CA2192771C - Process for preparing a cycloolefin copolymer - Google Patents
Process for preparing a cycloolefin copolymer Download PDFInfo
- Publication number
- CA2192771C CA2192771C CA002192771A CA2192771A CA2192771C CA 2192771 C CA2192771 C CA 2192771C CA 002192771 A CA002192771 A CA 002192771A CA 2192771 A CA2192771 A CA 2192771A CA 2192771 C CA2192771 C CA 2192771C
- Authority
- CA
- Canada
- Prior art keywords
- eta
- dimethylamido
- propylidene
- bis
- zirconium bis
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F10/14—Monomers containing five or more carbon atoms
-
- 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
- C08F232/00—Copolymers of cyclic compounds containing no unsaturated aliphatic radicals in a side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic ring system
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F17/00—Metallocenes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F210/02—Ethene
-
- 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
- C08F4/642—Component covered by group C08F4/64 with an organo-aluminium compound
- C08F4/6428—Component covered by group C08F4/64 with an organo-aluminium compound with an aluminoxane, i.e. a compound containing an Al-O-Al- group
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F4/00—Polymerisation catalysts
- C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
- C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
- C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
- C08F4/62—Refractory metals or compounds thereof
- C08F4/64—Titanium, zirconium, hafnium or compounds thereof
- C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
- C08F4/6592—Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring
- C08F4/65922—Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring containing at least two cyclopentadienyl rings, fused or not
- C08F4/65927—Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring containing at least two cyclopentadienyl rings, fused or not two cyclopentadienyl rings being mutually bridged
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S526/00—Synthetic resins or natural rubbers -- part of the class 520 series
- Y10S526/943—Polymerization with metallocene catalysts
Abstract
The present invention relates to a process for preparing a cycloolefin copolymer by polymerization of at least one cyclic olefin and at least one acyclic olefin in the presence of a catalyst comprising at least one metallocene compound of the formula I, where L is a n-ligand, L' is a .pi.-ligand, T is a bridge between L and L', M
is a tetravalent transition metal, m is 1 or 2 and R1, R2, R3 and R4 are, independently of one another, identical or different and are each a hydrogen atom or a C1-C20-hydrocarbon radical.
is a tetravalent transition metal, m is 1 or 2 and R1, R2, R3 and R4 are, independently of one another, identical or different and are each a hydrogen atom or a C1-C20-hydrocarbon radical.
Description
_ 219277 HOECHST AKTIENGESELLSCHAFT HOE 95/F 285 Dr. LV/rh Description Process for preparing a cycloolefin copolymer The present invention relates to a process for preparing a cycloolefin copolymer in the presence of a metallocene compound.
Metallocene compounds of the 4th transition group of the Periodic Table of the Elements are, in combination with methylaluminoxane (MAO), active catalysts for the polymerization of olefins. The literature discloses the preparation of polyolefins using soluble metallocene compounds in combination with aluminoxanes or other cocatalysts which, owing to their Lewis acidity, can convert the neutral metallocene into a ration and stabilize it (EP-A-129 368).
Metallocene and semisandwich complexes are of great interest not only in respect of the polymerization or oligomerization of olefins. They can also be used as hydrogenation, epoxidation, isomerization and C-C coupling catalysts CChem.
Rev.
1992, 92, 965-994).
It is known from the literature that CpH can be reacted with zirconium or hafnium dimethyltetraamide, directly and without addition of a base, to give metallocenes of the type described in EP-A-595 390 and EP-A-283 164 (J. Chem. Soc. (A), 1968, 1940-1945). Furthermore, it is known that cycloolefi~n copolymers can be prepared in the presence of bridged metallocenes (EP-A-283 164, EP-A-407 870). It is an object of the invention to provide an economical process for preparing cycloolefin copolymers. This object is achieved by the present invention.
The present invention accordingly provides a process for preparing a cycloolefin copolymer by polymerization of at least one cyclic olefin and at least one acyclic olefin in the presence of a catalyst comprising at least one metallocene compound of the formula I, ~i92~71 T ~M~ (I) L, ~ ~ NR3R4 m where L is a n-ligand, L' is a n-ligand, T is a bridge between L and L', M is a tetravalent transition metal, m is 1 or 2 and R~, R2, R3 and R4 are, independently of one another, identical or different and are each a hydrogen atom or a C~-C2o-hydrocarbon radical.
