CA2055216C - Process for the preparation of a high molecular weight olefin polymer - Google Patents
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- 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
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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
- C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
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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
- 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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- 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
- C08F110/02—Ethene
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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
- C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F210/04—Monomers containing three or four carbon atoms
- C08F210/06—Propene
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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
- 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
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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
- 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
Abstract
Process for the preparation of a high molecular weight olefin polymer A very active catalyst system for olefin polymerization is composed of an aluminoxane and a metallocene of the formula I
(see formula I) wherein preferably M1 is Zr or Hf, R1 and R2 are alkyl or halogen, R3 and R4 are hydrogen, R5 and R6 are alkyl or haloalkyl, -(CR8R9)m-R7-(CR8R9)n- is a single-membered or multimembered chain in which R7 may also be a (sub-stituted) hetero atom, and m+n is zero or 1. The catal-yst system gives polymers having a high molecular weight and high stereospecificity.
(see formula I) wherein preferably M1 is Zr or Hf, R1 and R2 are alkyl or halogen, R3 and R4 are hydrogen, R5 and R6 are alkyl or haloalkyl, -(CR8R9)m-R7-(CR8R9)n- is a single-membered or multimembered chain in which R7 may also be a (sub-stituted) hetero atom, and m+n is zero or 1. The catal-yst system gives polymers having a high molecular weight and high stereospecificity.
Description
~~~~~ ~.t HOECHST AKTIENGESELLSCHAFT HOE 90/F 334 Dr.LO/PP
Description Process for the preparation of a high molecular weight olefin polymer The invention relates to a process for the preparation of olefin polymers having high isotacticity, a narroc~
molecular weight distribution and a high molecular weight.
Polyolefins having a high molecular weight are par-ticularly important far the production of films, sheets 1d or large hollow articles, such as, fox example, pipes or moldings.
The literature discloses soluble metallocene compounds based on bis(cyclopentadienyl)zirconiumalkyl or halide in combination with oligomeric aluminoxanes. With these systems, ethylene and propylene can be polymerized with moderate activity, but isotactic polypropylene is not obtained.
It is also known that the catalyst system bis(cyclopenta-dienyl)titaniumdiphenyl/methylaluminoxane is capable of converting propylene into stereo block polymers, i.e.
polypropylene having longer or shorter isotactic sequen-ces (cf. U>S. Patent 4,522,952). Substantial advantages of this catalyst system are the fact that the polymeriza-tion temperatures ( 0°C to -60°C) are irrelevant on a large industrial scale, and the completely unsatisfactory catalyst activities.
Isotactic poly~,ropylene can be prepared with the aid of ethylenebis(4,5,6,7-tetrahydro-1-indenyl)zirconium dichloride together with an aluminoxane in a suspension polymerization (cf. E1P-A 185 91~). The polymer has a narrow molecular weight distribution, which i.s advan-tageous for certain applications, for example for high-performance in;jec~tion molding.
Description Process for the preparation of a high molecular weight olefin polymer The invention relates to a process for the preparation of olefin polymers having high isotacticity, a narroc~
molecular weight distribution and a high molecular weight.
Polyolefins having a high molecular weight are par-ticularly important far the production of films, sheets 1d or large hollow articles, such as, fox example, pipes or moldings.
The literature discloses soluble metallocene compounds based on bis(cyclopentadienyl)zirconiumalkyl or halide in combination with oligomeric aluminoxanes. With these systems, ethylene and propylene can be polymerized with moderate activity, but isotactic polypropylene is not obtained.
It is also known that the catalyst system bis(cyclopenta-dienyl)titaniumdiphenyl/methylaluminoxane is capable of converting propylene into stereo block polymers, i.e.
polypropylene having longer or shorter isotactic sequen-ces (cf. U>S. Patent 4,522,952). Substantial advantages of this catalyst system are the fact that the polymeriza-tion temperatures ( 0°C to -60°C) are irrelevant on a large industrial scale, and the completely unsatisfactory catalyst activities.
Isotactic poly~,ropylene can be prepared with the aid of ethylenebis(4,5,6,7-tetrahydro-1-indenyl)zirconium dichloride together with an aluminoxane in a suspension polymerization (cf. E1P-A 185 91~). The polymer has a narrow molecular weight distribution, which i.s advan-tageous for certain applications, for example for high-performance in;jec~tion molding.
At the same time, the catalyst system has a number of deficiences.
The polymerization is carried out in toluene, which has to be purified by an expensive procedure and freed from moisture and oxygen. Furthermore, the bulk density of the polymer is too low and the particle morphology and the particle size distribution are unsatisfactory.
7However, a particular disadvantage of the known process is that, at polymerization temperatures of interest industrially, it is possible to prepare only polymers having an unacceptably low molecular weight.
A special preactivation method for the metallocene with an aluminoxane was also proposed, which method leads to a considerable increase in the activity of the catalyst system and to a substantial improvement in the particle morphology of the polymer (cf. DE 37 26 067). Although the preactivation increases the molecular weight, no substantial increase can be achieved.
A further, but still insufficient increase in the molecu-lar weight can be realized by using specially hetero atom-bridged metallocenes having high metallocene activ-ity (EP-A 0 336 128).
Catalysts based on ethylenebisindenylhafnium dichloride and ethyl~nebis(4,5,6,7-tetrahydro-1-indenyl)hafnium dichloride and methylaluminoxane are also known, by means of which relatively high molecular weight polypropylenes can be prepared by suspension polymerization (cf. J.A.
Ewen et al., J. Am. Chem. Soc: 109 (1987), 6544). Among industrially relevant polymerization conditions, however, the particle morphology of the polymers thus produced is unsatisfactory and the activity of the catalysts used is comparatively low. In cox~~unction with the high catalyst costs, economical polymerization is thus impossible with these systems.
The polymerization is carried out in toluene, which has to be purified by an expensive procedure and freed from moisture and oxygen. Furthermore, the bulk density of the polymer is too low and the particle morphology and the particle size distribution are unsatisfactory.
7However, a particular disadvantage of the known process is that, at polymerization temperatures of interest industrially, it is possible to prepare only polymers having an unacceptably low molecular weight.
A special preactivation method for the metallocene with an aluminoxane was also proposed, which method leads to a considerable increase in the activity of the catalyst system and to a substantial improvement in the particle morphology of the polymer (cf. DE 37 26 067). Although the preactivation increases the molecular weight, no substantial increase can be achieved.
A further, but still insufficient increase in the molecu-lar weight can be realized by using specially hetero atom-bridged metallocenes having high metallocene activ-ity (EP-A 0 336 128).
Catalysts based on ethylenebisindenylhafnium dichloride and ethyl~nebis(4,5,6,7-tetrahydro-1-indenyl)hafnium dichloride and methylaluminoxane are also known, by means of which relatively high molecular weight polypropylenes can be prepared by suspension polymerization (cf. J.A.
Ewen et al., J. Am. Chem. Soc: 109 (1987), 6544). Among industrially relevant polymerization conditions, however, the particle morphology of the polymers thus produced is unsatisfactory and the activity of the catalysts used is comparatively low. In cox~~unction with the high catalyst costs, economical polymerization is thus impossible with these systems.
- 3 _ Tt was the object to find a catalyst which produces polymers having good particle morphology and a high molecular weight in a high yield.
It was found that this object can be achieved using bridged metallocene systems substituted in a certain manner in the ligand sphere.
The invention thus relates to a process for the prepara-tion of olefin polymers by polymerization or copolymeriz-ation of an olefin of the formula R°-CH~CH-Rb, wherein R~
and Rb are identical or different and are a hydrogen atom or a hydrocarbon radical having 1 to 14 C atoms, or R° and Rb, together with the atoms binding them, may form a ring, at a temperature of _60 to 200°C, at a pressure of 0.5 to 100 bar, in solution, in suspension ~r in the gas phase, in the presence of a catalyst which is eomposed of a metallocene as the transition metal compound and an aluminoxane of the formula (II) R1~ R14 R
~, , ~4 ( ) ~l - o A1 - o A1°~ II
R14 r p ~ R14 for the linear type andlor of the formula ZIT
ZO Rl~ (zTT) Al - o for the cyclic type, wherein, in the formulae (II) and (III), the radicals R14 may be identical or different and are a Cl-GB-alkyl group, a CB-C1~-aryl group or hydrogen, and p is an integer of from 2 to 50, wherein the metallocene is a compound of the formula I
It was found that this object can be achieved using bridged metallocene systems substituted in a certain manner in the ligand sphere.
The invention thus relates to a process for the prepara-tion of olefin polymers by polymerization or copolymeriz-ation of an olefin of the formula R°-CH~CH-Rb, wherein R~
and Rb are identical or different and are a hydrogen atom or a hydrocarbon radical having 1 to 14 C atoms, or R° and Rb, together with the atoms binding them, may form a ring, at a temperature of _60 to 200°C, at a pressure of 0.5 to 100 bar, in solution, in suspension ~r in the gas phase, in the presence of a catalyst which is eomposed of a metallocene as the transition metal compound and an aluminoxane of the formula (II) R1~ R14 R
~, , ~4 ( ) ~l - o A1 - o A1°~ II
R14 r p ~ R14 for the linear type andlor of the formula ZIT
ZO Rl~ (zTT) Al - o for the cyclic type, wherein, in the formulae (II) and (III), the radicals R14 may be identical or different and are a Cl-GB-alkyl group, a CB-C1~-aryl group or hydrogen, and p is an integer of from 2 to 50, wherein the metallocene is a compound of the formula I
d rR~R~ ) ~
fI) ~~~ M ° R6 R~
g'~ ~ 8 9 ~rdcR ~ )~
wherein Ml is a metal of group I~lb, ~1b or VIb of the Periodic 'able, Rl and R2 are identical or different and are a hydreagen atom, a Cl-Clo-alkyl group, a Cl-Coo-alkoxy group, a C6-Coo-aryl group, a Cs-Clo-arylo~y group, a Cz_~C~o alkenyl group, a C,-C4o-arylalkyl group, a C~-~C4o alkylaryl group, a Ce-Caa-arylalkenyl group or a halogen atom, Ro and 12'' are identical or different and are a hydrogen atom, a halogen atom, a Cz-Cl°-alkyl group wrhich may be halogen~~ted, a CB-C~o-aryl group, an -NFt2lo, ~~
-OSiR3~a, -SiR3~a or -PR~lo radical, wherein Rl° as a halogen atom, a Cl-Coo-al~y'1 group or a Cs-Clo--aryl grOllp, RS and RB are .~dentie:al or dif ferent and have the rn~araing stated fog R3 and R", with the proviso that R5 anal RB
are riot hydrogen, ~~~a~~
R7 i s R11 Rll Rll Rll R11 _ ~q2 _ , _ M2 _ Dq2 _ , _ 1v~2 ( CR213) ! ~ ~, ,C ~ ~2 R12 X12 R12 R12' X12 s o2 .. C _ . _ 0 _ M
=BR~11 =AlRll, -Ge-, -Sn-, -~-, -S-, =SC7, =SOZ, =NR11, =CO, =PRia or =~~p)Ry~
wherein R'I, R12 and R~~ are identical or different and are a hydro-qen atom, a halogen atom, a Cl-C~o-alkyl group, ~. ~
Clo-fluoroalkyl gxoup, a CB-Clo-aryl group, a Ce._Cxo-flu~roaa:yl groaxp, a Cl-Clo-alkoxy group, a ~'Z-Clo-alkenyl group, a C~-C4o-arylalkyl group, a Co~C,,o-1~D arylalk~nyl group or a C7-C4o-alkylaryl group, or R11 and R~Z or Rl~ and R~3, together with the atoms binding ahem, each form a ring, MZ is silicon, germanium or tin, Ra end R9 are identical or different and have the ~5 meaning stated for R11 and m and n are id~nt3cal ox dif~arent and are zero, 1 or 2, m plus n b~~ing zero, 1 or 2.
Alkyl is straight:-chain ox branohad alkyl. Halogen (halogenat~d) is fluorine, chlorine, bromine or 2d iodine, preferably fluorin~ or ohlorine.
The present invantion furthermore relates to the poly-olefins prepared by t:~e process described.
«
~ ~~~
The catalyst to be used for the process according to the invention is composed of an aluminoxane and a metallocene of the formula I
CR8R9 D ~
R~
.R
,, R ~ ~ 1 .7 R2r M R6 R
~1) R4 ~ 8 9 ' ( CR R ) n In the formula I, M1 is a metal of group IVb, Vb or VIb of the Periodic Table, for example titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, moly-bdentun ar tungsten, preferably zirconium, hafnium or titanium.
R~ and R~ are identical or different and are a hydrogen atom, a Cl-Clo~alkyl group, preferably a Cl-.C3-alkyl group, a Cl-C1°-al7cox~ grougs, preferably a C,-C~-~l~COxy group, a Cs-C~o-a~'Yl group, Preferably a Cs-C~-aryl graup, a C6-Clo-arYloxy group, preferably a Cs-C~-aryloxy group, a C2-Cl°-alk~nyl group, preferably a C~-Ca~alkenyl group, a C~-Cao-arYlalklrl group, Preferably a C~~Clo-arylalkyl group, a C~-C4o-alkylaryl . group, preferably a Cy~Cl2-alkylaryl group, a Cg-~~o-a~lalkenYl group, preferably a Cs-C12-arYlalkenyl group, or a halogan atom, preferably chlorine.
R3 and R4 are i~3entical or different and are a hydrogen atom, a halogen atom, preferably a fluorine, chlorine ar bramine atom, a Cl-C1°-alkyl groug, preferably a C1-C4-alkyl group, which may be halogenated, a Cs-Gl°-aryl group, pref~rably a Cs-Cs-aryl .group, an -NRxI°, -SRi°, ~OoS1R310, -SiR~~° or -PRa~° radical, wherein Rl° is a halogen atom, preferably a chloxine atom, or ~ Cl-Clo-alkYl group, ~~~~~.~.r _~_ preferably a C1-C3-alkyl group, or a CB-Cao-aryl groups preferably a C6-Ce-aryl group. R3 and R4 are particularly preferably hydrogen.
RS and R6 are identical or different, preferably identi-cal, and have the meanings described for R3 and. R4, with the proviso that RS and R6 may not be hydrogen. RS and Ro are preferably (C1-C4)-alkyl which may be halogenated, such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl or trifluoromethyl, in particular methyl.
R' i s M2 ' - M2 ' M2 - . - M2 - ( CR 1.3 ) _ . _ 0 _ M2 _ O _ Ra2 R12 ' R22 R12 2 ~ 12 ' R
~lI R11 _ C _ ' _ a . Nt2 _ =HR11, =A1R11, -Ge-, -Sn-, -0-, -S-, =S0, =SO2, =NRlx, =C0, =PRl~ or =P ( 0 ) Rll, wherein Rli, Rl2 and Rl~ are identical or different and are a hydrogen atom, a halogen atom, a C1-Clo°alkyl group, preferably a C1-C4-alkyl group, ~.n par-titular a methyl group, a Cl-Clo-fluoroalkyl group, preferably a CF3 group, a CB-Clo-aryl group, preferably a C6-C$--aryl group, a C6-Clo-fluoro~ryl group, preferably a pentafluarophenyl groug, a Cl-Clo-alko~cy group, preferably a Ci-~C~-alkoxy group, in particular a methoxy group, a C~-Coo-alkenyl group, Preferably a C2-C~-alkenyl group, a C7 C4o-arylalkyl group, preferably a C~-Cio-axylalkyl group, a Ce-Coo-arylalkenyl group, preferably a C8-C12-axylalkenyl group, or a C~-C4o-alkylaryl group, preferably a C~-Clz alkylaryl group, or Rll and R'~Z or Rll and RI3, together with the atoms binding them, each form a ring.
