).
After 15 minutes, the solution was metered into the reactor and the polymerization temperature was brought to 60C. Polymerization was carried out for 1 hour. 1.0 kg of polypropylene, corresponding to a metallocene activity of 18.0 kg of polypropylene/g of metallocene x hour, wa6 obtained.
VN = 745 cm3/g; SI = 97.5%; M~ = 978,000, N~ = 251,500, M~/M~ = 3.9; melt flow index 230/5 = ~ 0.1 dg/minute.
_ 18 -According to I3C-MMR, the polymer chain6 had no unsatura-ted chain ends.
Esample 11 The procedure was analogous to Example 10, but 48.7 mg (0.084 mmol) of (phenyl(methyl)methylene)(fluorenyl)-(cyclopentadienyl)-hafnium dichloride were employed. 1.91 kg of polypropylene, corre~ponding to ~ metallocene activity of 7.8 kg of polypropylene/g of metallocene x hour, were obtained.
VN = 492 cm3/g; N~ = 697,500; X~ = 131,000; ~/Xb ~ 5.3, the molecular weight distribution was bimodal; SI =
97.5%; melt flow index 230/5 = Q.l dg/minute.
According to l3CoNMR, the polymer chain~ had no unsatura-ted chain ends.
Esample 12 The procedure was analogous to Example 10, but 40 dm3 (corresponding to 2.5 bar) of hydrogen and 60.7 mg (0.104 mmol) of (phenyl(methyl)methylene)(fluorenyl)-(cyclopentadienyl)-hafnium dichloride were employed.
2.47 kg of polypropylene, corre~ponding to a ~etallocene activity of 8.1 kg of polypropylene/g of metallocene x hour, were obtained.
VN = 215 cm3~g; X~ = 218,500; N~ - 75,500; M~/M~ = 2.9; SI
- 98.0%; melt flow ind~x 230/5 = 8.1 dg/minute.
According to l3C-NMR, the polymer chains had no un~atu-rated chain ends.
Examples 10 to 12 demonstrate the possibility of regulat-ing the molecular weight by means of addition of hydrogen during the polymerization.
~ R3 R5 Hf \ ~I) wherein Rl and R2 are identical or different and denote a hydrogen atom, a C~-C10-, preferably Cl-C3-alkyl group, a Cl-C10-, preferably Cl-C3-alkoxy group, a C6-C10-, prefer-ably C6-C8-aryl group, a C6-C10-, preferably CB-C~-aryloxy group, a C2-C10-, preferably C2-C4-alkenyl group, a C7-C40-1~ preferably C7-C10-arylalkyl group, a C7-C~o-~ preferably C7-Cl2-alkylaryl group, a CB-C40-~ preferably Ct-C12-arylalk-enyl group or a halogen ~tom, preferably ~hlorine.
R3 and R4 are different and denote a mono- or polynuclear hydrocarbon radical, which can form a ~andwich 6tructure with the hafnium. R3 and R4 are preferably fluorenyl and cyclopentadienyl, it al60 being pos~ible for the fluor-enyl or cyclopentadienyl base structures additionally to carry sub~ituent~.
R5 i~ a single- or multi-membered bridge which link~ the radicals R3 and R4 and denotes Ml ~1 -, - Ml - CR2 -, - C -, _ o _ ~ C - C - ,-R7 R7 ~7 - BR6, z AlR6, -Ge-, -Sn-, -O-, -S-, = SO, = SO2, = NR6, = CO, = PR5 or = P(o)R6, in which R~, R7 and R~ are identi-cal or different and denote a hydrogen atGm, a halogen 20~1~8~
atom, preferably chlorine, a C1-C~O-, preferably Cl-C3-alkyl group, in particular a methyl group, a Cl-C10-fluoroalkyl group, preferably a CF3 group, a C6-C1O-fluoro-aryl group, preferably a pentafluorophenyl group, a C6-C10-, preferably C6-C6-aryl group, a Cl-C~O-, preferably Cl-C4-alkoxy group, in particular a methoxy group, a Cz-C1o-, preferably C2-C4-alkenyl group, a C,-C~O-, preferably C,-C10-arylalkyl group, a C8-C~O-, preferably C8-C~-arylalk-enyl group or a C7-c~o-~ preferably C,-C~-alkylaryl group, or R6 and R' or R6 and R8, in each ca~e together with the ato~s ~oining them, form a ring.