M is preferably titanium, zirconium, hafnium, vanadium, niobium, tantalum, scandium, yttrium or a rare earth metal, particularly preferably titanium, zirconium or hafnium. L is preferably a substituted or unsubstituted cyclopentadienyl group. L' is preferably a substituted or unsubstituted cyclopentadienyl group. When m = 1, T is preferably [RSRsX]~, where X are, independently of one another, identical or different and are carbon, silicon, germanium or tin, the radicals R5 and Rs are, independently of one another, identical or different and are each a hydrogen atom or a C~-C3o- hydrocarbon radical such as C~-C2o-alkyl or Cs-C2o-aryl and n is 1, 2, 3 or 4, preferably 1 or 2. When m = 2, T is preferably carbon, silicon, germanium or tin.
R~ and R3 are, independently of one another, identical or different and are each a hydrogen atom or a C~-C2o-hydrocarbon radical, preferably a C~-C2o-hydrocarbon radical such as C~-CZO-alkyl or C6-C~4-aryl, in particular methyl.
R2 and R4 are, independently of one another, identical or different and are preferably each a C~-CZO-hydrocarbon radical such as C~-C2o-alkyl or Cs-C~4-aryl, in particular methyl.
~192~71 The radicals R~, R2, R3 and R4 are, independently of one another, identical or different. Preferably, the radicals R~, R2, R3 and R4 are identical and are C~-C2o-alkyl or Cs-C~4-aryl, in particular methyl.
Examples of substituted cyclopentadienyl groups L or L' are:
tetramethylcyclopentadienyl, methylcyclopentadienyl, methyl-tert-butylcyclopentadienyl, tert-butylcyclopentadienyl, isopropylcyclopentadienyl, dimethylcyclopentadienyl, trimethylcyclopentadienyl, trimethylethylcyclopentadienyl, phenylcyclopentadienyl, diphenylcyclopentadienyl, indenyl, 2-methylir,~enyl, 2-ethylindenyl, 3-methylindenyl, 3-tert-butylindenyl, 3-trimethylsilylindenyl, 2-methyl-4-phenylindenyl, 2-ethyl-4-phenylindenyl, 2-methyl-4-naphthylindenyl, 2-methyl-4-isopropylindenyl, 4,5-benzoindenyl, 2-methyl-4,5-benzoindenyl, 2-methyl-a-acenaphthindenyl, 2-methyl-4,6-diisopropylindenyl, fluorenyl, 4-methylfluorenyl or 2,7-di-tert-butylfluorenyl.
Examples of bridges T are:
dimethylsilanediyl, methylphenylsilanediyl, diphenylsilanediyl, dimethylgermanediyl, 1,2-tetramethyldisilanediyl, 1,2-ethylidene, 1,2-propylidene, 1,2-butylidene, 1,3-propylidene, 1,4-butylidene or 2,2-propylidene.
Examples of metallocene compounds of the formula I are:
bis(dimethylamido)[r~5: n5-2,2-(cyclopentadienyl)(indenyl)propylidene)]-zirconium bis(dimethylamido)[r)5:n5-2,2-(cyclopentadienyl)(indenyl)propylidene)]-hafnium bis(dimethylamido)[05:05-2,2-(cyclopentadienyl)(fluorenyl)propylidene)]-zirconium bis(dimethylamido)[~S:rIS-2,2-(cyclopentadienyl)(fluorenyl)propylidene)]-hafnium bis(dimethylamido)[rt5: rt5-2,2-(fluorenyl)(indenyl)propylidene)]zirconium bis(dimethylamido)[rt5: r~5-2,2-(fluorenyl)(indenyl)propylidene)]hafnium bis(dimethylamido)[r)5:~5-2,2-(methylcyclopentadienyl)(indenyl)propyli-dene)]zirconium bis(dimethylamido)[~5: ~5-2,2-(methylcyclopentadienyl)(fluorenyl)propyli-dene)]-zirconium 2192~1~