M2 is silicon, germanium or tin, preferably silicon or germanium.
R' is preferably =CR1''Rlz~ aSiRllRiz' =GeRllRxz, -C~,, .-g_, =SC r =PRm ox _-P ~ O ) Rm .
Re and R9 are identical or different and hare the meaning stated for Rli.
m tend n are identical or different and are zero, I or 2, preferably zero or 1, m plus n being zero, 1 or 2, preferably zero or 1.
The particularly preferred metallocenes are thus the compounds of the formulae A, B and C
R5 ~.
RgR9C i R1 ~,--' M1\R2 (A) . R11\Si M1~R2 (B) .
R1 1 g12C i R12/ ~"~R
,".. R6 ~ R~
i I
i R~ 1~ ' ,/R1 R 12s'C' ~''d ~ 2 ( C ) o ~ R
in which Ml is Zr or Hf, R1 and RZ are methyl or chlorine, RS and Rs are methyl, ethyl or trifluoromethyl and R°, R~, Rll and Rxa have the abovementioned meanings, in particular the compounds T mentioned in the Illustrative Rxamples.
The chiral metallocenes are used as a racemate for the preparation of highly isotactic poly--1-olefins. However, it is also possible to use the pure R or 8 form. Opti-cally active polymers can be prepared with these pure stereoisomeric forms. However, the meso form of the metallocenes should be separated off, since the center which is active in polymerization (the metal atom) is no longer chiral in these compounds owing to mirror symmetry at the central metal and therefore cannot produce the highly isotactic polymer. If the meso form is not sepaxated off, an atactic polymer is formed in addition to isotactic polymers . ~'or certain applica.~tions - fox example flexible moldings - this may be quite desirable.
The separation of stereoisomers is known in principle.
2p The metallocenes described above can be prepared accord-ing to the following reaction schemes HZRc + ButylLi -~ HRCLi X_(CRBRg)m-R~ (CR8R9) X
H2Rd + RutylLi --~----y~ HRdLi HRC- ( CRBRg ) m- R~~ ( CRBR~ ) n RAH 2 8u~tyl L
LiRC-(CRBRg)m-R~-.(CR8R9)ri-RdLi M~C1 (RBRgC)m _ Rc (R8R9C)m _ Rc ~, C1 ~ r R1 R' Mle, R~ R7 M2\
Cl ~ Cl (R8R9C)n _ Rd (R8R9C)n _ Rd _, (R~R~C)m _ Rc R2Li D R7 MZr R~
(RBR~C)n - Rd X = C1, Br, I, O-Tosyl; I32R° --x H2R~ ~ ~ 6 The preparation processes are known from the literature;
cf. Journal of Organom~t~113.c Chem. 288 (1985) 63.-67, EP-A 320 762 and the Illustrative Examples.
According to the invention, the cocatalyst used is an 5 aluminoxane of the. formula (Ix) R14' R1~ Rlg .~ pal _ o Al _ C ~l'' ( II ) Rig r 'R~~
for this linear type and/or of the formula (III) O ---- 111 p ( I I I
for the cyclic fiype, wherein, in the formu~,ae (II) and (III), the radicals Rz~ may be identiaal or different and are a Cl-~Ce-a7.ky1 group, a CB-C~~-ar~rl group or hydrogen, arid p is an integer of from 2 to 50, preferably from ~.0 tp 35.
The radicals Rl4 ire preferably identical and are methyl, isobutyl, phenyl ar benzyl, particularly preferably methyl.
If the radicals R14 are different, they are preferably methyl and hydrogen or alternatively methyl and isobutyl, hydrogen or isobutyl preferably being present in an amount of 0.01-40~ (number of radicals R1''j.
The aluminaxane can be prepared in various ways by known processes. One of the methods comprises, for example, reacting an aluminum-hydrocarbon compound and/or a hydridoaluminum-hydrocarbon compound with water (gaseous, solid, liquid or bound - fox example as water of crystal-lization) in an inert solvent (such as, for example, toluene). ~'ar the preparation of an aluminoxane having different alkyl groups R14, two different aluminum~tri-alkyls (A1R3 + A1R~3) are reacted with water, depending an the desired composition (cf. S. Pasynkiewi.cz, Polyhedron 9 (1990) 429 and EP-A 302 424).
The exact structure of the aluminoxanes IT and III is not known.
Regardless of the method of preparation, the common feature of all alumi.nox~ne solutions is a chancing content of unconverted aluminum starting compound, which is present in free form ar as an adduct.
It is possible to preactivate the metallacene before use a:n the polymerization reaction with an aluminoxane of the formula (LI) and/or (III). This substantially increases the polymer3:zatian aotivity and improves the particle morphology.
The preactivatian of the transition metal compound is carried cut in solution. The me~tallocene is preferably dissolved in a solution of tae aluminoxane in an inert hydrocarbon. A suitable inert hydrocarbo.l is an aliphat-ic or aromatic hydrocarbon. Toluene is preferably used.
The concentration of the aluminoxane in the solution is in the range from about 1% by weight to the saturation limit, preferably from 5 to 30% by weight, based in each case on the total solution. The metallocene may be used in the same concentration, but is preferably employed in an amount of 10-" - 1 mol per mol of aluminoxane. The preactivation time is 5 minutes to 60 hours, preferably from 5 to 60 minutes. It is carried out at a temperature of -78°C to 100°C, preferably 0 to 70°C.
The metallocene can also be prepolymerized or applied to a support. For prepolymerization, the olefin used in the polymerization, or one of the olefins used in the polymerization, is preferably used.
Suitable supports are, for example, silica gels, aluminas, solid aluminoxane or other inorganic supports. Another suitable support is a polyolefin powder in finely divided form.
A further possible embodiment of the process according to the invention comprises using a salt-like compound of the formula R=NH,_xHR', or of the formula R3PHBR', as a cocatal-yst, instead of or in addition to an aluminoxane. In the formulae, x is 1, 2 or 3, the radicals R are identical or different and are alkyl or aryl and R' is aryl which may also be fluorinated or partially fluorinated. In this case, the catalyst is composed of the reaction product of a metallocene With one of the stated compounds (cf.
EP-A 277 004 and the Preparation Examples C and F).
To remove catalyst poisons present in the olefin, purifi-cation with an aluminumalkyl, for example AlMe3 or AlEt3, is advzntageous. This purification may be carried out in the polymerization system itself, or the olefin is brought into contact with the A1 compound prior to addition to the polymerization system and is then separated off again.
The polymerization or copolymerization is carried out in c~ ~ 3 .~ ~ .~ ~
a known manner in solution, in suspension or in the gas phase, continuously or batchwise, in one or more stages, at a temperature of 0 to 150°C, preferably 30 to 80°C.
olefins of the formula R~-CH=CH-Rb are polymerized or copolymerized. In this formula, R° and R~ are identical or different and are a hydrogen stem or an alkyl radical having Z to 14 C atoms. However, Ra and Rb, together with the C atoms binding them, may also farm a ring. Examples of such olefins are ethylene, propylene, ZO 1-butane, 1-hexane, 4-methyl-1-pentane, 3-octane, norbornene or narbornadiene. In particular, propylene and ethylene are polymerized.
If required, hydrogen is added as a molecular weight regulator. The fatal pressure in the polymerization system is 0.5 to 100 bar. Polymerization in the indus-trially particularly interesting pressure range from 5 to 64 bar is preferred.
The metallocene is used here in a concentration, based on the transition metal, of 10-3 to 10-e, preferably 10~° to 20-', mol of transition metal per dm3 of solvent ar per dm3 of reactor volume. The aluminoxane a.s used in a concent-ration of 3.05 to 10-1 mal, preferably 10"° to ~.O~a mol, per dm3 of solvent or per dm3 of reactor volume. In prin-ciple, however, higher concent~atians are also possible.
Tf the polymerization is carried out as a suspension or solution polymerization, an inert solvent conventionally used far the Ziegler low pressure process is employed.
For example, the r~actian is carried out in an aligha~tic or cyclaaliphatic hydrocarbono butane, pentane, hexame, heptane, isooctane, cyclohexane and methylcyclohexane may be mentioned as examples of these.
A gasoline or hydrogenated diesel ail fracti.an may furthermore be used. Toluene can also b~ used., Polymer-ization is preferably carried out in the liquid monomer.
- 1~ _ F ~~~~ f'3 If inert solvents are used, the monomers are metered in as a gas or liquid.
The polymerization can be carried out far any desired time, since the catalyst system to be used according to the invention shows only a slight time-dependent decrease in the polymerization activity.
Tn the process according to the invention, the metallo-cenes described produce polymers having a high molecular weight, high stereospecificity and good particle morphol-.
ogy in the industrially interesting temperature range between 30 and S0°C.
In particular, the zirconocenes according to the inven-tion provide a molecular weight range which, in the prior art, was provided only by the hafnocenes. However, these IS have the disadvantage of only low polyrn~rization activity and very high catalyst costs, and the polymers prepared therewith had a poor powder morphology.
'the Examples which follow ar~ intended to illustrate the invention in more detail.
V.~1 - Viscosity number in cm3/g M" = Weight avexage molecular Determined by weight in g/mol gel permeation M%/Mn = Molecular weight dispersity chromatography m.p. _~ Melting point determined DSC (20C/min by heating/cooling rate) TI - Isotactic index (TT = mm+1/2 determined mr) by 13'voNMR SpACtrOBCOpy - Polymer bulk density in g/dm3 .
.MFI (23 0/5) = M~lt.flaw index, measuredaccording to DINV53,735, in g/10 min Synthesis of the metallocenes used in the Exampless ~7~~~'i - 15 - r Starting substances:
The preparation of the indenyls HZR° and HZRd used as starting compounds is carried out according to or analog-ously to:
J. Org. Chem., 49 (1984) 4226-4237, J. Chem. Soc., Perkin 11,-1981, 403-408, J. Am. Chem. Soc., 106 (1984) 6702, J.
Am. Chem. Soc., 65 (1943) 567, J. Med. Chem., 30 (1987) 1303-1308, Chem. Her. 85 (1952) 78-85.
The preparation of the chalets ligands I0 LiR°- ( CR~R9 ) ~-R'- ( CRBRa )n°F2'~Li iS described in print iple in Bull. Sot. Chim., 1967, 2954, J. Am. Chem. Sot., 1I2 (1990) 2030-2031, ibid. 110 (1988) 6255-6256, ibid. 109 ( 1987 ) , 6544-6545, J. Organomet. chew. , 322 ( 1987 ) 65-70, New. J. Chem. 14 (1990} 499-503.
I5 I) Synthesis of 2-M~-indene 110.45 g (0.836 mol) of 2-indanone were dissolved in 500 cm3 of diethyl ether, and 290 cm3 of 3 N (0.87 mol) ethereal methylgrignard solution were added dropwise so that gentle refluxing occurred. After boiling for 2 20 hours with a gentle refluxing, the mixture was poured onto an ice/hydrochloric acid mixture and adjusted to pH 2-3 with ammonium chloride. The organic phas~ was separated off, washed with NaHC03 and sodium chloride solution and~dried. 98 g of crude product (Z-hydroxy-2-25 methyl3,ndane) were obtained, which was not further purified.
This pxoduct was dissolved in 500 cm3 of toluene and heated with 3 g of p-toluenesulfonic acid under a water separator until the elimination of water was complete, 30 the mixture was evaporated doom, the residue was taken up in dichloromethane, the solution was filtered over silica gel and the filtrate was disti.lle~i in vacuo ( 80°C/10 mbar) .
Yield: 28.49 g (0.22 mol-26~).
r~~~~~3~ ~_O
The synthesis of this compound is also described ins C.F. Koelsch, P.R. Johnson, J. l~rn. Chem. Soc., 65 (1943) 56?-573 Iz} Synthesis of (2-Me-Indene)ZSiMe2 13 g (100 mol} of 2-Me-indene were dissolved in 400 cm3 of diethyl ether, and 62.5 cm3 of 1.6 N (100 mmol) of n-butyllithium/n-hexane solution were added dropwise in the course of 1 hour while cooling with ice, after which stirring was continued for 1 hour at "35°C.
1O 6.1 cm3 (50 mmol) of dimethyldichlorosilane in 50 cm3 of EtzO were initially ta3cen, and the lithio salt solution was added dropwise in the course of 5 hours at 0°C, stirring was carried out overnight at raom temperature and the mixture was allowed to stand over the weekend.
The solid which had settled out was filtered off and the filtrate was evaporated to dryness. After extraction with small portions of n-hexane, filtration eras carried out and the filtrate was evaporated down. 5.7 g (18.00 mmol) of white crystals were obtained. The mother liquor was evaporated down and then purified by column chromatography ( n-hexane/HZCC12 9 . 1 parts by volume ) , 2.5 g (7.9 mmol - 52~) of product being obtained (as an isomer mixture).
r~ (Si02; n-hexane/HZCC12 9 r 1 parts by volume) = 0.37 The lH-NMR spectrum shows the signals to be expected fox an isomer mixture, in shift and integration ratio.
III ) Synthesis of ( 2-Me-Ind) zCH2CH2 3 g (23 mmol) of 2-Me-indene were dissolved in 50 cm~ of THF, 14.4 cm3 of 1.6 N (23.04 mmol) n-butyllithium/
n-hexane solution were added dropwise and stirring was then carried out . for 1 hour at 65°C. Thereafter, 1 ml ~~~aa _ 17 _ (11.5 mmol) of 1,2-dibromoethane was added at -78°C, and the mixture was allowed to warm to room temperature and was stirred for 5 hours. It was evaporated down and then purified by column chromatography (SiOz; n-hexane/HZCC12 9 . 1 parts by volume).
The product-containing fractions were combined and evaporated down, the residue was taken up in dry ether, the solution was dried over .MgS04 and filtered and the solvent was stripped off.
Yield: 1.6 g (5.59 mmol - 49~) of isomer mixture rF ( Si02; n-hexane/HzGClz 9 . 1 parts by volume ) = 0 , 46 The 1H-NMR spectrum meets the expectation for an isomer mixture in signal shift and integration.
A) Synthesis of rac-dimethylsilyl(2-Me-.1-indenyl)Z-zircanium dichloride 1.68 g (5.31 mmol) of the chalets ligand dimethylsilyl(2-methylindene)z were added to 50 cma of THF, and 6.63 cm3 of a 1.6 N (10.61 mmol) n-Bu~i/n-hexane solution were added dropwise. The addition was carried out at ambient temperature in the course of 0.5 hour. The mixture was stirred for 2 hours at about 35°C, after which the solvent was stripped off in vacuo, the residue was stirred with n-pentane and the solid was filtered off and dried.