M~ is ~ilicon, germanium or tin, preferably 6ilicon or germanium.
Rs i6 preferably =CR6R', =SiR6R', =GeR6R', -O-, -S-, =SO, =pR6 or =P(o)R6.
The metallocenes described akove can be prepared in accordance with the following general equation:
H2R3~ButylL1 -~HR3L1 5~ X-R5-X
H2R4~ButylL1-i~HR4LlJ
HR3-RS-R4H 2 ButvlLi~
LiR3-R5-R4Li Hf C14_~
tR
2~8~
(X = Cl, ~r, J, O-Tosyl) or H2R3~ButylLi ~HR3Li R6 R7 ~ R4H
\C a HR3L1 R6R7c R4 b H20 1 ~ R3H
2 8utylL1 6R7C lLi2 ~ H~C14 C ~
~R4 ~l ~c ~r R2Li, .
201~8g~
Metallocene~whicharepreferablyemployedare(arylalkyli-dene)(fluorenyl)(cyclopentadienyl)-hafniumdichlorideand (diarylmethylene)(fluorenyl)(cyclopentadienyl)-hafnium dichloride. (Methyl(phenyl)methylene)(fluorenyl)(cyclo-pentadienyl)-hafnium dichloride and (diphenylmethylene)-(fluorenyl)(cyclopentadienyl)-hafnium dichloride are particularly preferred here.
The cocataly~t is an aluminoxane of the formula II
--Al- O _EA1- Ol~Al ( I I ) ~0 for the linear type and/or of the formula III
_ rAl~O (III) ~ n~2 for the cyclic typs. In these formulae, the radicals R~
denote a Cl-C6-alkyl group, pxeferably methyl, ethyl, isobutyl, butyl or neopentyl, or a C~-C1O-aryl ~roup, preferably phenyl or benzyl. Methyl iB particularly preferred. n is an integer from 2 to 50, preferably 5 to ~0. However, the exact structure of the sluminoxane i8 not known.
~he aluminoxane can be prepared in variou~ ways.
One possibility is careful addition of water to a dilute ~olution of an aluminum trialkyl by introducing in each ca~e small portion~ of the ~olution of the nluminum trialkyl, preferably aluminum trimethyl, and the water into an initially introduced relatively l~rge amount of an inert solvent and waiting for the evolution of gas to end between each addition.
In another process, finely powdered copper sulfate penta-20~ ~8~
hydrate i8 suspended in toluene in a gla6s ~lask, and aluminum trialkyl i8 added under an inert ga6 at about -20C in an amount such that about 1 mole of CuSO4 5H20 i~
available for every 4 Al atoms. After 810w hydrolysi~, alkane being split off, the reaction mixture i8 left at room temperature for 24 to 48 hour6, during wh~ch it must be cooled, if appropriate, 80 that the temperature does not rise above 30~C. The ~luminoxane di6solved in the toluene i6 then filtered off from the copper sulfate and the solution i~ concentrated in vacuo. It is assumed that in this preparation process the low molecular weight aluminoxanes undergo condenæation to higher oligomer6, aluminum trialkyl being split off.
Aluminoxane6 are furthermore obtained by a procedure in which aluminum trialkyl, preferably aluminum trLmethyl, dis601ved in an inert aliphatic or aromatic solvent, preferably heptane or toluene, i6 reacted with aluminum ~alt6 containing water of cry6tallization, preferably aluminum sulfate, at a temperature of -20 to 100C. The volume ratio here between solvent and the aluminum 81kyl used i6 1:1 to 50:1 - preferably 5:1 - and the reaction time, which can be controlled by the ~plitting off of the alkane, i6 1 to 200 hours - preferably 10 to 40 hour6.
Of the aluminum ~alts containing water of crystalliza-tion, tho6e which have a high content of water of cry8-tallization are u~ed in particular. Aluminum sulfAte hydrate is particularly preferred, above all the com-pound6 Al2(SO4)3-16H20 and Al2~SO~)3 18H20, with the parti-cularly high water of cry6tallization content of 16 and 18 mole~ of H20/mole of Al2(SO4)3 re6pectively.
Another variant for the preparation of aluminoxanes compri6es di6solving aluminum trialkyl, preferably aluminum trimethyl, in heptane or toluene in the suspend-ing sgent which ha6 been initially introduced into the polymerization ve~sel, preferably in the liquid monomer, and then reacting the aluminum compound with water.