bis(dimethylamido)(n5: n5-2,2-(fluorenyl)(2-methylindenyl)propylidene)]-zirconium bis(dimethylamido)[~5: n5-2,2-(tetramethylcyclopentadienyl)(indenyl)-propylidene)]zirconium bis(dimethylamido)[~5: n5-2,2-(tetramethylcyclopentadienyl)(fluorenyl)-propylidene)]zirconium bis(dimethylamido)(n5: n5-2,2-(fluorenyl)(2-ethylindenyl)propylidene)]-zirconium bis(dimethylamido)[n5: n5-2,2-(cyclopentadienyl)(2-methylindenyl)-propylidene)]zirconium bis(dimethylamido)[ns: ~5-2,2-(cyclopentadienyl)(2-ethylindenyl)-propylidene)]zirconium bis(dimethylamido)[ris: ~5-2,2-(cyclopentadienyt)(3-trimethylsilylindenyl)-propylidene)]zirconium bis(dimethylamido)[rt5: ~5-2,2-(methylcyclopentadienyl)(2-methylindenyl)-propylidene)]zirconium bis(dimethylamido)[ri5:n5-2,2-(methylcyclopentadienyl)(2-ethylindenyl)-propylidene)]zirconium bis(dimethylamido)[~5: ~5-2,2-(methylcyclopentadienyl)(3-trimethylsilyl-indenyl)propylidene)]zirconium bis(dimethylamido)[dimethylsilanediyl(rts: ~5-(cyclopentadienyl)(indenyl)]-zirconium bis(dimethylamido)(dimethylsilanediyl(~S:r)5-(cyclopentadienyl)(indenyl)]-zirconium bis(dimethylamido)[dimethylsilanediyl(rt5: rt5-(fluorenyl)(indenyl)]zirconium bis(dimethylamido)[dimethylsilanediyl(~5: ~s-2,2-(methylcyclopentadienyl)-(indenyl))]zirconium bis(dimethylamido)[dimethylsilanediyl(n5: n5-2,2-(methylcyclopentadienyl)-(fluorenyl))]zirconium bis(dimethylamido)[dimethylsilanediyl(~5: n5-2,2-(fluorenyl)(2-methyl-indenyl))]zirconium bis(dimethylamido)[dimethylsilanediyl(n5: r~5_2,2-(tetramethylcyclopenta-dienyl)(indenyl))]zirconium bis(dimethylamido)[dimethylsilanediyl(n5:r~5_2,2_(tetramethylcyclopenta-dienyl)(fluorenyl))]zirconium bis(dimethylamido)[dimethylsilanediyl(r~5: n5-2,2-(fluorenyl)(2-ethylindenyl))]-zirconiu m 2I92~7~
bis(dimethylamido)[dimethylsilanediyl(~5:~5-2,2-(cyclopentadienyl)(2-methylindenyl)))zirconium bis(dimethylamido)[dimethylsilanediyl(~5:n5-2,2-(cyclopentadienyl)(2-ethyl-indenyl))]zirconium 5 bis(dimethylamido)[dimethylsilanediyl(~5:rt5-2,2-(cyclopentadieny1)(3-trimethylsilylindenyl))]zirconium bis(dimethylamido)[dimethylsilanediyl(n5: ~5-2,2-(methylcyclopentadienyl)-(2-methylindenyl))Jzirconium bis(dimethylamido)[dimethylsilanediyl(rt5: n5-2,2-(methylcyclopentadienyl)-(2-ethylindenyl))]zirconium bis(dimethylamido)[dimethylsilanediyl(n5: ~5-2,2-(methylcyclopentadienyl)-(3-trimethylsilylindenyl))]zirconium stanntetraylbis[(rt5: n5-bis(cyclopentadienyl)bis(dimethylamido)zirconium].
The preferred form of metallocene compound of the formula (I) used in the process of the invention is a metallocene compound of the formula (II) 5 6 Ind~ /NR1R2 R R C /M~ 3 4 k 1 Cp NR R
m where Cp is an unsubstituted or substituted cyclopentadienyl group, Ind is unsubstituted or substituted indenyl, M is a tetravalent transition metal, R~, R2, R3 and R4 are, independently of one another, identical or different and are each a hydrogen atom or a C~-C2o-hydrocarbon radical, R5 and R6 are, independently of one another, identical or different and are each a hydrogen atom or a C~-C3o-hydrocarbon radical, m is 1 or 2 and k and I are 1 when m is 1 and k and I are zero when m is 2.
In formula II, M is preferably titanium, zirconium, hafnium, vanadium, niobium, tantalam, scandium, yttrium or a rare earth metal, particularly preferably titanium, zirconium or hafnium.
Cp is an unsubstituted or substituted cyclopentadienyl group.