The dilithio salt thus obtained was added at -78°C to a suspension of 1.24 g {5.32 mmol) of ZrCl4 in 50 cm3 of CHzCl2 and the mixture was stirred for 3 hours at this temperature. After warming up to room temperature overnight, the mixture was evaporated down. The zH-N.MR
spectrum indicated a rac-meso mixture in addition to the presence of a little ZrCl4(thf)2. After stirring with n-pentane and drying, t)ie solid, yellow residue was suspen-ded in THF, filtered off and investigated by NCR spec-troscopy. These three operations were repeated several s'~
!.n ,~ eJ' m_ ~,~
times; finally 0.35 g (0.73 mmol-1~~) of product was obtained, in which, according to 1H-NMR, the rac form had been concentrated to more than 17 a 1.
The compound gave a correct elemental analysis and the following NMR signals (CDC13, 100 MHz)a 6 = 1.25 (s, 6H, Si-Me); 2.18 (s, 6H, 2-Me), S.8 (s, 2H, 3~-H-Ind); 6.92-7.'75 (m, 8H, ~-7-H-Ind).
B) Synthesis of rac-damethylsilyl(2-Me-1-iridenyl)2-zirconiumdimethyl 1.3 cm3 of a 1.6 N (2.08 rnmol) ethereal Me7Gi solution were added dropwise to 0.29 g (0.58 mmol) of rac-di.methylsilyl (2-Me-1-iridenyl)ZZirconium dichloride in 40 cm3 of EtzO
at -50°C, and stirring was carried out for 2 hours at -10°C. After exchanging the solvent for n-pentane, ~~tir-ring was continued for a further 1.5 hours at room temperature and the filtered residue was sublimed in vacuo. 0.19 g (0.44 mmol-81~) of sublimate with a correct elemental analysis was obtained.
C) Reaction of rac-dimethylsilyl(2-Me-1-indenyl)Z-2 0 zirconiumdimethyl with [ Bu3NH ~ [ B ( CsHS ) a ]
0.17 g (0.39 mmol) of rac-dimethylsilyl(2-Me-1-indenyl)2-zireoniumdimethyl was added at 0°C to 0.18 g (0.36 mmol) of L Bu3NH ] f B ( C6H5 ) a 7 in 25 cm3 of toluene . The mixture was warmed up to.ambient temperature while stirring for one hour. The deeply coloured mixture was then evaporated to dryness.
An aliquot part of the reaction mixture was used for 'the polymerization.
D) Synthesis of rac-ethylene(2-Me-1-indenyl)ZZirconium dichloride 14.2 cm3 of 2.5 N (35.4 mmol) n-BuLi/n-hexane Solution were added dropwise to 5.07 g (17.7 mmol) of the ligand ethylene(2-methylindene)2 in 200 cm3 of THF at room temperature in the course of 1 hour, and stirring was then carried out for 3 hours at about 50°C. A precipitate which was formed in the meantime goes into solution again. The solution was allowed to stand overnight.
fI) ~~~ M ° R6 R~
g'~ ~ 8 9 ~rdcR ~ )~
wherein Ml is a metal of group I~lb, ~1b or VIb of the Periodic 'able, Rl and R2 are identical or different and are a hydreagen atom, a Cl-Clo-alkyl group, a Cl-Coo-alkoxy group, a C6-Coo-aryl group, a Cs-Clo-arylo~y group, a Cz_~C~o alkenyl group, a C,-C4o-arylalkyl group, a C~-~C4o alkylaryl group, a Ce-Caa-arylalkenyl group or a halogen atom, Ro and 12'' are identical or different and are a hydrogen atom, a halogen atom, a Cz-Cl°-alkyl group wrhich may be halogen~~ted, a CB-C~o-aryl group, an -NFt2lo, ~~
-OSiR3~a, -SiR3~a or -PR~lo radical, wherein Rl° as a halogen atom, a Cl-Coo-al~y'1 group or a Cs-Clo--aryl grOllp, RS and RB are .~dentie:al or dif ferent and have the rn~araing stated fog R3 and R", with the proviso that R5 anal RB
are riot hydrogen, ~~~a~~
R7 i s R11 Rll Rll Rll R11 _ ~q2 _ , _ M2 _ Dq2 _ , _ 1v~2 ( CR213) ! ~ ~, ,C ~ ~2 R12 X12 R12 R12' X12 s o2 .. C _ . _ 0 _ M
=BR~11 =AlRll, -Ge-, -Sn-, -~-, -S-, =SC7, =SOZ, =NR11, =CO, =PRia or =~~p)Ry~
wherein R'I, R12 and R~~ are identical or different and are a hydro-qen atom, a halogen atom, a Cl-C~o-alkyl group, ~. ~
Clo-fluoroalkyl gxoup, a CB-Clo-aryl group, a Ce._Cxo-flu~roaa:yl groaxp, a Cl-Clo-alkoxy group, a ~'Z-Clo-alkenyl group, a C~-C4o-arylalkyl group, a Co~C,,o-1~D arylalk~nyl group or a C7-C4o-alkylaryl group, or R11 and R~Z or Rl~ and R~3, together with the atoms binding ahem, each form a ring, MZ is silicon, germanium or tin, Ra end R9 are identical or different and have the ~5 meaning stated for R11 and m and n are id~nt3cal ox dif~arent and are zero, 1 or 2, m plus n b~~ing zero, 1 or 2.
Alkyl is straight:-chain ox branohad alkyl. Halogen (halogenat~d) is fluorine, chlorine, bromine or 2d iodine, preferably fluorin~ or ohlorine.
The present invantion furthermore relates to the poly-olefins prepared by t:~e process described.
«
~ ~~~
The catalyst to be used for the process according to the invention is composed of an aluminoxane and a metallocene of the formula I
CR8R9 D ~
R~
.R
,, R ~ ~ 1 .7 R2r M R6 R
~1) R4 ~ 8 9 ' ( CR R ) n In the formula I, M1 is a metal of group IVb, Vb or VIb of the Periodic Table, for example titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, moly-bdentun ar tungsten, preferably zirconium, hafnium or titanium.
R~ and R~ are identical or different and are a hydrogen atom, a Cl-Clo~alkyl group, preferably a Cl-.C3-alkyl group, a Cl-C1°-al7cox~ grougs, preferably a C,-C~-~l~COxy group, a Cs-C~o-a~'Yl group, Preferably a Cs-C~-aryl graup, a C6-Clo-arYloxy group, preferably a Cs-C~-aryloxy group, a C2-Cl°-alk~nyl group, preferably a C~-Ca~alkenyl group, a C~-Cao-arYlalklrl group, Preferably a C~~Clo-arylalkyl group, a C~-C4o-alkylaryl . group, preferably a Cy~Cl2-alkylaryl group, a Cg-~~o-a~lalkenYl group, preferably a Cs-C12-arYlalkenyl group, or a halogan atom, preferably chlorine.
R3 and R4 are i~3entical or different and are a hydrogen atom, a halogen atom, preferably a fluorine, chlorine ar bramine atom, a Cl-C1°-alkyl groug, preferably a C1-C4-alkyl group, which may be halogenated, a Cs-Gl°-aryl group, pref~rably a Cs-Cs-aryl .group, an -NRxI°, -SRi°, ~OoS1R310, -SiR~~° or -PRa~° radical, wherein Rl° is a halogen atom, preferably a chloxine atom, or ~ Cl-Clo-alkYl group, ~~~~~.~.r _~_ preferably a C1-C3-alkyl group, or a CB-Cao-aryl groups preferably a C6-Ce-aryl group. R3 and R4 are particularly preferably hydrogen.
RS and R6 are identical or different, preferably identi-cal, and have the meanings described for R3 and. R4, with the proviso that RS and R6 may not be hydrogen. RS and Ro are preferably (C1-C4)-alkyl which may be halogenated, such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl or trifluoromethyl, in particular methyl.
R' i s M2 ' - M2 ' M2 - . - M2 - ( CR 1.3 ) _ . _ 0 _ M2 _ O _ Ra2 R12 ' R22 R12 2 ~ 12 ' R
~lI R11 _ C _ ' _ a . Nt2 _ =HR11, =A1R11, -Ge-, -Sn-, -0-, -S-, =S0, =SO2, =NRlx, =C0, =PRl~ or =P ( 0 ) Rll, wherein Rli, Rl2 and Rl~ are identical or different and are a hydrogen atom, a halogen atom, a C1-Clo°alkyl group, preferably a C1-C4-alkyl group, ~.n par-titular a methyl group, a Cl-Clo-fluoroalkyl group, preferably a CF3 group, a CB-Clo-aryl group, preferably a C6-C$--aryl group, a C6-Clo-fluoro~ryl group, preferably a pentafluarophenyl groug, a Cl-Clo-alko~cy group, preferably a Ci-~C~-alkoxy group, in particular a methoxy group, a C~-Coo-alkenyl group, Preferably a C2-C~-alkenyl group, a C7 C4o-arylalkyl group, preferably a C~-Cio-axylalkyl group, a Ce-Coo-arylalkenyl group, preferably a C8-C12-axylalkenyl group, or a C~-C4o-alkylaryl group, preferably a C~-Clz alkylaryl group, or Rll and R'~Z or Rll and RI3, together with the atoms binding them, each form a ring.
M2 is silicon, germanium or tin, preferably silicon or germanium.
R' is preferably =CR1''Rlz~ aSiRllRiz' =GeRllRxz, -C~,, .-g_, =SC r =PRm ox _-P ~ O ) Rm .
Re and R9 are identical or different and hare the meaning stated for Rli.
m tend n are identical or different and are zero, I or 2, preferably zero or 1, m plus n being zero, 1 or 2, preferably zero or 1.
The particularly preferred metallocenes are thus the compounds of the formulae A, B and C
R5 ~.
RgR9C i R1 ~,--' M1\R2 (A) . R11\Si M1~R2 (B) .
R1 1 g12C i R12/ ~"~R
,".. R6 ~ R~
i I
i R~ 1~ ' ,/R1 R 12s'C' ~''d ~ 2 ( C ) o ~ R
in which Ml is Zr or Hf, R1 and RZ are methyl or chlorine, RS and Rs are methyl, ethyl or trifluoromethyl and R°, R~, Rll and Rxa have the abovementioned meanings, in particular the compounds T mentioned in the Illustrative Rxamples.
The chiral metallocenes are used as a racemate for the preparation of highly isotactic poly--1-olefins. However, it is also possible to use the pure R or 8 form. Opti-cally active polymers can be prepared with these pure stereoisomeric forms. However, the meso form of the metallocenes should be separated off, since the center which is active in polymerization (the metal atom) is no longer chiral in these compounds owing to mirror symmetry at the central metal and therefore cannot produce the highly isotactic polymer. If the meso form is not sepaxated off, an atactic polymer is formed in addition to isotactic polymers . ~'or certain applica.~tions - fox example flexible moldings - this may be quite desirable.
The separation of stereoisomers is known in principle.
2p The metallocenes described above can be prepared accord-ing to the following reaction schemes HZRc + ButylLi -~ HRCLi X_(CRBRg)m-R~ (CR8R9) X
H2Rd + RutylLi --~----y~ HRdLi HRC- ( CRBRg ) m- R~~ ( CRBR~ ) n RAH 2 8u~tyl L
LiRC-(CRBRg)m-R~-.(CR8R9)ri-RdLi M~C1 (RBRgC)m _ Rc (R8R9C)m _ Rc ~, C1 ~ r R1 R' Mle, R~ R7 M2\
Cl ~ Cl (R8R9C)n _ Rd (R8R9C)n _ Rd _, (R~R~C)m _ Rc R2Li D R7 MZr R~
(RBR~C)n - Rd X = C1, Br, I, O-Tosyl; I32R° --x H2R~ ~ ~ 6 The preparation processes are known from the literature;
cf. Journal of Organom~t~113.c Chem. 288 (1985) 63.-67, EP-A 320 762 and the Illustrative Examples.
According to the invention, the cocatalyst used is an 5 aluminoxane of the. formula (Ix) R14' R1~ Rlg .~ pal _ o Al _ C ~l'' ( II ) Rig r 'R~~
for this linear type and/or of the formula (III) O ---- 111 p ( I I I
for the cyclic fiype, wherein, in the formu~,ae (II) and (III), the radicals Rz~ may be identiaal or different and are a Cl-~Ce-a7.ky1 group, a CB-C~~-ar~rl group or hydrogen, arid p is an integer of from 2 to 50, preferably from ~.0 tp 35.
The radicals Rl4 ire preferably identical and are methyl, isobutyl, phenyl ar benzyl, particularly preferably methyl.
If the radicals R14 are different, they are preferably methyl and hydrogen or alternatively methyl and isobutyl, hydrogen or isobutyl preferably being present in an amount of 0.01-40~ (number of radicals R1''j.
The aluminaxane can be prepared in various ways by known processes. One of the methods comprises, for example, reacting an aluminum-hydrocarbon compound and/or a hydridoaluminum-hydrocarbon compound with water (gaseous, solid, liquid or bound - fox example as water of crystal-lization) in an inert solvent (such as, for example, toluene). ~'ar the preparation of an aluminoxane having different alkyl groups R14, two different aluminum~tri-alkyls (A1R3 + A1R~3) are reacted with water, depending an the desired composition (cf. S. Pasynkiewi.cz, Polyhedron 9 (1990) 429 and EP-A 302 424).
The exact structure of the aluminoxanes IT and III is not known.
Regardless of the method of preparation, the common feature of all alumi.nox~ne solutions is a chancing content of unconverted aluminum starting compound, which is present in free form ar as an adduct.
It is possible to preactivate the metallacene before use a:n the polymerization reaction with an aluminoxane of the formula (LI) and/or (III). This substantially increases the polymer3:zatian aotivity and improves the particle morphology.
The preactivatian of the transition metal compound is carried cut in solution. The me~tallocene is preferably dissolved in a solution of tae aluminoxane in an inert hydrocarbon. A suitable inert hydrocarbo.l is an aliphat-ic or aromatic hydrocarbon. Toluene is preferably used.
The concentration of the aluminoxane in the solution is in the range from about 1% by weight to the saturation limit, preferably from 5 to 30% by weight, based in each case on the total solution. The metallocene may be used in the same concentration, but is preferably employed in an amount of 10-" - 1 mol per mol of aluminoxane. The preactivation time is 5 minutes to 60 hours, preferably from 5 to 60 minutes. It is carried out at a temperature of -78°C to 100°C, preferably 0 to 70°C.
The metallocene can also be prepolymerized or applied to a support. For prepolymerization, the olefin used in the polymerization, or one of the olefins used in the polymerization, is preferably used.
Suitable supports are, for example, silica gels, aluminas, solid aluminoxane or other inorganic supports. Another suitable support is a polyolefin powder in finely divided form.