In addition to the proces~e6 described above for the preparation of aluminoxanes, there are others which can be used. Regardless of the nature of the preparation, all the aluminoxane ~olutions have the common feature of a varying content of unreacted aluminum trialkyl which is in free form or as an adduct. This content has an influ-ence on the catalytic activity which ha6 not yet been clarified precisely and differs according to the metal-locene compound employed.
It is possible for the metallocene to be preactivated before use in the polymerization reaction with an alumin-oxane of the formula (II) and/or (III). The polymeriza-tion ac~ivity is in this way increased significantly and the grain morphology is improved.
The preactivation of the transition metal compound is carried out in solution. Preferably, in thi6 procedure, the metallocene is dissolved in a solution of the alumin-oxane in an inert hydrocarbon. An aliphatic or aromatic hydrocarbon is suitable as the inert hydrocarbon. Toluene is preferably used.
The concentration of the aluminoxane in the solution i8 in the range from about 1% by weight up to the ~atura~ion limit, preferably 5 to 30% by weight, in each case based on the total solution. The metallocene can be employed in the sam6 concentration, but it is preferably employed in an amount of 10-~ - 1 mole per mole of aluminoxane. The preactivation time i8 5 minutes to 60 hours, preferably S to 60 minutes. The reaction i~ carried out at a tem-perature of -78 to 100C, preferably 0 to 70~C.
A significantly longer preactivation is possible, but this usually has neither an activity-increasing nor an activity-reducing effect, although it may be entirely appropriate for storage purposes.
The polymerization is carried out in a known manner in 201~8801 solution, in suspension or in the gas phase, continuously or discontinuously, in one or more stage~ at a tempera-ture of -60 to 200C, preferably -30 to lOO-C, in parti-cular 0 to 80C.
The total pressure in the polymerization ~ystem i8 0.5 to 100 bar. The polymerization in the pressure range of 5 to 60 bar, which is of particular interest industrially, is preferred. Monomers of boiling points higher than the polymerization temperature are preferably polymerized under normal pressure.
In this reaction, the metallocene compound is u~ed in a concentration, based on the transition metal, of 10-3 to 10-', preferably 10-4 to 10-6 mol of transition metal per dm3 of solvent or per dm3 of reactor volume. The aluminox-ane is used in a concentration of 10-5 to 10~1 ~ol, prefer-ably 10-5 to 10-2 mol per dm3 of ~olvent or per dm3 of reactor volume. In principle, however, higher concentra-tions are also possible.
If the polymerization is carried out as su~pen~ion or ~olution polymerization, an inert ~ol~ent which iB
customary for the Ziegler low pressure process i~ u~ed.
For example, the polymerization is carried out in an aliphatic or cycloaliphatic hydrocarbon; examples of these which may be mentioned are butane, pentane, hexane, heptane, isooctane, cyclohexane and methylcyclohexane.
A benzihe or hydrogenated diesel oil fraction can furthermore be u~ed. Toluene can also ba used. The poly-merization is preferably carried out in ~he liquid monomer.
Olefins of the formula R-CH = CH*, in which R- and Rb are identical or different and denote a hydrogen atom or an alkyl radical having 1 to 28 carbon atoM~, it also being possible for R- and Rb to be bonded as a ring, are poly-merized or copolymerized. Examples of ~uch olefins are .
2~
ethylene, propylene, l-butene, l-hexene, 4-methyl-1-pentene, l-octene, norbornene or norbornad$ene. Propyl-ene, l-butene and 4-methyl-1-pentene are preferred.
The molecular weight of the polymer can be regulated in a known manner. For example, the molecular weight can be regulated with excess trialkylaluminum, preferably tri-methylaluminum present in the aluminoxane 801ution.
Hydrogen i~ preferably used.
The polymeriz~tion can be of any desired duration, since the catalyst sy~tem to be used according to the invention exhibits only a slight time-dependent decrease in poly-merization activity.