Examples of substituted cyclopentadienyl groups Cp are:
tetramethylcyclopentadienyl, methylcyclopentadienyl, methyl-tert-butylcyclopentadienyl, tert-butylcyclopentadienyl, isopropylcyclopentadienyl, dimethylcyclopentadienyl, trimethylcyclopentadienyl, trimethylethylcyclopentadienyl, phenylcyclopentadienyl, diphenylcyclopentadienyl, indenyl, 2-methylindenyl, 2-ethylindenyl, 3-methylindenyl, 3-tert-butylindenyl, 3-trimethylsilylindenyl, 2-Methyl-4-phenylindenyl, 2-ethyl-4-phenylindenyl, 2-methyl-4-naphthylindenyl, 2-methyl-4-isopropylindenyl, 4,5-benzoindenyl, 2-methyl-4,5-benzoindenyl, 2-methyl-a-acena~hthindenyl, 2-methyl-4,6-diisopropylindenyl, fluorenyl, 4-methylfluorenyl or 2,7-di-tert-butylfluorenyl.
Ind is unsubstituted or substituted indenyl. Examples of substituted indenyl are:
2-methylindenyl, 2-ethylindenyl, 3-methylindenyl, 3-tert-butylindenyl, 3-trimethylsilylindenyl, 2-methyl-4-phenylindenyl, 2-ethyl-4-phenylindenyl, 2-methyl-4-naphthylindenyl, 2-methyl-4-isopropylindenyl, 4,5-benzoindenyl, 2-methyl-4,5-benzoindenyl, 2-methyl-a-acenaphthindenyl, 2-methyl-4,6-diisopropylindenyl. Ind is preferably unsubstituted indenyl.
The radicals R5 and Rs are, independently of one another, identical or different, preferably identical, and are each a hydrogen atom or a C~-C3o-hydrocarbon radical such as C~-CZO-alkyl or Cs-C2o-aryl. Preferably, R5 and R6 are methyl or phenyl, in particular methyl.
R~ and R3 are, independently of one another, identical or different and are each a h dro en atom or a C -C h drocarbon radical, preferabl a C -C -h drocarbon Y 9 ~ 20- Y Y ~ 2o Y
radical such as C~-C2o-alkyl or C6-C~4-aryl, in particular methyl.
R2 and R4 are, independently of one another, identical or different and are preferably a C~-C2o-hydrocarbon radical such as C~-C2o-alkyl or C6-C~4-aryl, in particular methyl.
2?9277?
The radicals R~, R2, R3 and R4 are, independently of one another, identical or different. Preferably, the radicals R~, R2, R3 and R4 are identical and are each a C~-C2o-hydrocarbon radical such as C~-CZO-alkyl or C6-C~4-aryl, in particular methyl.
Examples of metallocene compounds of the formula II are:
bis(dimethylamido)[n5: rt5-2,2-(cyclopentadienyl)(indenyl)propylidene)]-zirconium bis(dimethylamido)(ns: r15-2,2-(cyclopentadienyl)(indenyl)propylidene)]-hafnium bis(dimethylamido)[n5: rt5-2,2-(fluorenyl)(indenyl)propylidene]zirconium bis(dimethylamido)[~5: ~5-2,2-(fluorenyl)(indenyl)propylidene)]hafnium bis(dimethylamido)[~5: rt5-2,2-(methylcyclopentadienyl)(indenyl)-propylidene)]zirconium bis(dimethylamido)[05:rt5-2,2-(fluorenyl)(2-methylindenyl)propylidene)]-zirconium bis(dimethylamido)[O5: rl5-2,2-(tetramethylcyclopentadienyl)(indenyl)-propylidene)]zirconium bis(dimethylamido)[n5: ~5-2,2-(fluorenyl)(2-ethylindenyl)propylidene)]-zirconium bis(dimethylamido)[r~5: rt5-2,2-(cyclopentadienyl)(2-methylindenyl)-propylidene)]zirconium bis(dimethylamido)[rt5: ~5-2,2-(cyclopentadienyl)(2-ethylindenyl)-propylidene)]zirconium bis(dimethylamido)[rt5: n5-2,2-(cyclopentadienyl)(3-trimethylsilylindenyl)-propylidene)]zirconium bis(dimethylamido)[~5: n5-2,2-(methylcyclopentadienyl)(2-methylindenyl)-propylidene)]zirconium bis(dimethylamido)[rt5:~5-2,2-(methylcyclopentadienyl)(2-ethylindenyl)-propylidene)]zirconium bis(dimethylamido)[rt5: ~5-2,2-(methylcyclopentadienyl)(3-trimethylsilyl-indenyl)propylidene)]zirconium bis(dimethylamido)[n5:~5-2,2-(2-methylindenyl)(indenyl)-propylidene)]zirconium bis(dimethylamido)(n5:n5-2,2-bis(indenyl)propylidene)]zirconium.