A further possible embodiment of the process according to the invention comprises using a salt-like compound of the formula R=NH,_xHR', or of the formula R3PHBR', as a cocatal-yst, instead of or in addition to an aluminoxane. In the formulae, x is 1, 2 or 3, the radicals R are identical or different and are alkyl or aryl and R' is aryl which may also be fluorinated or partially fluorinated. In this case, the catalyst is composed of the reaction product of a metallocene With one of the stated compounds (cf.
EP-A 277 004 and the Preparation Examples C and F).
To remove catalyst poisons present in the olefin, purifi-cation with an aluminumalkyl, for example AlMe3 or AlEt3, is advzntageous. This purification may be carried out in the polymerization system itself, or the olefin is brought into contact with the A1 compound prior to addition to the polymerization system and is then separated off again.
The polymerization or copolymerization is carried out in c~ ~ 3 .~ ~ .~ ~
a known manner in solution, in suspension or in the gas phase, continuously or batchwise, in one or more stages, at a temperature of 0 to 150°C, preferably 30 to 80°C.
olefins of the formula R~-CH=CH-Rb are polymerized or copolymerized. In this formula, R° and R~ are identical or different and are a hydrogen stem or an alkyl radical having Z to 14 C atoms. However, Ra and Rb, together with the C atoms binding them, may also farm a ring. Examples of such olefins are ethylene, propylene, ZO 1-butane, 1-hexane, 4-methyl-1-pentane, 3-octane, norbornene or narbornadiene. In particular, propylene and ethylene are polymerized.
If required, hydrogen is added as a molecular weight regulator. The fatal pressure in the polymerization system is 0.5 to 100 bar. Polymerization in the indus-trially particularly interesting pressure range from 5 to 64 bar is preferred.
The metallocene is used here in a concentration, based on the transition metal, of 10-3 to 10-e, preferably 10~° to 20-', mol of transition metal per dm3 of solvent ar per dm3 of reactor volume. The aluminoxane a.s used in a concent-ration of 3.05 to 10-1 mal, preferably 10"° to ~.O~a mol, per dm3 of solvent or per dm3 of reactor volume. In prin-ciple, however, higher concent~atians are also possible.
Tf the polymerization is carried out as a suspension or solution polymerization, an inert solvent conventionally used far the Ziegler low pressure process is employed.
For example, the r~actian is carried out in an aligha~tic or cyclaaliphatic hydrocarbono butane, pentane, hexame, heptane, isooctane, cyclohexane and methylcyclohexane may be mentioned as examples of these.
A gasoline or hydrogenated diesel ail fracti.an may furthermore be used. Toluene can also b~ used., Polymer-ization is preferably carried out in the liquid monomer.
- 1~ _ F ~~~~ f'3 If inert solvents are used, the monomers are metered in as a gas or liquid.
The polymerization can be carried out far any desired time, since the catalyst system to be used according to the invention shows only a slight time-dependent decrease in the polymerization activity.
Tn the process according to the invention, the metallo-cenes described produce polymers having a high molecular weight, high stereospecificity and good particle morphol-.
ogy in the industrially interesting temperature range between 30 and S0°C.
In particular, the zirconocenes according to the inven-tion provide a molecular weight range which, in the prior art, was provided only by the hafnocenes. However, these IS have the disadvantage of only low polyrn~rization activity and very high catalyst costs, and the polymers prepared therewith had a poor powder morphology.
'the Examples which follow ar~ intended to illustrate the invention in more detail.
V.~1 - Viscosity number in cm3/g M" = Weight avexage molecular Determined by weight in g/mol gel permeation M%/Mn = Molecular weight dispersity chromatography m.p. _~ Melting point determined DSC (20C/min by heating/cooling rate) TI - Isotactic index (TT = mm+1/2 determined mr) by 13'voNMR SpACtrOBCOpy - Polymer bulk density in g/dm3 .
.MFI (23 0/5) = M~lt.flaw index, measuredaccording to DINV53,735, in g/10 min Synthesis of the metallocenes used in the Exampless ~7~~~'i - 15 - r Starting substances:
The preparation of the indenyls HZR° and HZRd used as starting compounds is carried out according to or analog-ously to:
J. Org. Chem., 49 (1984) 4226-4237, J. Chem. Soc., Perkin 11,-1981, 403-408, J. Am. Chem. Soc., 106 (1984) 6702, J.
Am. Chem. Soc., 65 (1943) 567, J. Med. Chem., 30 (1987) 1303-1308, Chem. Her. 85 (1952) 78-85.
The preparation of the chalets ligands I0 LiR°- ( CR~R9 ) ~-R'- ( CRBRa )n°F2'~Li iS described in print iple in Bull. Sot. Chim., 1967, 2954, J. Am. Chem. Sot., 1I2 (1990) 2030-2031, ibid. 110 (1988) 6255-6256, ibid. 109 ( 1987 ) , 6544-6545, J. Organomet. chew. , 322 ( 1987 ) 65-70, New. J. Chem. 14 (1990} 499-503.
I5 I) Synthesis of 2-M~-indene 110.45 g (0.836 mol) of 2-indanone were dissolved in 500 cm3 of diethyl ether, and 290 cm3 of 3 N (0.87 mol) ethereal methylgrignard solution were added dropwise so that gentle refluxing occurred. After boiling for 2 20 hours with a gentle refluxing, the mixture was poured onto an ice/hydrochloric acid mixture and adjusted to pH 2-3 with ammonium chloride. The organic phas~ was separated off, washed with NaHC03 and sodium chloride solution and~dried. 98 g of crude product (Z-hydroxy-2-25 methyl3,ndane) were obtained, which was not further purified.
This pxoduct was dissolved in 500 cm3 of toluene and heated with 3 g of p-toluenesulfonic acid under a water separator until the elimination of water was complete, 30 the mixture was evaporated doom, the residue was taken up in dichloromethane, the solution was filtered over silica gel and the filtrate was disti.lle~i in vacuo ( 80°C/10 mbar) .
Yield: 28.49 g (0.22 mol-26~).
r~~~~~3~ ~_O
The synthesis of this compound is also described ins C.F. Koelsch, P.R. Johnson, J. l~rn. Chem. Soc., 65 (1943) 56?-573 Iz} Synthesis of (2-Me-Indene)ZSiMe2 13 g (100 mol} of 2-Me-indene were dissolved in 400 cm3 of diethyl ether, and 62.5 cm3 of 1.6 N (100 mmol) of n-butyllithium/n-hexane solution were added dropwise in the course of 1 hour while cooling with ice, after which stirring was continued for 1 hour at "35°C.
1O 6.1 cm3 (50 mmol) of dimethyldichlorosilane in 50 cm3 of EtzO were initially ta3cen, and the lithio salt solution was added dropwise in the course of 5 hours at 0°C, stirring was carried out overnight at raom temperature and the mixture was allowed to stand over the weekend.
The solid which had settled out was filtered off and the filtrate was evaporated to dryness. After extraction with small portions of n-hexane, filtration eras carried out and the filtrate was evaporated down. 5.7 g (18.00 mmol) of white crystals were obtained. The mother liquor was evaporated down and then purified by column chromatography ( n-hexane/HZCC12 9 . 1 parts by volume ) , 2.5 g (7.9 mmol - 52~) of product being obtained (as an isomer mixture).
r~ (Si02; n-hexane/HZCC12 9 r 1 parts by volume) = 0.37 The lH-NMR spectrum shows the signals to be expected fox an isomer mixture, in shift and integration ratio.
III ) Synthesis of ( 2-Me-Ind) zCH2CH2 3 g (23 mmol) of 2-Me-indene were dissolved in 50 cm~ of THF, 14.4 cm3 of 1.6 N (23.04 mmol) n-butyllithium/
n-hexane solution were added dropwise and stirring was then carried out . for 1 hour at 65°C. Thereafter, 1 ml ~~~aa _ 17 _ (11.5 mmol) of 1,2-dibromoethane was added at -78°C, and the mixture was allowed to warm to room temperature and was stirred for 5 hours. It was evaporated down and then purified by column chromatography (SiOz; n-hexane/HZCC12 9 . 1 parts by volume).
The product-containing fractions were combined and evaporated down, the residue was taken up in dry ether, the solution was dried over .MgS04 and filtered and the solvent was stripped off.
Yield: 1.6 g (5.59 mmol - 49~) of isomer mixture rF ( Si02; n-hexane/HzGClz 9 . 1 parts by volume ) = 0 , 46 The 1H-NMR spectrum meets the expectation for an isomer mixture in signal shift and integration.
A) Synthesis of rac-dimethylsilyl(2-Me-.1-indenyl)Z-zircanium dichloride 1.68 g (5.31 mmol) of the chalets ligand dimethylsilyl(2-methylindene)z were added to 50 cma of THF, and 6.63 cm3 of a 1.6 N (10.61 mmol) n-Bu~i/n-hexane solution were added dropwise. The addition was carried out at ambient temperature in the course of 0.5 hour. The mixture was stirred for 2 hours at about 35°C, after which the solvent was stripped off in vacuo, the residue was stirred with n-pentane and the solid was filtered off and dried.
The dilithio salt thus obtained was added at -78°C to a suspension of 1.24 g {5.32 mmol) of ZrCl4 in 50 cm3 of CHzCl2 and the mixture was stirred for 3 hours at this temperature. After warming up to room temperature overnight, the mixture was evaporated down. The zH-N.MR
spectrum indicated a rac-meso mixture in addition to the presence of a little ZrCl4(thf)2. After stirring with n-pentane and drying, t)ie solid, yellow residue was suspen-ded in THF, filtered off and investigated by NCR spec-troscopy. These three operations were repeated several s'~
!.n ,~ eJ' m_ ~,~
times; finally 0.35 g (0.73 mmol-1~~) of product was obtained, in which, according to 1H-NMR, the rac form had been concentrated to more than 17 a 1.
The compound gave a correct elemental analysis and the following NMR signals (CDC13, 100 MHz)a 6 = 1.25 (s, 6H, Si-Me); 2.18 (s, 6H, 2-Me), S.8 (s, 2H, 3~-H-Ind); 6.92-7.'75 (m, 8H, ~-7-H-Ind).
B) Synthesis of rac-damethylsilyl(2-Me-1-iridenyl)2-zirconiumdimethyl 1.3 cm3 of a 1.6 N (2.08 rnmol) ethereal Me7Gi solution were added dropwise to 0.29 g (0.58 mmol) of rac-di.methylsilyl (2-Me-1-iridenyl)ZZirconium dichloride in 40 cm3 of EtzO
at -50°C, and stirring was carried out for 2 hours at -10°C. After exchanging the solvent for n-pentane, ~~tir-ring was continued for a further 1.5 hours at room temperature and the filtered residue was sublimed in vacuo. 0.19 g (0.44 mmol-81~) of sublimate with a correct elemental analysis was obtained.
C) Reaction of rac-dimethylsilyl(2-Me-1-indenyl)Z-2 0 zirconiumdimethyl with [ Bu3NH ~ [ B ( CsHS ) a ]
0.17 g (0.39 mmol) of rac-dimethylsilyl(2-Me-1-indenyl)2-zireoniumdimethyl was added at 0°C to 0.18 g (0.36 mmol) of L Bu3NH ] f B ( C6H5 ) a 7 in 25 cm3 of toluene . The mixture was warmed up to.ambient temperature while stirring for one hour. The deeply coloured mixture was then evaporated to dryness.
An aliquot part of the reaction mixture was used for 'the polymerization.
D) Synthesis of rac-ethylene(2-Me-1-indenyl)ZZirconium dichloride 14.2 cm3 of 2.5 N (35.4 mmol) n-BuLi/n-hexane Solution were added dropwise to 5.07 g (17.7 mmol) of the ligand ethylene(2-methylindene)2 in 200 cm3 of THF at room temperature in the course of 1 hour, and stirring was then carried out for 3 hours at about 50°C. A precipitate which was formed in the meantime goes into solution again. The solution was allowed to stand overnight.
6.68 g (17.7 mmol) of ZrCI,,(thf)z in 250 cm3 of THF were added dropwise, simultaneously with 'the above dilithio salt solution, to about 50 cm3 of THF at 50°C, and stir-ring was then carried out for 20 hours at this tempera-ture. The toluene extract of the evaporation residue was evaporated down. After extraction of the residue with a small amount of THF, recrystallization was effected from toluene. 0.44 g (0.99 mmol-5.6~) of product was obtained, the rac form having been concentrated to more than 15 s 1.
The compound gave a correct elemental analysis and the following NMR signals ( CDC13, 100 MHz ) : 8 - 2 . 08 ( 2s, 6H, 2-Me) ; 3 . 45-4 .18 (m, 4Fi, -CHZCHZ-) , 6 . 65 ( 2H, 3-H-Ind) ;
The compound gave a correct elemental analysis and the following NMR signals ( CDC13, 100 MHz ) : 8 - 2 . 08 ( 2s, 6H, 2-Me) ; 3 . 45-4 .18 (m, 4Fi, -CHZCHZ-) , 6 . 65 ( 2H, 3-H-Ind) ;
7.05-7.85 (m, 8H, 4-7-H-znd).
F) Synthesis of rac-ethylene(2-Me-1-indenyl)ZZirconium-dimethyl 1.5 cm3 of a 1.6 N (2.4 mmol) et~aereal MeT~i solution were added to 0.31 g (0.68 mmol) of rac-ethylene(2-Me-1-indenyl)ZZirconium dichloride in 40 cm3 of Rt20, and stirring was carried out for 2 hours at -40°C. After exchanging the solvent for n-pentane, stirring was carried out for 1.5 houxs at ambient temperature and the mixture was filtered and the filtrate evaporated down.
0.22 g (0.54 mmol-80~) of sublimate with the correct elemental analysis was obtained.
F) Reaction of rac-ethylene(2-Me-1-indenyl)zzirconium-dimethyl with [ Bu33~1HH ] C B ( p-tolyl ) 41 2~i~~:~~t - 20 _ 0.13 g (0.32 mmol) of rac-ethylene(2-methyl-1-indenyl)z-zirconiumda.methyl was added to 0.16 g (0.28 mmol) of [ Bu3NH ] [ B ( p-tolyl ) y ] in 2 0 cm3 of toluene and stirring was carried out for 1 hour at ambient temperature. The solvent was stripped off and drying was then carried out in vacuo.
An aliquot part of the reaction mixture was used for the polymerization.
Example 1 A dry 24 dm3 reactor was flushed with nitrogen and filled with 12 dm3 of liquid propylene.
35 cm3 of a solution of methylaluminoxane in toluene (corresponding~to 52 mmol of AI, mean degree of oligomer ization n = 17) were then added and the batch was stirred at 30°C for 15 minutes.
At the same time, 6.9 mg (0.015 mmol) of rac-ethylene(2 Me-1-indenyl)zzirconium dichloride were dissolved in 13.5 cm3 of a solution of methylaluminoxane in toluene (20 mmol of A1) and preactivated by allowing the solution to stand for 15 minutes.
The solution was then introduced into the reactor and heated to 70°C by supplying heat (10°C/min), and the polymerization system was kept at 70°C for 1 hour by cooling. ~'he polymerization was stopped by allowing the excess gaseous monomer to escape. 1.56 kg of propylene were obtained. The activity of the metallocene was thus 226 kg of PP per g of metallocene per h.