If the polymerization time i8 relatively long, the high molecular weight content in the polymer increases sig-nificantly. A longer residence time in the polymerization~ystem i~ therefore advi~able~n order to achieve high average molecular weights. In order to achieve high mole-cular weights, it i6 advantageous to maintain a high polymerization temperature, ~ince, in contrast to known processe~, 8~ the polymerization temperature increa~es in the polymerization ~y~tem to be used according to the invention, a higher molecular weight ha~ also simultane-ously been found. Furthermore, a hi~her metallocene activity is al~o simultaneously achieved at a higher polymerization temperature. This means that lower resi-dual ash contents are obtained in the polymer.
The molecular weight distribution is broad to bimodal at a higher polymerization temperature, and is narrow and monomodal at a lower temperature.
The polymers prepared accord.ing to the invention moreover generally exhibit a very high syndiotactic index of more than 90~; in this, the process according to the invention is significantly superior to the kn~wn processes.
2 ~
The followin~ example~ are intended to illustrate the invention. In these examples VN - viscosity number in cm3/g k~ - weight-average molecular weight in g/mol N~ = n~ er-average molecular weight in g/mol N~/M~ = molecular weight distribution The molecular weight was determined by gel permeation chromatography~
SI - syndiotactic index, determined by l3C-NMR
I0 spectroscopy n~ = average ~yndiotactic block length (l+ ~F) All the following working operations of metallocene ~ynthesis were carried out under an inert gas atmosphere using absolute colvent~.
~ample 1 (Phenyl(methyl)methylene)(9-fluorenyl)(cyclopentadienyl)-hafnium dichloride Ph ~ ~ ~ Cl ~ C ~ Hf A ~olution of 67.8 mmol of lithium-fluorene in 50 cm3 of tetrahydrofuran was added to a solution of 11.4 g (67.8 mmol) of 6-methyl-6-phenylfulvene in 40 cm3 of tetrahydrofuran at room temperature. After the mixture had been ~tirred at room temperature for 2 hour~, 60 cm3 of water were added. The ~ub~tance which precipitated out wa~ filtered off with ~uction, washed with diethyl ether and dried under an oil pump vacuum. 19.1 g (84.2%) of 1-cyclopentadienyl-l-(9-fluorenyl)-ethylbenzene were 2`~
_ 13 -obtained (correct elemental analyses; ~H-NMR spectrum).
10.0 g (19.9 mmol) of the compound were dis~olved in 60 cm3 of tetrahydrofuran and 26 cm3 (65 mmol) of a 2.5 molar hexane ~olution of n-butyllithium were added at 0C. After the mixture had been stirred for 15 minutes, the solvent was ~tripped off in vacuo. The dark red residue which remained was washed several times with hexane and drie~ under an oil pump vacuum. 15.6 g of the red dilithium ~alt were obtained as the tetrahydrofur~n adduct which contained about 30% of tetrahydrofuran. A
su~pension of 4.78 q (14.9 mmol) of HfCl~ in 70 cm3 of CH2CH2 was reacted with~14.9 mmol of the dilithium salt and the reaction product wa~ worked up. Cry~tallization at -35-C gave 2.6 g (30~) of the hafnocene dichloride compound as orange crystal~.
Correct elemental analy~is.
1 H-NMR 8pectrum (100 MHz, CDC13)s 7.17 - 8.20 (m, 11 H, Flu-H,Ph-H), 6.87 (m, 1, Ph-H), 6.12 - 6.42 (m,3, Ph-H,CpH), 5.82, 5.67 (2xdd,2xl,Cp-H), 2.52 (s,3,CH3).
~ample 2 Diphenylmethylene(9-fluorenyl)(cyclopentadienyl)-hafnium dichloride Ph ~ ~ ~ Cl ~ C Hf~
Ph ~ Cl 12.3 cm3 (30.7 mmol) of a 2.5 molar hexane solution of n-butyllithium were ~lowly added to a solution of 5.10 g(30.7 mmol) of fluorene in 60 cm3 of tetrahydrofur~n at room temperature. After 40 minutes, 7.07 q (30.7 mmol) of diphenylfulvene were added to the orange solution and the m~xture was ~t~rred overnight. 60 cm3 of water were added to the dark red ~olution, whereupon the ~olution became yellow-colored, and the mixture was extracted with ether.
The ether phase was dried over MgS04 and concentrated and the residue was left to crystallize at -35C. 5.1 g (42%) of l-cyclopentadienyl-l-(9-fluorenyl)-diphenylmethane were obtained as a beige powder. 1.25 g (3.15mmol) of 1-cyclo-pentadienyl-l-(9-fluorenyl)-diphenylmethane were reacted with 6.3 mmol of butyllithium analogously to Example 1.