The metallocene compound of the formula I or II can be prepared by reacting a compound of the formula III, where L is a rr-ligand, L' is a n-ligand, T is a bridge and 2~9277i s m is 1 or 2, with a compound of the formula IV, where M is a tetravalent metal and R~, R2, R3 and R4 are, independently of one another, identical or different and are each a hydrogen atom or a C~-C2o-hydrocarbon radical LH
T M(NR12NR22NR32NR42) ~L'H
m (III) ( The reaction is preferably carried out in an aprotic solvent such as toluene or hexane. The temperature can be between -78 and 140°C, preferably from 0°C to 110°C. The compound of the formula III can be used in excess;
preference is given to using 1 equivalent of the compound of the formula III and 1 equivalent of the metal tetramide of the formula IV.
Methods of preparing compounds of the formula III are known CChem. Ber. 1990, 123, 1649-1651 ). Methods of preparing compounds of the formula IV are likewise known (J. Chem. Soc. 1960, 3857-3861 ).
In the process of the invention, preference is given to using a catalyst which comprises at least one metallocene compound of the formula I and at least one cocatalyst. It is also possible to use mixtures of two or more metallocene compounds, in particular for preparing reactor blends or cycloolefin copolymers having a broad or multimodal molecular weight distribution.
A suitable cocatalyst in the process of the invention is in principle any compound which, owing to its Lewis acidity, cari convert the neutral metallocene compound into a ration and stabilize the latter ("labile coordination"). In addition, the cocatalyst or the anion formed therefrom should undergo no further reactions with the ration formed (EP-A-427 697). As cocatalyst, preference is given to using an aluminum compound and/or a boron compound.
The boron compound preferably has the formula RaXNH4_XBRb4, RaXPH4_xBRb4, Ra3CBRb~ or BRb3, where x is from 1 to 4, preferably 3, the radicals Ra are identical or different, preferably identical, and are C~-Coo-alkyl or Cs-C~8-aryl, or two radicals Ra together with the atoms connecting them form a ring, and the radicals Rb are identical or different, preferably identical, and are Cs-C~8-aryl which may be substituted by alkyl, haloalkyl or fluorine. In particular, Ra is ethyl, propyl, butyl or phenyl and Rb is phenyl, pentafluorophenyl, 3,5-bis(trifluoromethyl)phenyl, mesityl, xylyl or tolyl (EP-A-277 003, EP-A-277 004 and EP-A-426 638).
The cocatalyst used is preferably an aluminum compound such as aluminoxane and/or an aluminum alkyl.
The cocatalyst used is particularly preferably an aluminoxane, in particular of the formula Va for the linear type and/or the formula Vb for the cyclic type, Rc Rc R
A1 O A1O A1 ~ (Va) R~ p Rc Rc '- -' p+2 (Vb) where, in the formulae Va and Vb, the radicals R~ are identical or different and are each hydrogen or a C~-C2o-hydrocarbon group such as a C~-C~8-alkyl group, a C6-C~$-aryl group or benzyl and p is an integer from 2 to 50, preferably from 10 to 35.
The radicals R~ are preferably identical and are hydrogen, methyl, isobutyl, phenyl or benzyl, particularly preferably methyl.
~i~2~~~
If the radicals R~ are different, then they are preferably methyl and hydrogen or alternatively methyl and isobutyl, with hydrogen or isobutyl preferably being present in a proportion of from 0.01 to 40% by number (of the radicals R°).
5 The methods of preparing the aluminoxanes are known. The exact spatial structure of the aluminoxanes is not known (J. Am. Chem. Soc. (1993) 115, 4971 ). For example, it is conceivable that chains and rings can join to form larger two-dimensional or three-dimensional structures.
10 Regardless of the method of preparation, all aluminoxane solutions';ave in common a varying content of unreacted aluminum starting compound, which is present in free form or as adduct.
It is possible to preactivate the metallocene compound with~a cocatalyst, in particular an aluminoxane, before use in the polymerization reaction. This significantly increases the polymerization activity. The preactivation of the metallocene compound is preferably carried out in solution. The metallocene compound is preferably dissolved in a solution of the aluminoxane in an inert hydrocarbon. Suitable inert hydrocarbons are aliphatic or aromatic hydrocarbons.
Preference is given to using toluene.
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, in each case based on the total amount of solution. The metallocene compound can be used in the same concentration, but it is preferably used in an amount of from 10~ to 1 mol per mol of aluminoxane. The preactivation time is from 5 minutes to 60 hours, preferably from 5 to 60 minutes. The preactivation is carried out at a temperature of from -78 to 150°C, preferably from 0 to 80°C.