VN = 67 cm3/g; Mv, = 58, 900 g/mol; M,o/Mr, = 2. 0; IT = 95.9;
HD = 350 g/dm3 r ~-~~~::~r~ ~ r.~
.-al-Example 2 Example 1 was repeated, except that 10.1 mg (0.023 mmol) of metallocene were used and polymerization was carried out at 50°C.
0.51 kg of polymer powder were obtained, corresponding to a metallocene activity of 50.5 kg of PP per g of metallo-cene per h.
VN - 100 cm3/g; Rs,, = 10$,500 g/mol; ~i~/M" - 2.2; II -96.4~~; MfT (230/5) = 210 gll0 min Example 3 Example 1 was repeated, except that 10.5 mg (0.023 mmol) of the metallocene were used and polymerization was carried out at 30°C for 10 hours.
1.05 kg of polymer powder were obtained, corresponding to a metallocene activity of 10.0 kg of PP per g of metallo cane per h.
~1 - 124 cm~lg; 1~, = 157, 000 g/mol; ~,,,/1~, = 2 .2; IT -96.3~5; MfI (230/5) = 104 g110 min Comparative Examphs A - C
Polymerization was carried ~ut analogously to Examples 1 to 3, using tie metallocene roc-ethylenebisindenyl-zirconium eliehloride. The viscosity numbers and molecu.-lar weights of the resulting polymer products wars:
Comparative Polym. temp. VN iH~
Example LC] [cm3/gJ [g/mo1]
A 70 30 19,900 50 46 38,500 C 30 ' 60 48,700 '~~ ~~~~ ~~, These Comgarative Examples show the effect of the sub-stituent in the 2-position on the indenyl ligand in respect of increasing the molecular weight.
Example 4 The procedure in Example 1 was followed, except that 4.0 mg (0.008 mmol) of roc-dimethylsilyl(2-methyl-1-indenyl)Zxirconium dichloride were used. The metallacene activity was 293 kg of PP per g of met~allocene per h.
VN - 171 cm3/g; Ma, = 197, 000 g/mol; Y~,/i~" - 2. 5; II
96.O~k; MFI (230/5) = 43.2 g/10 min; B~ = 460 g/dm3; m.p.
- 145°C
Example 5 The procedure in Example 1 was followed, except that 6.0 mg (0.013 moral) of roc-dimethylsilyl(2-methyl-1 indenyl)2zirconium dichloride were used.
The polymerization temperature was 60°C and the polymeri-zation time was l hour. The metallocene activity was 178 kg of PP per g of metallocene per h.
VN - 217 cm3/g; M% _ 297, 000 g/mol; 1~/M=, = 2 . 3; II --96.4; MFI (230/5) = 12.9 g/10 min; m.p. - 248°C
Example 6 The procedure in Example 1 was followed, except that 2.4 mg (0.0052 mmcrl) of roc-dime~thylsilyl(2-methyl-1-indenyl)ZZirconium dichloride were used. The polymeri.za-Lion temperature was 50°C and ~th~ polymerisation time was 3 hours. The metallocene activity was 89 kg of PP per g of matallocene per h.
VN - 259 cm3/g; P~" = 342,500 ~g/mol; M~,/T~, = 2:1; II
96.8~; MFI (230/5) = 8.1 g/10 m~.n; m.p. 150°C
j'' !' ~ n - 23 - ~~f~~~~~:
Example 7 The procedure in Example 1 was followed, except that 9.9 mg (0.021 mmol) of roc-dimethylsilyl(2-methyl-1-indenyl)ZZirconium dichloride were used.
The polymerization temperature was 30°C and the poly-merization time was 2 hours. The metallocene activity was 26.5 kg of PP per g of metallocene per h.
VTV = 340 cm3/g; M,p = 457, 000 g/mol; 1~,/1~, = 2.4, II -96.0~; MFI (230/5) = 2.5 g/10 min; m.p. - 153°C
20 Example 8 A dry 24 dm3 reactor was flushed with nitrogen and filled with 6 dm3 of a gasoline cut from wha.ch aromatics had been removed and which had a boiling range of 100-120°C and 6 dm3 of liquid propylene. 35 cm3 of a solution of methyl-aluminoxane in toluene (corresponding to 52 moral of A1, mean degree of oligomerization n = 17) were then added and the batch was stirred at 30°C for 30 minutes.
At the same time, 14.7 mg (0.031 mmol) of roc-dimethyl-silyl(2-methyl-1-indenyl)ZZirconium dichloride were dissolved in 13.5 cm3 of a solution of methylaluminoxane in toluene (20 mmol of A1) and preactivated by allowing the solution to stand for 30 minutes.
The solution was then introduced into the reactor and the polymerization system was kept at 50°C for 1 hour by cooling. The polymerization was stopped by adding 50 cm3 of isopropanol. The metallocene activity was 159.2 kg of PP per g of metallocene per h.
VN = 188 cm3/g; Mv, = 240, 000 g/mol; l.~,lMx, = 2 .1; TI -96.0~; MFI (230/5) = 28.5 g/10 min; m.p. - 149°C
Example 9 Example 8 was repeated, except that 15.2 mg (0.032 mmol) of the metallocene were used, the polymerizatian time was 2 hours and the polymerization temperature was 30°C.
The metallacene activity was 24.1 kg of PP per g of metallocene per h.
VT~T - 309 cm3/g; Mw = 409, 000 g/mol; M~fl~, = 2 . 3; II
97.0~; MFI (230!5) = 3.5 g/10 min; m.p. - 153°C
Camparative Examples D - F
Polymerization was carried out analogously to Examples 4, 6 and 7 using the metallocene dimethylsilylbisindenyl-zirconium dichloride. The viscosity numbers and molacu-lar weights of the resulting polymer products weree Comparative Polym. t~rrnp.VN 1~,, Example [C] [cm3/g] [g/mol]
70 47 37,500 E 50 60 56,000 F 30 77 76,900 These Examples show the effect of the substituent in 'the 2-position on the indenyl ligand in respect of inGreas.ing the molecular weight.
Example 10 A dry l6 dm~ reactor was flushed with nitrogen. 40 dm3 (corresponding to 2.5 bar) of hydrogen and finally 10 drn3 of liquid propylene and 29.2 cm~ of a salu~tion of methyl-alumi:noxane in toluene (corresponding to 40 mmol of Al, mean degree of oligom~srization l7) were then metered in, and stirring was carried out at 30°C for 10 minutes.
At the same time, 2.? mg (0.006 mmol) of roc-dimethyl-silyl(2-Me-1-indenyl)Zxirconium dichloride were dissolved 1 .~ J .:
'~ c.~ e~ id ~. ;.~
in 11.2 cm3 of a solution of rnethylaluminoxane in toluene ( 20 mmol ) and introduced into the reactor after 10 minutes .
Polymerization was carried out for 3 hours after heating to 50°C. The polymerization was stopped by adding COZ gas, and excess gaseous monomer was alowed to escape. The metallocene activity was 102.9 kg of PP per g of metal--locene per h.
VN = 25 cm'/g; Mp, = 8,500 g/mol; Ps~,/Mn = 2.4; no olefinic chain ends according to ~3C-NMFL; II = 9'7.8; m.p. - 149°C
Example 11 Example 10 was repeated, except that 5.0 mg (0.011 mmol) of rac-dimethylsilyl(2-Me-1-indenyl)ZZirconiumdimethyl and 16 dm3 (corresponding to 1 bar) of hydrogen were used.
Polymerization was carried out at 60°C for 50 minutes.
The metallocene activity was 204 kg of PP per g of metallocene per h.
VN = 47 cm3/g; M~,, = 41,100 g/mol; M~,/I~, = 2.2; no olefinic chain ends according t0 '3C-NMR; TI = 96.9; m,p. -- 148°C
Example 12 Example 11 was repeated with 4.2 mg (0.01 mmol) of rac-disnethyls ilyl ( 2-Tie-1-inde:~yl ) Zzirconiumdimethyl . However, the polymerization temperature was 70°C and the poly-merization time was 1 hour. The metallocene activity was 354 kg of PP per g of metallocene per h.
vN = 38 cm3/g; Mp, = 34, 900 g/mol; M"h'~, = Z .1; no olefinic chain ends according to '3C-Nl~; II = 96.7; m.p. = 146°C
Examples 10 to 12 show the good regulatability of the molecular weight with hydrogen when the polymerization process according to the invention was used.
- 2s -Example 13 Example 11 was repeated, except that no hydrogen was used. The metallocene activity was 182.4 kg of PP per g of metallocene per h.
STN - 210 cm3/g; MN, = 288, 000 g/mol; MN,/Mn = 2.2; TI -96.2~.
Example 14 Example 11 was repeated, except that 4.2 mg (0.01 mmol) of rac-ethylene(2-Me-1-ind~nyl)zzirconiumdi.methyl were used. The metallocene activity was 144.3 kg of pP per g of metallocene per h.
VN = 16 cm~lg; M~, - 8;900 g/mol; Mi"/M~, = 2.0; II m 96.0$;.
Example 15 A dry 24 dm~ reactor was flushed with nitrogen and filled with 12 dm3 of liquid propylene and with 4.0 cm3 of a solution of methylaluminoxane in toluene (corresponding to 6 mmol of Al, mean degree of oligomerization 17), and stirring was carried out at 30°C far 15 minutes. 2.5 cm~
of the reaction miacture of rac-dimethylsilyl(2-Men-1-2 0 indenyl ) ~z irconiumdianethyl and [ Bu3NH ] [ B ( C6H3 ) a ] , v~rhich mixture was described in Section C) of the metallocene synthesis and corresponds to 17 mg. (0.04 mmol) of me~allocen~, in toiuenca, were metered into the vessel:
Polymerization was carried out at 50°C for 1 hour: ~'he me~all,ocene activity was 61.4 kg of ~P per g of metallocene peg h:
VN = 238 cm~/g; ~k~'" = 328, 500 g/mol; Mo,/M" = 2 .2; IT --96.O~k.
27 _ ~~~~~~J
Example 16 Example 15 was repeated, except that 2.5 cm3 of the reaction mixture of rac-.ethylene ( 2-methyl-1-l.ndenyl ) 2-z irconiumdi methyl and [ Bu3I~H ] [ B ( p-tolyl ) 4 ] , which mixture was described in Section F) of the metallocene synthesis and corresponds to 16.3 mg (0.04 mmol) of metallocene, in toluene, were used. The metallocene activity was 42.9 kg of PP per g of metallocene per h.
VN - 105 cm3/g; 1~,, = 110, 500 g/mol; i~~,,/Mn - 2 . 3; II -96Ø
Example 17 Example 15 was repeated, except that a solution of tri-methylaluminum in toluene (8 mmol of A1) was used instead of the methylaluminoxane solution. The metalloc:ene activity was 55.3 kg of PP per g of metallocene per h.
VN - 264 cm3/g; 1~., = 367, 000 glmol; M~"/I~, = 2 .3; II -96.2~.
Example 18 Example 17 was repeated, except that no trimethylaluminum was used in the polymerizat~.on.
The propylene used was purified with triethylaluminum (1 mmol of AlEt3/dm3 of propylene) before being added to the polymerization system, and the reaction products and AlEt~ were separated off by distillation. The metallocene activity was 56.9 kg of PP peg g of metallncene per h.
VN = 278 cm3/g; IMO = 3f2,000 glmol; Ma,/T~, = Z.3; II -96.3~.
n,r .y.
Example 19 A dry 16 dm3 reactor was flushed with nitrogen and filled at 20°C with 10 dm3 of a gasoline cut from which aromatics had been removed and which had a boiling range of 100 120°C.
The gas space of the vessel was then flushed nitrogen-free by forcing in 2 bar of ethylene and letting down the pressure, these operations being carried out 5 times.
Thereafter, 30 cm3 of a solution of methylaluminoxane in toluene (corresponding to 45 mmol of A1, molecular weight according to cryoscopic determination 750 g/mol) were added.
The reactor content was heated to 60°C in the course of minutes while stirring, and the total pressure was 1S adjusted to 5 bar at a stirring speed of 250 xpm by adding ethylene.
.fit the same 'tame, 2.3 mg (0.005 mmol) of rac-ethylene(2-methyl-1-indenyl)Z~iroonium dichloride were dissolved in cm3 of a solution of methylalum~.noxane in toluene and 20 preactivated by allowing the solution to stand for 15 minutes. The solution was then introduced into 'the reactor, and tha polymerization system was :brought to a temperature of 70°C and kept at this temperature for 1 hour by appropriate cooling. The total pressure was kept at 5 bar dining this time by appropriate supply of ethylene.
420 g of polyethylene were obtained, corresponding to a metallocene activity of 182.6 kg of PE per g of metallo-cene per h.~ The viscosity number was 300 cm3/g.
Camparative Example G
Polymerization was carried out with the metallocene 2g .-rac-ethylene(1-indenyl)ZZirconium dichloride under conditions analogous ~to Example 19. A polyethylene having a viscosity number of 210 cm3/g was obtained.
The Comparative Example demonstrates the effect of substitution in the 2-position of the indenyl ligand in respect of increasing the molecular weight.
Example 20 Example 7 was repeated, except that the aluminoxane used was isobutylmethylaluminoxane in the same A1 concentra-tion and amount. The metallocene activity was 27.4 kg of PP per g of metallocene per h, M" was 477,500 g/mol, the V1~1 was 340 cm3/g an 1~"/ri° was 2.2. xsobutylrnethyl~-aluminoxane was obtained by reacting a mixture of iso-butyl-AlMe2 and AlMe3 with water in heptane and contained 9 mol ~ of isobutyl units and 91 mol ~ of methyl units.
Example 21 Example 7 was repeated, except that the aluminoxane used was hydridomethylaluminoxane (prepared from Me2AlH and water in toluene) in the same A1 concentration and amount. The activity was 22.9 kg of PP per g of metallo-cene per h, M~ was 469,500 g/mol, the VN was 339 cm3/g and MW/Mn was 2Ø
Example 22 A dry 150 dm3 reactor was flushed with nitrogen and filled, at 20°C, with 80 dm~ ~f a gasol3.ne cut from which aromatics had been removed and which had a boiling range of 100 - 120°C. Thereafter, the gas space way flushed nitragen-free by forcing in 2 bar of propylene and lett3.ng down the pressure, these operations being carried out 5 times.
After the addition of 50 1 of liquid propylene, 64 cm3 of _ 30 _ s~~~~~~.~3 a solution of methylaluminoxane in toluene (corresponding to 100 mmol of Al, molecular weight according to cryo-scopic determination 990 g/mol) were added and the reactor content was heated to 30°C.
By metering in hydrogen, a hydrogen content in ~he gas space of the reactor of 0.3~ was established and was subsequently maintained during the entire polymerization time by further metering (on-line monitoring by gas chromatography).
Z0 24.3mg of rac«dimethylsilyl(2-methyl~1-indenyl)ZZirconium dichloride (0.05 mmol) were dissolved in 32 ml of a solu-tion of methylaluminoxane in toluene (corresponding to 50 mmol of A1), and the solution was introduced into the reactor after 15 minutes.