The dilithium salt was reacted with 1.0 g (3.15 mmol) of HfCl4 analogously to Example 1. Filtration of the orange reaction mixture over a G4 frit and extraction of the filtrate with lO0 cm3 of toluene gave 0.70 g (34~) of the hafnocene dichloride complex ~s ~ yellow-orange powder.
Correct elemental analysis. The mass spectrum gave M+ - 644.
1 H-NNR spectrum ~100 NHz,CDCl3): 6.85 - 8.25 (m,16,Flu-H,Ph-H), 6.37 (m,2,Ph-H), 6.31 (t,2,Cp-H), 5.75 (t,2,Cp-I5 M).
8xample 3 A dry 16 dm3 reactor was flushed with nitrogen and filledwith 10 dm3 of liquid propylene. ~0 cm3 of a toluene-~olution of methylaluminoxane (corresponding ~o 40 mmol of Al, average degree of oligomeri~ation of the methyl-aluminoxsne n = 20) were then added and the mixture wa~
stirred for 15 minutes.
In parallel to thi~, 53.0 mg (O.082 mmol) of diphenyl-methylene(fluorenyl)(cyclopentedienyl)-hafnium dichloride were di~solved in 15 cm3 of a toluene Qolution of methyl-aluminoxane (20 mmol of Al). After 15 minutes, the ~olution was introduced into the reactor and the polymer-ization temperature was brought to 60C. Polymerization was carried out for 5 hours. 3.20 kg of polypropylene, corre~ponding to a metallocene activity of 12.0 kg of polypropylene/g of metallocene x hour, were obtained.
VN = 1254 cm3/g; M~ = 2.34-10~, N~ = 580,000, ~/M~ = 4.0, bimodal molecular weight di~tribution; SI = 96.9~, n.~ =
39.4; melt fl~w index 230/5 s 0.1 dg/minute.
2 ~ 8 ~
~aJple ~
The procedure was analogous to Example 3, but 64.4 mg (O.10 mmol) of diphenylmethylenetfluorenyl)(cyclopentadi-enyl)-hafnium dichloride were employed, the polymeriza-tion temperature wa6 50~C and the polymerization time was 1 hour. 0.34 kg of polypropylene, corresponding to a metallocene activity of 5.3 kg of polypropylene/g of metallocene x hour, was obtained.
VN = 978 cm3/g; N~ = 2.01-106, ~ = 0.61-106, X~/M~ z 3.3, bimodal molecular weiqht distribution; SI = 97.0%, n~m =
40.0; melt flow index 230/5 s 0.1 dg/minute.
B~ample 5 The process wa~ analogous to Example 3, but 126.4 mg (0.196 mmol) of diphenylmethylene(fluorenyl)(cyclopenta-dienyl)-hafnium dichloride were employed, the polymeriza-tion temperature was 30~C and the polymerization time was 2 hours. 0.35 kg of polypropylene, corresponding to a metallocene activity of 1.4 kg of polypropylene/g of metallocene x hour, were obtained.
VN - 487 c~3/g; M~ = 672,500, ~ = 196,500, N~/M~ - 3.4, monomodal molecular weight distribution; SI - 97.5%, n,~
- 48.0; melt flow index 230/5 z 0.1 dg/~inute.
ExaMples 3 to 5 ~how that a high polymerization tempera-ture must be used to achieve a high molecular weight. At the same time, at the higher polymerization temperature the polymerization activity of the metallocens catalyst system i~ advantageously higher.
~ample 6 The procedure was analogous to ~xample 3, but 66.6 mg (0.114 mmol) of (phenyl(methyl)methylene)(fluorenyl)-(cyclopentadienyl)-hafnium dichloride were employed.
1.89 kg of polypropylene, corresponding to a metallocene activity of 5.7 kg of polypropylene/g of metallocene x 2~ 8~
hour, were obtained.
VN = 603 cm3/g; M~ = 806,000, N~ - 175,000, ~/N~ - 4.6, the molecular weight distribution was bimodal; SI =
96.4%, n~m = 38.0; melt flow index 230/5 s 0.1 dg/minute.