Z5 The reactor was kept at the polymerization temperature of 30°C for 24 hours by cooling, and the polymerization was then stopped by add~.ng 2 bar of Cn2 gas and the polymer formed was isolated from the suspension medium over a pressure falter. The product was dried for 24 hours at 20 80°/200 mbar. 10.5 kg of polymer powder, corresponding to a metallocene activity of 18.0 kg of PP per g of metalla--cene per h, were obtained.
VN -- 256 cm3/c~; M" = 340, 500 g/mol; 1~,/M° = 2 .2; II -97.3~; 1S~'I (230!5) = 5.5 g/10 min; m.p. - 156°C
25 Example 23 Example 22 was repeated, except that 0.6~ of B2 was established in the gas spaae,.20.6 mg (0.043 mmol) of the metallocene were used and the polymerization temperature was 50°C.
30 19.2 kg of polymer powder, corresponding to a metallocene activity of 38.8 kg of PP pc~r g of metallocene per h, were obtained.
-31_ Vt~1 - 149 cm3/g; M~ = 187, 500 g/mol; Mq,/Mr, - 2 . 3; II -97.0~; MFI (230/5) = 82 g/10 min; m.p. - 150°C
Example 24 Example 23 was repeated, except that no hydrogen was used, the weight of metallocene was 31.0 mg (0.065 mmol) and the polymerization time was 4 hours.
F) Synthesis of rac-ethylene(2-Me-1-indenyl)ZZirconium-dimethyl 1.5 cm3 of a 1.6 N (2.4 mmol) et~aereal MeT~i solution were added to 0.31 g (0.68 mmol) of rac-ethylene(2-Me-1-indenyl)ZZirconium dichloride in 40 cm3 of Rt20, and stirring was carried out for 2 hours at -40°C. After exchanging the solvent for n-pentane, stirring was carried out for 1.5 houxs at ambient temperature and the mixture was filtered and the filtrate evaporated down.
0.22 g (0.54 mmol-80~) of sublimate with the correct elemental analysis was obtained.
F) Reaction of rac-ethylene(2-Me-1-indenyl)zzirconium-dimethyl with [ Bu33~1HH ] C B ( p-tolyl ) 41 2~i~~:~~t - 20 _ 0.13 g (0.32 mmol) of rac-ethylene(2-methyl-1-indenyl)z-zirconiumda.methyl was added to 0.16 g (0.28 mmol) of [ Bu3NH ] [ B ( p-tolyl ) y ] in 2 0 cm3 of toluene and stirring was carried out for 1 hour at ambient temperature. The solvent was stripped off and drying was then carried out in vacuo.
An aliquot part of the reaction mixture was used for the polymerization.
Example 1 A dry 24 dm3 reactor was flushed with nitrogen and filled with 12 dm3 of liquid propylene.
35 cm3 of a solution of methylaluminoxane in toluene (corresponding~to 52 mmol of AI, mean degree of oligomer ization n = 17) were then added and the batch was stirred at 30°C for 15 minutes.
At the same time, 6.9 mg (0.015 mmol) of rac-ethylene(2 Me-1-indenyl)zzirconium dichloride were dissolved in 13.5 cm3 of a solution of methylaluminoxane in toluene (20 mmol of A1) and preactivated by allowing the solution to stand for 15 minutes.
The solution was then introduced into the reactor and heated to 70°C by supplying heat (10°C/min), and the polymerization system was kept at 70°C for 1 hour by cooling. ~'he polymerization was stopped by allowing the excess gaseous monomer to escape. 1.56 kg of propylene were obtained. The activity of the metallocene was thus 226 kg of PP per g of metallocene per h.
VN = 67 cm3/g; Mv, = 58, 900 g/mol; M,o/Mr, = 2. 0; IT = 95.9;
HD = 350 g/dm3 r ~-~~~::~r~ ~ r.~
.-al-Example 2 Example 1 was repeated, except that 10.1 mg (0.023 mmol) of metallocene were used and polymerization was carried out at 50°C.
0.51 kg of polymer powder were obtained, corresponding to a metallocene activity of 50.5 kg of PP per g of metallo-cene per h.
VN - 100 cm3/g; Rs,, = 10$,500 g/mol; ~i~/M" - 2.2; II -96.4~~; MfT (230/5) = 210 gll0 min Example 3 Example 1 was repeated, except that 10.5 mg (0.023 mmol) of the metallocene were used and polymerization was carried out at 30°C for 10 hours.
1.05 kg of polymer powder were obtained, corresponding to a metallocene activity of 10.0 kg of PP per g of metallo cane per h.
~1 - 124 cm~lg; 1~, = 157, 000 g/mol; ~,,,/1~, = 2 .2; IT -96.3~5; MfI (230/5) = 104 g110 min Comparative Examphs A - C
Polymerization was carried ~ut analogously to Examples 1 to 3, using tie metallocene roc-ethylenebisindenyl-zirconium eliehloride. The viscosity numbers and molecu.-lar weights of the resulting polymer products wars:
Comparative Polym. temp. VN iH~
Example LC] [cm3/gJ [g/mo1]
A 70 30 19,900 50 46 38,500 C 30 ' 60 48,700 '~~ ~~~~ ~~, These Comgarative Examples show the effect of the sub-stituent in the 2-position on the indenyl ligand in respect of increasing the molecular weight.
Example 4 The procedure in Example 1 was followed, except that 4.0 mg (0.008 mmol) of roc-dimethylsilyl(2-methyl-1-indenyl)Zxirconium dichloride were used. The metallacene activity was 293 kg of PP per g of met~allocene per h.
VN - 171 cm3/g; Ma, = 197, 000 g/mol; Y~,/i~" - 2. 5; II
96.O~k; MFI (230/5) = 43.2 g/10 min; B~ = 460 g/dm3; m.p.
- 145°C
Example 5 The procedure in Example 1 was followed, except that 6.0 mg (0.013 moral) of roc-dimethylsilyl(2-methyl-1 indenyl)2zirconium dichloride were used.
The polymerization temperature was 60°C and the polymeri-zation time was l hour. The metallocene activity was 178 kg of PP per g of metallocene per h.
VN - 217 cm3/g; M% _ 297, 000 g/mol; 1~/M=, = 2 . 3; II --96.4; MFI (230/5) = 12.9 g/10 min; m.p. - 248°C
Example 6 The procedure in Example 1 was followed, except that 2.4 mg (0.0052 mmcrl) of roc-dime~thylsilyl(2-methyl-1-indenyl)ZZirconium dichloride were used. The polymeri.za-Lion temperature was 50°C and ~th~ polymerisation time was 3 hours. The metallocene activity was 89 kg of PP per g of matallocene per h.
VN - 259 cm3/g; P~" = 342,500 ~g/mol; M~,/T~, = 2:1; II
96.8~; MFI (230/5) = 8.1 g/10 m~.n; m.p. 150°C
j'' !' ~ n - 23 - ~~f~~~~~:
Example 7 The procedure in Example 1 was followed, except that 9.9 mg (0.021 mmol) of roc-dimethylsilyl(2-methyl-1-indenyl)ZZirconium dichloride were used.
The polymerization temperature was 30°C and the poly-merization time was 2 hours. The metallocene activity was 26.5 kg of PP per g of metallocene per h.
VTV = 340 cm3/g; M,p = 457, 000 g/mol; 1~,/1~, = 2.4, II -96.0~; MFI (230/5) = 2.5 g/10 min; m.p. - 153°C
20 Example 8 A dry 24 dm3 reactor was flushed with nitrogen and filled with 6 dm3 of a gasoline cut from wha.ch aromatics had been removed and which had a boiling range of 100-120°C and 6 dm3 of liquid propylene. 35 cm3 of a solution of methyl-aluminoxane in toluene (corresponding to 52 moral of A1, mean degree of oligomerization n = 17) were then added and the batch was stirred at 30°C for 30 minutes.
At the same time, 14.7 mg (0.031 mmol) of roc-dimethyl-silyl(2-methyl-1-indenyl)ZZirconium dichloride were dissolved in 13.5 cm3 of a solution of methylaluminoxane in toluene (20 mmol of A1) and preactivated by allowing the solution to stand for 30 minutes.
The solution was then introduced into the reactor and the polymerization system was kept at 50°C for 1 hour by cooling. The polymerization was stopped by adding 50 cm3 of isopropanol. The metallocene activity was 159.2 kg of PP per g of metallocene per h.
VN = 188 cm3/g; Mv, = 240, 000 g/mol; l.~,lMx, = 2 .1; TI -96.0~; MFI (230/5) = 28.5 g/10 min; m.p. - 149°C
Example 9 Example 8 was repeated, except that 15.2 mg (0.032 mmol) of the metallocene were used, the polymerizatian time was 2 hours and the polymerization temperature was 30°C.
The metallacene activity was 24.1 kg of PP per g of metallocene per h.
VT~T - 309 cm3/g; Mw = 409, 000 g/mol; M~fl~, = 2 . 3; II
97.0~; MFI (230!5) = 3.5 g/10 min; m.p. - 153°C
Camparative Examples D - F
Polymerization was carried out analogously to Examples 4, 6 and 7 using the metallocene dimethylsilylbisindenyl-zirconium dichloride. The viscosity numbers and molacu-lar weights of the resulting polymer products weree Comparative Polym. t~rrnp.VN 1~,, Example [C] [cm3/g] [g/mol]
70 47 37,500 E 50 60 56,000 F 30 77 76,900 These Examples show the effect of the substituent in 'the 2-position on the indenyl ligand in respect of inGreas.ing the molecular weight.
Example 10 A dry l6 dm~ reactor was flushed with nitrogen. 40 dm3 (corresponding to 2.5 bar) of hydrogen and finally 10 drn3 of liquid propylene and 29.2 cm~ of a salu~tion of methyl-alumi:noxane in toluene (corresponding to 40 mmol of Al, mean degree of oligom~srization l7) were then metered in, and stirring was carried out at 30°C for 10 minutes.
At the same time, 2.? mg (0.006 mmol) of roc-dimethyl-silyl(2-Me-1-indenyl)Zxirconium dichloride were dissolved 1 .~ J .:
'~ c.~ e~ id ~. ;.~
in 11.2 cm3 of a solution of rnethylaluminoxane in toluene ( 20 mmol ) and introduced into the reactor after 10 minutes .
Polymerization was carried out for 3 hours after heating to 50°C. The polymerization was stopped by adding COZ gas, and excess gaseous monomer was alowed to escape. The metallocene activity was 102.9 kg of PP per g of metal--locene per h.
VN = 25 cm'/g; Mp, = 8,500 g/mol; Ps~,/Mn = 2.4; no olefinic chain ends according to ~3C-NMFL; II = 9'7.8; m.p. - 149°C
Example 11 Example 10 was repeated, except that 5.0 mg (0.011 mmol) of rac-dimethylsilyl(2-Me-1-indenyl)ZZirconiumdimethyl and 16 dm3 (corresponding to 1 bar) of hydrogen were used.
Polymerization was carried out at 60°C for 50 minutes.
The metallocene activity was 204 kg of PP per g of metallocene per h.
VN = 47 cm3/g; M~,, = 41,100 g/mol; M~,/I~, = 2.2; no olefinic chain ends according t0 '3C-NMR; TI = 96.9; m,p. -- 148°C
Example 12 Example 11 was repeated with 4.2 mg (0.01 mmol) of rac-disnethyls ilyl ( 2-Tie-1-inde:~yl ) Zzirconiumdimethyl . However, the polymerization temperature was 70°C and the poly-merization time was 1 hour. The metallocene activity was 354 kg of PP per g of metallocene per h.
vN = 38 cm3/g; Mp, = 34, 900 g/mol; M"h'~, = Z .1; no olefinic chain ends according to '3C-Nl~; II = 96.7; m.p. = 146°C
Examples 10 to 12 show the good regulatability of the molecular weight with hydrogen when the polymerization process according to the invention was used.
- 2s -Example 13 Example 11 was repeated, except that no hydrogen was used. The metallocene activity was 182.4 kg of PP per g of metallocene per h.
STN - 210 cm3/g; MN, = 288, 000 g/mol; MN,/Mn = 2.2; TI -96.2~.
Example 14 Example 11 was repeated, except that 4.2 mg (0.01 mmol) of rac-ethylene(2-Me-1-ind~nyl)zzirconiumdi.methyl were used. The metallocene activity was 144.3 kg of pP per g of metallocene per h.
VN = 16 cm~lg; M~, - 8;900 g/mol; Mi"/M~, = 2.0; II m 96.0$;.
Example 15 A dry 24 dm~ reactor was flushed with nitrogen and filled with 12 dm3 of liquid propylene and with 4.0 cm3 of a solution of methylaluminoxane in toluene (corresponding to 6 mmol of Al, mean degree of oligomerization 17), and stirring was carried out at 30°C far 15 minutes. 2.5 cm~
of the reaction miacture of rac-dimethylsilyl(2-Men-1-2 0 indenyl ) ~z irconiumdianethyl and [ Bu3NH ] [ B ( C6H3 ) a ] , v~rhich mixture was described in Section C) of the metallocene synthesis and corresponds to 17 mg. (0.04 mmol) of me~allocen~, in toiuenca, were metered into the vessel:
Polymerization was carried out at 50°C for 1 hour: ~'he me~all,ocene activity was 61.4 kg of ~P per g of metallocene peg h:
VN = 238 cm~/g; ~k~'" = 328, 500 g/mol; Mo,/M" = 2 .2; IT --96.O~k.
27 _ ~~~~~~J
Example 16 Example 15 was repeated, except that 2.5 cm3 of the reaction mixture of rac-.ethylene ( 2-methyl-1-l.ndenyl ) 2-z irconiumdi methyl and [ Bu3I~H ] [ B ( p-tolyl ) 4 ] , which mixture was described in Section F) of the metallocene synthesis and corresponds to 16.3 mg (0.04 mmol) of metallocene, in toluene, were used. The metallocene activity was 42.9 kg of PP per g of metallocene per h.
VN - 105 cm3/g; 1~,, = 110, 500 g/mol; i~~,,/Mn - 2 . 3; II -96Ø
Example 17 Example 15 was repeated, except that a solution of tri-methylaluminum in toluene (8 mmol of A1) was used instead of the methylaluminoxane solution. The metalloc:ene activity was 55.3 kg of PP per g of metallocene per h.
VN - 264 cm3/g; 1~., = 367, 000 glmol; M~"/I~, = 2 .3; II -96.2~.
Example 18 Example 17 was repeated, except that no trimethylaluminum was used in the polymerizat~.on.
The propylene used was purified with triethylaluminum (1 mmol of AlEt3/dm3 of propylene) before being added to the polymerization system, and the reaction products and AlEt~ were separated off by distillation. The metallocene activity was 56.9 kg of PP peg g of metallncene per h.
VN = 278 cm3/g; IMO = 3f2,000 glmol; Ma,/T~, = Z.3; II -96.3~.
n,r .y.
Example 19 A dry 16 dm3 reactor was flushed with nitrogen and filled at 20°C with 10 dm3 of a gasoline cut from which aromatics had been removed and which had a boiling range of 100 120°C.
The gas space of the vessel was then flushed nitrogen-free by forcing in 2 bar of ethylene and letting down the pressure, these operations being carried out 5 times.
Thereafter, 30 cm3 of a solution of methylaluminoxane in toluene (corresponding to 45 mmol of A1, molecular weight according to cryoscopic determination 750 g/mol) were added.
The reactor content was heated to 60°C in the course of minutes while stirring, and the total pressure was 1S adjusted to 5 bar at a stirring speed of 250 xpm by adding ethylene.
.fit the same 'tame, 2.3 mg (0.005 mmol) of rac-ethylene(2-methyl-1-indenyl)Z~iroonium dichloride were dissolved in cm3 of a solution of methylalum~.noxane in toluene and 20 preactivated by allowing the solution to stand for 15 minutes. The solution was then introduced into 'the reactor, and tha polymerization system was :brought to a temperature of 70°C and kept at this temperature for 1 hour by appropriate cooling. The total pressure was kept at 5 bar dining this time by appropriate supply of ethylene.
420 g of polyethylene were obtained, corresponding to a metallocene activity of 182.6 kg of PE per g of metallo-cene per h.~ The viscosity number was 300 cm3/g.
Camparative Example G
Polymerization was carried out with the metallocene 2g .-rac-ethylene(1-indenyl)ZZirconium dichloride under conditions analogous ~to Example 19. A polyethylene having a viscosity number of 210 cm3/g was obtained.
The Comparative Example demonstrates the effect of substitution in the 2-position of the indenyl ligand in respect of increasing the molecular weight.
Example 20 Example 7 was repeated, except that the aluminoxane used was isobutylmethylaluminoxane in the same A1 concentra-tion and amount. The metallocene activity was 27.4 kg of PP per g of metallocene per h, M" was 477,500 g/mol, the V1~1 was 340 cm3/g an 1~"/ri° was 2.2. xsobutylrnethyl~-aluminoxane was obtained by reacting a mixture of iso-butyl-AlMe2 and AlMe3 with water in heptane and contained 9 mol ~ of isobutyl units and 91 mol ~ of methyl units.
Example 21 Example 7 was repeated, except that the aluminoxane used was hydridomethylaluminoxane (prepared from Me2AlH and water in toluene) in the same A1 concentration and amount. The activity was 22.9 kg of PP per g of metallo-cene per h, M~ was 469,500 g/mol, the VN was 339 cm3/g and MW/Mn was 2Ø
Example 22 A dry 150 dm3 reactor was flushed with nitrogen and filled, at 20°C, with 80 dm~ ~f a gasol3.ne cut from which aromatics had been removed and which had a boiling range of 100 - 120°C. Thereafter, the gas space way flushed nitragen-free by forcing in 2 bar of propylene and lett3.ng down the pressure, these operations being carried out 5 times.
After the addition of 50 1 of liquid propylene, 64 cm3 of _ 30 _ s~~~~~~.~3 a solution of methylaluminoxane in toluene (corresponding to 100 mmol of Al, molecular weight according to cryo-scopic determination 990 g/mol) were added and the reactor content was heated to 30°C.
By metering in hydrogen, a hydrogen content in ~he gas space of the reactor of 0.3~ was established and was subsequently maintained during the entire polymerization time by further metering (on-line monitoring by gas chromatography).
Z0 24.3mg of rac«dimethylsilyl(2-methyl~1-indenyl)ZZirconium dichloride (0.05 mmol) were dissolved in 32 ml of a solu-tion of methylaluminoxane in toluene (corresponding to 50 mmol of A1), and the solution was introduced into the reactor after 15 minutes.
Z5 The reactor was kept at the polymerization temperature of 30°C for 24 hours by cooling, and the polymerization was then stopped by add~.ng 2 bar of Cn2 gas and the polymer formed was isolated from the suspension medium over a pressure falter. The product was dried for 24 hours at 20 80°/200 mbar. 10.5 kg of polymer powder, corresponding to a metallocene activity of 18.0 kg of PP per g of metalla--cene per h, were obtained.
VN -- 256 cm3/c~; M" = 340, 500 g/mol; 1~,/M° = 2 .2; II -97.3~; 1S~'I (230!5) = 5.5 g/10 min; m.p. - 156°C
25 Example 23 Example 22 was repeated, except that 0.6~ of B2 was established in the gas spaae,.20.6 mg (0.043 mmol) of the metallocene were used and the polymerization temperature was 50°C.
30 19.2 kg of polymer powder, corresponding to a metallocene activity of 38.8 kg of PP pc~r g of metallocene per h, were obtained.
-31_ Vt~1 - 149 cm3/g; M~ = 187, 500 g/mol; Mq,/Mr, - 2 . 3; II -97.0~; MFI (230/5) = 82 g/10 min; m.p. - 150°C
Example 24 Example 23 was repeated, except that no hydrogen was used, the weight of metallocene was 31.0 mg (0.065 mmol) and the polymerization time was 4 hours.
8.0 kg of polymer powder, corresponding to a metallocene activity of 64.5 kg of PP per g of metallocene per h, were obtained.
VN - 175 cm3lg; M~, = 229, 000 g/mol; 1~,/1~, = 2.2; II -97.1~; MFT (230/5) = 35 g/10 min; m.p. - 150°C
Example 25 Example l was repeated, except that 4.1 mg (0.008 mmol) of the metallocene rac_phenyl(methyl)silyl(2-methyl_1 indenyl ) ZZrCl2 were used.
1.10 kg of polypropylene were obtained, corresponding to an activity of the metallocene of 269 kg of PP per g of metallocene per h.
VN = 202 cm~/g; M" = 230,000 glmol; I~,IM" = 2.3; II = 97~;
M~'I (23015) = 36 g/10 min; m.p. 147°C
Example 26' Example 25 was repeated with 11.0 mg (0.02 mmol) of the metallocene, but the polymerization temperature was 50°C.
1.05 kg of polypropylene were obtained. The activity of the metallocene was 95.5 kg of PP per g of metallocene per h.
VN - 347 cm3/g; ' M~ - 444, 000 g/mol; I~,/M" 2 .5; MFI
- 32 - ~~~ 8~~ ~J
(230!5) = 5.2 g/10 min; m.p. = 149°C
Example 27 Example 25 was repeated with 22.5 mg (0.04 mmol) of the metallocene, but the polymerization temperature was 30°C.
0.57 kg of polyprapylene was obtained and the actieity of the metallocene was thus 25.3 kg of PP per g of metallo-cene per h.
VN - 494 cm3/g; M~,, -.. 666, 000 g/mol; 1~,,/MT, - 2.5; MfI
(230/5) = 1.3 8110 min; m.p. - 152°C
Example 28 Example 1 was repeated, except that 5.2 mg (0.009 mmol) of the metallocene rac-diphenylsilyl(2-methyl-1--indenyl)ZZrCl2 were used.
1.14 kg of polypropylene were obtained. The metallocene activity was thus 219 kg of PP per g of metallocene per h.
VN - 298 am~/g; 1~,, ° 367, 000 g/mol; Mf,/Mr, - 2. 2; MFT
(230/5) = 7.1 g/10 min Example 29 Example 28 was repeated with 12.6 ang (0.02 mmol) of the metallocene but the polymerization temperature was 40°C.
0.44 kg of polypropylene was obtained and the metalloc~ene activity was thus 34 :9 kg of PP per g of m~taJ.locene per h.
vN - 646 cm3/g; M" = 845,000 g/mol; 1~,/M~, - 2.4; MFT
(230/5) = O.l g/!0 min; m.p. - 155°C
S
Example 30 Example 1 was repeated, except that 17.4 mg (0.038 mmol) of the metallocene rac-methylethylene(2-methyl-1-indenyl } z2rClz were used.
2.89 kg of polypropylene were obtained. The metallocene activity was thus 165.9 kg of PP per g of metallocene per h.
VN = 238 cm3/g; M~ = 129,000 g/mol; M"/Mn = 2.2; m.p. -150°C
Example 31 Example 30 was repeated with 1506 mg (0.034 mmol) of the metallocene but the polymerization temperature was 50°C
and the polymerization time was 2 hears.
2.86 kg of polypropylene were obtained. The metallocene I5 activity was thus 91. 7 kg of PP per g of metallocene per h.
V1V = 244 cm3lg; M", = 243,500 g/mol; M~,/M~, = 2.1; m.p. -255°C
Example 32 Example 30 was repeated with 50.8 mg (0.120 mmol) of the metallo~ene but the polymerization temperature was 30°C.
2.78 kg of polypropylene wore obtained and the metallo-cene activity eras thus 27.5 kg of PP per g of metalloceue per h.
VN - 409 cm~/g; 1~ ° 402, 000 g/mol; M"/M~, - 2 .2; 1~'I
(230/5) = 3.5 g/20 min; m.p. = 260°C
Example 33 Example 1 was repeated, except that 9.6 mg (0.02 mmol) of the metallocene rac-dimethylsilyl(2-methyl-1-indenyl)z-zirconium dichloride were used.
1.68 kg of polypropylene, corresponding to a metallocene activity of 175.0 kg of PP per g of metallocene per h were obtained.
VN = 143 cm3/g; 1~" = 132, 000 g/mol; N.~"/'MI, = 2. 3, m.p. -14 0°C
Example 34 Example 33 was repeated, except that 10.4 mg (0.021 mmol) of the metallocene were used and the polymerization temperature was 50°C.
1.00 kg of polypropylene, corresponding to a metallocene activity of 96.2 kg of PP per g of metallocene per h, were obtained.
VN = 303 cm~/g; kiz" = 449,500 g/mol; Mw,/M" = 2.2; m.p. -145°C
Example 35 Example 33 was repeated with 24.5 mg (0.049 mmol) of 'the metallocene at a polymerization temperature of 30°C.
0.49 kg of polypropylene, corresponding to a metallocene activity of 19.6 kg of PP per g of metallocene per h, was obtained.
VPI = 442 cm3/g; I~,, = 564,000 glmol; TH~,/i~i" = 2.2; m.p. -15 0°C
- 35 ' Example 36 A dry 24 dm3 reactor was flushed with nitrogen and filled with 2.4 dm3 (S.T.P.) of hydrogen and 12 dm3 of liguid propylene.
35 crn3 of a solution of methylaluminaxane in toluene (corresponding to 52 moral of Al, mean degree of oligomerization p = 17) were then added.
.At the same time, 8.5 mg (0.02 mmol) of roc-dimethyl-silyl(2-methyl-1-indenyl)ZZirconium dichloride were In dissolved in 13.5 cm3 of a solution of methylalumino7cane in toluene (20 mmol of Al) and preactivated by allowing the solution to stand far 5 minutes.
The solution was then introduced into the reactor.
Polymerization was carried out for 1 hour at 55°C with continuous addition of 50 g of ethylene.
The metalloeene activity was 134 kg of C2/C3--copolymer per g of metallocene per h.
The ethylene content of the copolymer was 4.3~.
VN - 2$9 cm3/g; M~, -- 402, 000 g/mol; ivi,~/Mn - 2. 0; 1~FI
(230/5) = 7.0 g/10 min The ethylene was substantially incorporated as isolated taiits ( 13C.-1~1MR, mean block length CZ < 1. 2 ) .
Example 37 A dry 150 dm~ reactor was prepared as described in Example 22 and charged with propylene and catalyst.
The polymerization was carried out in a first stage at 50°C for 10 hours.
In a second stage, 1 kg of ethylene was first rapidly added and a further 2 kg of ethylene were metered in continuously in the course of 4 hours.
21.5 kg of block copolymer powder were obtained.
VN - 326 cm3/g; M~,, - 407, 000 g/mol; P~"/~i,., - 3.1; MfI
(230/5) = 4.9 g/10 min The block copolymer contained 12.5 of ethylene.
Fractionation gave a content of 24~ of ethylene/propylene rubber in the copolymer. The mechanical data of the copolymer were:
Ball indentation hardness (DIN 53,456, pressed sheets, heated at 140°C for 3 h, 132 N) 60 Nmm Z, notched iatipact strength (ax", injection molded specimens according to DIN 53, 453 ) 23°C: na fracture, 0°C: 39 . a mJ'mtti Z, ~40°C: 20.1 mJmm 2.
The product is distinguished by an exceptional hardness/
impact strength relationship and can be used for struc-tural components, for example in automotive construction (e. g, bumpers), where high rigidity coupled with high impact strength, in particular at low temperatures, is required.
Abbreviations:
Me ~ Methyl, Et = Ethyl, Hu = Butyl, Fh = Fhenyl, THF =
Tetrahydrofuran, PE = Polyethylene, PP = Polypropylene.
VN - 175 cm3lg; M~, = 229, 000 g/mol; 1~,/1~, = 2.2; II -97.1~; MFT (230/5) = 35 g/10 min; m.p. - 150°C
Example 25 Example l was repeated, except that 4.1 mg (0.008 mmol) of the metallocene rac_phenyl(methyl)silyl(2-methyl_1 indenyl ) ZZrCl2 were used.
1.10 kg of polypropylene were obtained, corresponding to an activity of the metallocene of 269 kg of PP per g of metallocene per h.
VN = 202 cm~/g; M" = 230,000 glmol; I~,IM" = 2.3; II = 97~;
M~'I (23015) = 36 g/10 min; m.p. 147°C
Example 26' Example 25 was repeated with 11.0 mg (0.02 mmol) of the metallocene, but the polymerization temperature was 50°C.
1.05 kg of polypropylene were obtained. The activity of the metallocene was 95.5 kg of PP per g of metallocene per h.
VN - 347 cm3/g; ' M~ - 444, 000 g/mol; I~,/M" 2 .5; MFI
- 32 - ~~~ 8~~ ~J
(230!5) = 5.2 g/10 min; m.p. = 149°C
Example 27 Example 25 was repeated with 22.5 mg (0.04 mmol) of the metallocene, but the polymerization temperature was 30°C.
0.57 kg of polyprapylene was obtained and the actieity of the metallocene was thus 25.3 kg of PP per g of metallo-cene per h.
VN - 494 cm3/g; M~,, -.. 666, 000 g/mol; 1~,,/MT, - 2.5; MfI
(230/5) = 1.3 8110 min; m.p. - 152°C
Example 28 Example 1 was repeated, except that 5.2 mg (0.009 mmol) of the metallocene rac-diphenylsilyl(2-methyl-1--indenyl)ZZrCl2 were used.
1.14 kg of polypropylene were obtained. The metallocene activity was thus 219 kg of PP per g of metallocene per h.
VN - 298 am~/g; 1~,, ° 367, 000 g/mol; Mf,/Mr, - 2. 2; MFT
(230/5) = 7.1 g/10 min Example 29 Example 28 was repeated with 12.6 ang (0.02 mmol) of the metallocene but the polymerization temperature was 40°C.
0.44 kg of polypropylene was obtained and the metalloc~ene activity was thus 34 :9 kg of PP per g of m~taJ.locene per h.
vN - 646 cm3/g; M" = 845,000 g/mol; 1~,/M~, - 2.4; MFT
(230/5) = O.l g/!0 min; m.p. - 155°C
S
Example 30 Example 1 was repeated, except that 17.4 mg (0.038 mmol) of the metallocene rac-methylethylene(2-methyl-1-indenyl } z2rClz were used.