~xample 7 The procedure wa~ ~nalogous to Example 3, but 63.9 mg (O.11 mmol) of (phenyl(methyl)methylene)(fluorenyl)-(cyclopentadienyl)-h~fnium dichloride were employed, ~he polymerization temper~ture was 50C and the polymeriza-tion time was 1 hour. 0~17 kg of polypropylene, corre~-ponding to a metallocene activity of 2.7 kg of polypro-pylene/g of me~allocene x hour, was obtained.
VN = 380 cm3/g; M~ = 434,000, ~ = 116,000, N~/M~ ~ 3.7, the molecular weight distribution was bimodal; SI -96.1%, n,~ - 37.0; melt flow index 230/5 = 0.24 dg/
minute.
~ample 8 The procedure was analogous to Example 3, but 110.3 mg (O.19 mmol) of (phenyl(methyl)methylene)(fluorenyl)-(cyclopentadienyl)-hafnium dichloride were employed and the polymerization temperature was 40C. 0.65 kg of polypropylene, corresponding to a metallocene activity of 1.2 kg of polypropylene/g of metsllocene x hour, was obtained~
VN = 576 cm3/g; M~ = 837,500, M~ = 131,500, M~M~ = 6.4;
the molecular weight distribution was bimodal; SI =
97.1%, n.~ = 40.0; melt flow index 230/5 < 0.1 dg/
minute.
~aople 9 The procedure wa~ analogous to ~xample 3, but 151.1 mg (0.26 mmol) of (phenyl(methyl)methylene)(fluorenyl)-(cyclopentadienyl)-hafnium dichloride were employed and the polymerization tempersture was 30C. 0.35 kg of 20~8~
polypropylene, corresponding to a metallocene activity of O.5 kg of polypropylene/g of metallocene x hour, was obtained. VN = 251 cm3/g; N~ ~ 280,500, ~ = 108,500, ~/N~
= 2.6; the molecul~r weight distribution was monomodal;
SI - 97.5~, n.~ c 49.4; melt flow index 230/5 = 1.1 dg/
minute.
The ex2mple6 ~how that a high polymerization temperature must be used to achieve the maximum possible molecular weight. At the eame time, the activity of the metallocene catalyst i8 higher at a h gher polymerization temperature than at a lower polyme~ization temperature. Example B
show6 that instead of a high polymeri~ation temperature, a long polymerization time also leads to a high molecular weight.
~ample 10 A dry 16 dm3 reactor wa~ flushed ~ith nitrogen and filled with 1.6 Ndm3 (corre6ponding to 0.1 bar) of hydrogen and with 10 dm3 of liquid propylene. 30 cm3 of a toluene solution of methylaluminumoxane (corresponding to 40 mmol of Al, average degree of oligomerization of the methyl-aluminumoxane n=20) were then added and the mixture wa~
stirred for 15 minutes.
In parallel with this, 55.7 mg (0.087 mmol) of diphenyl-methylene(fluorenyl)(cyclopentadienyl)-hafnium dichloride were dissolved in 15 cm3 of a toluene 301ution of methyl-aluminoxane (20 mmol of Al).
After 15 minutes, the solution was metered into the reactor and the polymerization temperature was brought to 60C. Polymerization was carried out for 1 hour. 1.0 kg of polypropylene, corresponding to a metallocene activity of 18.0 kg of polypropylene/g of metallocene x hour, wa6 obtained.
VN = 745 cm3/g; SI = 97.5%; M~ = 978,000, N~ = 251,500, M~/M~ = 3.9; melt flow index 230/5 = ~ 0.1 dg/minute.
_ 18 -According to I3C-MMR, the polymer chain6 had no unsatura-ted chain ends.
Esample 11 The procedure was analogous to Example 10, but 48.7 mg (0.084 mmol) of (phenyl(methyl)methylene)(fluorenyl)-(cyclopentadienyl)-hafnium dichloride were employed. 1.91 kg of polypropylene, corre~ponding to ~ metallocene activity of 7.8 kg of polypropylene/g of metallocene x hour, were obtained.
VN = 492 cm3/g; N~ = 697,500; X~ = 131,000; ~/Xb ~ 5.3, the molecular weight distribution was bimodal; SI =
97.5%; melt flow index 230/5 = Q.l dg/minute.
According to l3CoNMR, the polymer chain~ had no unsatura-ted chain ends.