2.89 kg of polypropylene were obtained. The metallocene activity was thus 165.9 kg of PP per g of metallocene per h.
VN = 238 cm3/g; M~ = 129,000 g/mol; M"/Mn = 2.2; m.p. -150°C
Example 31 Example 30 was repeated with 1506 mg (0.034 mmol) of the metallocene but the polymerization temperature was 50°C
and the polymerization time was 2 hears.
2.86 kg of polypropylene were obtained. The metallocene I5 activity was thus 91. 7 kg of PP per g of metallocene per h.
V1V = 244 cm3lg; M", = 243,500 g/mol; M~,/M~, = 2.1; m.p. -255°C
Example 32 Example 30 was repeated with 50.8 mg (0.120 mmol) of the metallo~ene but the polymerization temperature was 30°C.
2.78 kg of polypropylene wore obtained and the metallo-cene activity eras thus 27.5 kg of PP per g of metalloceue per h.
VN - 409 cm~/g; 1~ ° 402, 000 g/mol; M"/M~, - 2 .2; 1~'I
(230/5) = 3.5 g/20 min; m.p. = 260°C
Example 33 Example 1 was repeated, except that 9.6 mg (0.02 mmol) of the metallocene rac-dimethylsilyl(2-methyl-1-indenyl)z-zirconium dichloride were used.
1.68 kg of polypropylene, corresponding to a metallocene activity of 175.0 kg of PP per g of metallocene per h were obtained.
VN = 143 cm3/g; 1~" = 132, 000 g/mol; N.~"/'MI, = 2. 3, m.p. -14 0°C
Example 34 Example 33 was repeated, except that 10.4 mg (0.021 mmol) of the metallocene were used and the polymerization temperature was 50°C.
1.00 kg of polypropylene, corresponding to a metallocene activity of 96.2 kg of PP per g of metallocene per h, were obtained.
VN = 303 cm~/g; kiz" = 449,500 g/mol; Mw,/M" = 2.2; m.p. -145°C
Example 35 Example 33 was repeated with 24.5 mg (0.049 mmol) of 'the metallocene at a polymerization temperature of 30°C.
0.49 kg of polypropylene, corresponding to a metallocene activity of 19.6 kg of PP per g of metallocene per h, was obtained.
VPI = 442 cm3/g; I~,, = 564,000 glmol; TH~,/i~i" = 2.2; m.p. -15 0°C
- 35 ' Example 36 A dry 24 dm3 reactor was flushed with nitrogen and filled with 2.4 dm3 (S.T.P.) of hydrogen and 12 dm3 of liguid propylene.
35 crn3 of a solution of methylaluminaxane in toluene (corresponding to 52 moral of Al, mean degree of oligomerization p = 17) were then added.
.At the same time, 8.5 mg (0.02 mmol) of roc-dimethyl-silyl(2-methyl-1-indenyl)ZZirconium dichloride were In dissolved in 13.5 cm3 of a solution of methylalumino7cane in toluene (20 mmol of Al) and preactivated by allowing the solution to stand far 5 minutes.
The solution was then introduced into the reactor.
Polymerization was carried out for 1 hour at 55°C with continuous addition of 50 g of ethylene.
The metalloeene activity was 134 kg of C2/C3--copolymer per g of metallocene per h.
The ethylene content of the copolymer was 4.3~.
VN - 2$9 cm3/g; M~, -- 402, 000 g/mol; ivi,~/Mn - 2. 0; 1~FI
(230/5) = 7.0 g/10 min The ethylene was substantially incorporated as isolated taiits ( 13C.-1~1MR, mean block length CZ < 1. 2 ) .
Example 37 A dry 150 dm~ reactor was prepared as described in Example 22 and charged with propylene and catalyst.
The polymerization was carried out in a first stage at 50°C for 10 hours.
In a second stage, 1 kg of ethylene was first rapidly added and a further 2 kg of ethylene were metered in continuously in the course of 4 hours.
21.5 kg of block copolymer powder were obtained.
VN - 326 cm3/g; M~,, - 407, 000 g/mol; P~"/~i,., - 3.1; MfI
(230/5) = 4.9 g/10 min The block copolymer contained 12.5 of ethylene.
Fractionation gave a content of 24~ of ethylene/propylene rubber in the copolymer. The mechanical data of the copolymer were:
Ball indentation hardness (DIN 53,456, pressed sheets, heated at 140°C for 3 h, 132 N) 60 Nmm Z, notched iatipact strength (ax", injection molded specimens according to DIN 53, 453 ) 23°C: na fracture, 0°C: 39 . a mJ'mtti Z, ~40°C: 20.1 mJmm 2.
The product is distinguished by an exceptional hardness/
impact strength relationship and can be used for struc-tural components, for example in automotive construction (e. g, bumpers), where high rigidity coupled with high impact strength, in particular at low temperatures, is required.
Abbreviations:
Me ~ Methyl, Et = Ethyl, Hu = Butyl, Fh = Fhenyl, THF =
Tetrahydrofuran, PE = Polyethylene, PP = Polypropylene.
Claims (7)
1. A process for the preparation of an olefin polymer by polymerization or copolymerization of an olefin of the formula R a-CH=CH-R b, wherein R a and R b are identical or different and are a hydrogen atom or a hydrocarbon radical having 1 to 14 C atoms, or R a and R b, together with the atoms binding them, may form a ring, at a temperature of -60 to 200°C, at a pressure of 0.5 to 100 bar, in solution, in suspension or in the gas phase, in the presence of a catalyst which is composed of a metallocene as the transition metal compound and a cocatalyst, the cocatalyst being an aluminoxane of the formula (II):
for the linear type and/or of the formula (III) for the cyclic type, wherein, in the formulae (II) and (III), the radicals R14 may be identical or different and are a C1-C6-alkyl group, a C6-C18-aryl group or hydrogen, and p is an integer from 2 to 50, and/or a salt-like compound of the formula R X NH 4-X BR'4 or of the formula R3PHBR'4 in which x is 1, 2 or 3, the radicals R are identical or different and are an alkyl or aryl group and R' is aryl, which, may also be fluorinated or partially fluorinated, wherein the metallocene is a compound of the formula I
wherein M1 is a metal of group lVb, Vb or Vlb of the Periodic Table, R1 and R2 are identical or different and are a hydrogen atom, a C1-C10-alkyl group, a C1-C10-alkoxy group, a C6-C10-aryl group, a C6-C10-aryloxy group, a C2-C10-alkenyl group, a C7-C40-arylalkyl group, a C7-C40-alkylaryl group, a C8-C40-arylalkenyl group or a halogen atom, R3 and R4 are identical or different and are a hydrogen atom, a halogen atom, a C1-C10-alkyl group which may be halogenated, a C8-C10-aryl group, a -NR2 10, -SR10, -OSi-R3 10, -SiR3 10 or -PR2 10 radical, wherein R 10 is a halogen atom, a C1-C10-alkyl group or a C6-C10-aryl group, R5 and R6 are identical or different and have the meaning stated for R3 and R4, with the proviso that R5 and R6 are not hydrogen, R7 is =BR11, =AIR11, -Ge-, -Sn-, -O-, -S-, =SO, =SO2, -NR11, =CO, =PR11 or =P(O)R11, wherein R11, R12 and R13 are identical or different and are a hydrogen atom, a halogen atom, a C1-C10-alkyl group, a C1-C10-fluoroalkyl group, a C6-C10-aryl group, a C6-C10-fluoroaryl group, a C1-C10-alkoxy group, C2-C10-alkenyl group, a C7-C40-arylalkyl group, C8-C40-arylalkenyl group or a C7-C40-alkylaryl group, or R11 and R12 or R11 and R13, together with the atoms binding them, each form a ring, M2 is silicon, germanium or tin, R8 and R9 are identical or different and have the meaning stated for R11 and m and n are identical or different and are zero, 1 or 2, m plus n being zero, 1 or 2.
for the linear type and/or of the formula (III) for the cyclic type, wherein, in the formulae (II) and (III), the radicals R14 may be identical or different and are a C1-C6-alkyl group, a C6-C18-aryl group or hydrogen, and p is an integer from 2 to 50, and/or a salt-like compound of the formula R X NH 4-X BR'4 or of the formula R3PHBR'4 in which x is 1, 2 or 3, the radicals R are identical or different and are an alkyl or aryl group and R' is aryl, which, may also be fluorinated or partially fluorinated, wherein the metallocene is a compound of the formula I
wherein M1 is a metal of group lVb, Vb or Vlb of the Periodic Table, R1 and R2 are identical or different and are a hydrogen atom, a C1-C10-alkyl group, a C1-C10-alkoxy group, a C6-C10-aryl group, a C6-C10-aryloxy group, a C2-C10-alkenyl group, a C7-C40-arylalkyl group, a C7-C40-alkylaryl group, a C8-C40-arylalkenyl group or a halogen atom, R3 and R4 are identical or different and are a hydrogen atom, a halogen atom, a C1-C10-alkyl group which may be halogenated, a C8-C10-aryl group, a -NR2 10, -SR10, -OSi-R3 10, -SiR3 10 or -PR2 10 radical, wherein R 10 is a halogen atom, a C1-C10-alkyl group or a C6-C10-aryl group, R5 and R6 are identical or different and have the meaning stated for R3 and R4, with the proviso that R5 and R6 are not hydrogen, R7 is =BR11, =AIR11, -Ge-, -Sn-, -O-, -S-, =SO, =SO2, -NR11, =CO, =PR11 or =P(O)R11, wherein R11, R12 and R13 are identical or different and are a hydrogen atom, a halogen atom, a C1-C10-alkyl group, a C1-C10-fluoroalkyl group, a C6-C10-aryl group, a C6-C10-fluoroaryl group, a C1-C10-alkoxy group, C2-C10-alkenyl group, a C7-C40-arylalkyl group, C8-C40-arylalkenyl group or a C7-C40-alkylaryl group, or R11 and R12 or R11 and R13, together with the atoms binding them, each form a ring, M2 is silicon, germanium or tin, R8 and R9 are identical or different and have the meaning stated for R11 and m and n are identical or different and are zero, 1 or 2, m plus n being zero, 1 or 2.
2. The process as claimed in claim 1, wherein M1 is Zr or Hf, R1 and R2 are identical or different and are methyl or chlorine, R3 and R4 are hydrogen, R5 and R6 are identical or different and are methyl, ethyl or trifluoromethyl, R7 is and n plus m is zero or 1.
3. The process as claimed in claims 1 or 2, wherein the compound of the formula 1 is rac-dimethylsilyl(2-methyl-1-indenyl)2zirconium dichloride, rac-ethylene(2-methyl-1-indenyl)2Zirconium dichloride, rac-dimethylsilyl(2-methyl-1-indenyl)2Zirconiumdimethyl, rac-ethylene(2-methyl-1-indenyl)2zirconiumdimethyl , rac-phenyl(methyl)silyl(2-methyl-1-indenyl)2zirconiumdimethyl, rac-diphenyl-silyl(2-methyl-1-indenyl)2zirconium dichloride, rac-methylethylene(2-methyl-1-indenyl)2zirconium dichloride or rac-dimethylsilyl(2-ethyl-1-indenyl)2Zirconium dichloride.
4. The process as claimed in claim any one of claims 1 to 3, wherein p is an integer from 10 to 35.
5. The process as claimed in any one of claims 1 to 4, in which the metallocene is applied to a support.
6. The process as claimed in any one of claims 1 to 5, in which the metallocene is prepolymerized.
7. A use of a catalyst which is composed of a metallocene of the formula f as claimed in any one of claims 1 to 3 as the transition metal compound and a cocatalyst, the cocatalyst being an aluminoxane of formula (II) as claimed in anvone of claims 1 to 4, and /or a salt-like compound of the formula R XNH4xBR'4 or of the formula R3PHBR'4 in which x is 1, 2 or 3, the radicals R are identical or different and are an alkyl group or an aryl group and R' is aryl, which may also be fluorinated or partially fluorinated, for the polymerization or copolymerization of an olefin of the formula R a-CH=CH-R b, in which R a and R b are identical or different and are a hydrogen atom or a hydrocarbon radical having 1 to 14 C atoms, or R a and R b, together with the atoms binding them, may form a ring.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEP4035886.0 | 1990-11-12 | ||
| DE4035886 | 1990-11-12 |
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| CA2055216A1 CA2055216A1 (en) | 1992-05-13 |
| CA2055216C true CA2055216C (en) | 2004-02-10 |
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| CA002055216A Expired - Fee Related CA2055216C (en) | 1990-11-12 | 1991-11-08 | Process for the preparation of a high molecular weight olefin polymer |
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| Country | Link |
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| EP (1) | EP0485822B1 (en) |
| JP (1) | JP3362153B2 (en) |
| AU (1) | AU640286B2 (en) |
| CA (1) | CA2055216C (en) |
| DE (1) | DE59107973D1 (en) |
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| EP3694811B1 (en) | 2017-10-11 | 2024-04-03 | Basell Polyolefine GmbH | Supported catalyst system |
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| WO2019173030A1 (en) | 2018-03-08 | 2019-09-12 | Exxonmobil Chemical Patents Inc. | Methods of preparing and monitoring a seed bed for polymerization reactor startup |
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Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3904468A1 (en) * | 1989-02-15 | 1990-08-16 | Hoechst Ag | POLYPROPYLENE WAX AND METHOD FOR THE PRODUCTION THEREOF |
-
1991
- 1991-11-01 DE DE59107973T patent/DE59107973D1/en not_active Expired - Lifetime
- 1991-11-01 ES ES91118681T patent/ES2091273T3/en not_active Expired - Lifetime
- 1991-11-01 EP EP91118681A patent/EP0485822B1/en not_active Expired - Lifetime
- 1991-11-08 CA CA002055216A patent/CA2055216C/en not_active Expired - Fee Related
- 1991-11-11 ZA ZA918925A patent/ZA918925B/en unknown
- 1991-11-11 JP JP29468691A patent/JP3362153B2/en not_active Expired - Fee Related
- 1991-11-11 AU AU87759/91A patent/AU640286B2/en not_active Ceased
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8153745B2 (en) | 2006-04-18 | 2012-04-10 | Borealis Technology Oy | Multi-branched polypropylene |
Also Published As
| Publication number | Publication date |
|---|---|
| AU8775991A (en) | 1992-05-14 |
| AU640286B2 (en) | 1993-08-19 |
| ZA918925B (en) | 1992-07-29 |
| EP0485822B1 (en) | 1996-07-03 |
| EP0485822A3 (en) | 1992-11-25 |
| CA2055216A1 (en) | 1992-05-13 |
| EP0485822A2 (en) | 1992-05-20 |
| JPH04268307A (en) | 1992-09-24 |
| ES2091273T3 (en) | 1996-11-01 |
| DE59107973D1 (en) | 1996-08-08 |
| JP3362153B2 (en) | 2003-01-07 |
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