Esample 12 The procedure was analogous to Example 10, but 40 dm3 (corresponding to 2.5 bar) of hydrogen and 60.7 mg (0.104 mmol) of (phenyl(methyl)methylene)(fluorenyl)-(cyclopentadienyl)-hafnium dichloride were employed.
2.47 kg of polypropylene, corre~ponding to a ~etallocene activity of 8.1 kg of polypropylene/g of metallocene x hour, were obtained.
VN = 215 cm3~g; X~ = 218,500; N~ - 75,500; M~/M~ = 2.9; SI
- 98.0%; melt flow ind~x 230/5 = 8.1 dg/minute.
According to l3C-NMR, the polymer chains had no un~atu-rated chain ends.
Examples 10 to 12 demonstrate the possibility of regulat-ing the molecular weight by means of addition of hydrogen during the polymerization.
Claims (3)
1. A process for the preparation of a syndiotactic polyolefin by polymerization or copolymerization of an olefin of the formula RaCH=CHRb, in which Ra and Rb are identical or different and denote a hydrogen atom or an alkyl radical having 1 to 28 carbon atoms, or Ra and Rb, with the atoms joining them, can form a ring, at a temperature of -60 to 200°C under a pressure of 0.5 to 100 bar in solution, in suspen-sion or in the gas phase in the presence of a cata-lyst which consists of a metallocene as the transi-tion metal component and an aluminoxane of the formula II
(II) for the linear type and/or of the formula III
(III) for the cyclic type, in which, in the formulae II
and III, R9 denotes a C1-C6-alkyl group or a C6-C10-aryl group or benzyl and n is an integer from 2 to 50, which comprises carrying out the polymeriza-tion in the presence of a catalyst, the transition.
metal component of which is a compound of the formula I
(I) in which R1 and R2 are identical or different and denote a hydrogen atom, a halogen atom, a C1-C10-alkyl group, a C1-C10-alkoxy group, a C6-C10-aryl group, a C5-C10-aryloxy group, a C2-C10-alkenyl group, a C7-C40-aryl-alkyl group, a C7-C40-alkylaryl group or a C8-C40-arylalkenyl group, R3 and R4 are different and denote a mono- or poly-nuclear hydrocarbon radical, which can form a sandwich structure with the hafnium, R5 is = BR6, = AlR6, -Ge-, -Sn-, -O-, -S-, - SO, = SO2, = NR6, - CO, - PR6 or = P(O)R6, in which R6, R7 and R8 are identical or different and denote a hydrogen atom, a halogen atom, n C1-C10-alkyl group, a C1-C10-fluoroalkyl group, a C6-C10-fluoroaryl group, a C6-C10-aryl group, a C1-C10-alkoxy group, a C2-C10-alkenyl group, a C7-C40-arylalkyl group, a C8-C40-arylalkenyl group or a C7-C40-alkylaryl group, or R5 and R7 or R5 and R8, in each case with the atoms joining them, form a ring, and M1 is silicon, germanium or tin.
(II) for the linear type and/or of the formula III
(III) for the cyclic type, in which, in the formulae II
and III, R9 denotes a C1-C6-alkyl group or a C6-C10-aryl group or benzyl and n is an integer from 2 to 50, which comprises carrying out the polymeriza-tion in the presence of a catalyst, the transition.
metal component of which is a compound of the formula I
(I) in which R1 and R2 are identical or different and denote a hydrogen atom, a halogen atom, a C1-C10-alkyl group, a C1-C10-alkoxy group, a C6-C10-aryl group, a C5-C10-aryloxy group, a C2-C10-alkenyl group, a C7-C40-aryl-alkyl group, a C7-C40-alkylaryl group or a C8-C40-arylalkenyl group, R3 and R4 are different and denote a mono- or poly-nuclear hydrocarbon radical, which can form a sandwich structure with the hafnium, R5 is = BR6, = AlR6, -Ge-, -Sn-, -O-, -S-, - SO, = SO2, = NR6, - CO, - PR6 or = P(O)R6, in which R6, R7 and R8 are identical or different and denote a hydrogen atom, a halogen atom, n C1-C10-alkyl group, a C1-C10-fluoroalkyl group, a C6-C10-fluoroaryl group, a C6-C10-aryl group, a C1-C10-alkoxy group, a C2-C10-alkenyl group, a C7-C40-arylalkyl group, a C8-C40-arylalkenyl group or a C7-C40-alkylaryl group, or R5 and R7 or R5 and R8, in each case with the atoms joining them, form a ring, and M1 is silicon, germanium or tin.
2. The use of the syndiotactic polyolefin prepared as claimed in claim 1 for the production of films and shaped articles by extrusion, injection molding, blow molding or compression sintering.
3. The process as claimed in claim 1, and substantially as described herein.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE3907964A DE3907964A1 (en) | 1989-03-11 | 1989-03-11 | METHOD FOR PRODUCING A SYNDIOTACTIC POLYOLEFIN |
| DEP3907964.3 | 1989-03-11 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2011880A1 true CA2011880A1 (en) | 1990-09-11 |
Family
ID=6376133
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002011880A Abandoned CA2011880A1 (en) | 1989-03-11 | 1990-03-09 | Process for the preparation of a syndiotactic polyolefin |
Country Status (8)
| Country | Link |
|---|---|
| US (2) | US5132381A (en) |
| EP (1) | EP0387691B1 (en) |
| JP (1) | JP3176609B2 (en) |
| AU (1) | AU641638B2 (en) |
| CA (1) | CA2011880A1 (en) |
| DE (2) | DE3907964A1 (en) |
| ES (1) | ES2076240T3 (en) |
| ZA (1) | ZA901845B (en) |
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| US4530914A (en) * | 1983-06-06 | 1985-07-23 | Exxon Research & Engineering Co. | Process and catalyst for producing polyethylene having a broad molecular weight distribution |
| DE3726067A1 (en) * | 1987-08-06 | 1989-02-16 | Hoechst Ag | METHOD FOR PRODUCING 1-OLEFIN POLYMERS |
| US4892851A (en) * | 1988-07-15 | 1990-01-09 | Fina Technology, Inc. | Process and catalyst for producing syndiotactic polyolefins |
| DE3825814A1 (en) * | 1988-07-29 | 1990-02-01 | Hoechst Ag | METHOD FOR PRODUCING L-OLEFIN POLYMERS |
| DE3907965A1 (en) * | 1989-03-11 | 1990-09-13 | Hoechst Ag | METHOD FOR PRODUCING A SYNDIOTACTIC POLYOLEFIN |
-
1989
- 1989-03-11 DE DE3907964A patent/DE3907964A1/en not_active Withdrawn
-
1990
- 1990-03-08 ES ES90104402T patent/ES2076240T3/en not_active Expired - Lifetime
- 1990-03-08 US US07/490,833 patent/US5132381A/en not_active Ceased
- 1990-03-08 DE DE59009311T patent/DE59009311D1/en not_active Expired - Fee Related
- 1990-03-08 JP JP05518290A patent/JP3176609B2/en not_active Expired - Lifetime
- 1990-03-08 EP EP90104402A patent/EP0387691B1/en not_active Expired - Lifetime
- 1990-03-09 ZA ZA901845A patent/ZA901845B/en unknown
- 1990-03-09 AU AU51179/90A patent/AU641638B2/en not_active Ceased
- 1990-03-09 CA CA002011880A patent/CA2011880A1/en not_active Abandoned
-
1994
- 1994-07-21 US US08/278,504 patent/USRE36103E/en not_active Expired - Lifetime
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5191132A (en) * | 1991-05-09 | 1993-03-02 | Phillips Petroleum Company | Cyclopentadiene type compounds and method for making |
| US5436305A (en) * | 1991-05-09 | 1995-07-25 | Phillips Petroleum Company | Organometallic fluorenyl compounds, preparation, and use |
Also Published As
| Publication number | Publication date |
|---|---|
| US5132381A (en) | 1992-07-21 |
| EP0387691A1 (en) | 1990-09-19 |
| JPH02274704A (en) | 1990-11-08 |
| USRE36103E (en) | 1999-02-16 |
| JP3176609B2 (en) | 2001-06-18 |
| DE3907964A1 (en) | 1990-09-13 |
| AU5117990A (en) | 1990-09-13 |
| DE59009311D1 (en) | 1995-08-03 |
| AU641638B2 (en) | 1993-09-30 |
| ZA901845B (en) | 1990-11-28 |
| ES2076240T3 (en) | 1995-11-01 |
| EP0387691B1 (en) | 1995-06-28 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| EEER | Examination request | ||
| FZDE | Discontinued |