The metallocene compound is preferably employed in a concentration, based on the transition metal, of from 10-3 to 10-$ mol, preferably from 10~ to 10-7 mol, of transition metal per dm3 of solvent or per dm3 of reactor volume. The aluminoxane is preferably used in a concentration of from 10~ to 10-~ mol, preferably from 10-5 to 2?92771 10-2 mol, per dm3 of solvent or per dm3 of reactor volume. The other cocatalysts mentioned are used in approximately equimolar amounts to the metallocene compound. However, higher concentrations are also possible in principle.
The aluminoxane can be prepared in various ways by known methods. One of the methods is, for example, reacting an aluminum hydrocarbon compound and/or a hydridoaluminum hydrocarbon compound with water (gaseous, solid, liquid or bound - for example as water of crystallization) in an inert solvent such as toluene. To prepare an aluminoxane having different radicals R°, for example, two or more different trialkylaluminums corresponding to the desired composition are reacted with water (S. Pazynkiewicz, Polyhedron 9 (1990) 429, EP-A 302 424).
To remove catalyst poisons present in the olefin, purification using an aluminum compound, preferably an aluminum alkyl such as trimethylaluminum or triethylaluminum, is advantageous. This purification can be carried out either in the polymerization system itself or the olefin is brought into contact with the aluminum compound and subsequently separated off again before addition to the polymerization system.
In the process of the invention, the metallocene compound is preferably reacted with the cocatalyst outside the polymerization reactor in a separate step using a suitable solvent. Application to a support can be carried out during this step.
If solvent is added to the reaction mixture, this is a customary inert solvent such as an aliphatic or cycloaliphatic hydrocarbon, a petroleum or hydrogenated diesel oil fraction or toluene.
The metallocene compound of the formula I is preferably used in the form of its racemate. The metallocene compound is preferably employed in a concentration, based on the transition metal, of from 10-3 to 10-8 mol, preferably from 10~
to 10-~
mol, of transition metal per dm3 of reactor volume. The aluminoxane is used in a concentration of from 10 4 to 10-~ mol, preferably from 10~ to 2 * 10-2 mol, per dm3 of reactor volume, based on the aluminum content. However, higher concentrations are also possible in principle.
In the process of the invention, at least one cyclic, preferably polycyclic, olefin is polymerized together with at least one acyclic olefin. Polycyclic olefins preferably have the formulae VI, VII, VIII, IX, X or XI
R~
/CH\
HC/ \CH
R 9 - C - R 1 0 ( V I ) HC ~ CH
CH
/cH\ cH2 HC
i (VII) HC ~ H
~CH~~CH
R~
/CH CH
HC ~~ \CH~
R9-C-R10 R11-C-R12 (VIII) HC ~ ~ H CH
CH ~ ~ g CH R
2;92171 /CH ~ CH CH
HC / ~ \CH' \CH ~ R
R9-C-R10 R11_C_R12 ( R13_C_R14 (IX) HC ~ ~ H 'C /CH\
g CH CH CH R
/C H ~ /C H
HC / CH / CH
R9_C_R10 (X) HC\ ~ ~CH~ /CH
CH CH CH R~
HC~ \CH \CH \CH
R9_C_R110 R13_C_R14 (XI).
HC~ /CH\ /CH\ /CH\
\CH CH CH \R8 where R~, R8, R9, R~°, R~~, R~2, R~3 and R~4 are identical or different and are each a hydrogen atom or a C~-C2°-hydrocarbon radical such as C~-C8-alkyl or Cs-C~°-aryl, or two or more radicals R7-R~~ together form a C4-C4°-ring system, where identical radicals R~-R~~ in the various formulae can have a different meaning.
Particular preference is given to cycloolefins of the formulae VI or VIII, where R7, R8, R9, R~°, R~~, R~2, R~3 and R~4 are identical or different and are each a hydrogen atom or a C~-C2°-hydrocarbon radical, in particular a C6-C~°-aryl radical or a C~-C8-alkyl radical, where identical radicals R~-R~4 in the various formulae VI -XI can have a different meaning.
Acyclic olefins are preferably 1-olefins having from 1 to 40, preferably 1 -20, carbon atoms. Particular preference is given to 1-olefins of the formula (X11) C\ (XII) R1~ R18 where R~ 5, R~s, R~ ~ and R~ 8 are identical or different and are each a hydrogen atom or a C~-C2°-hydrocarbon radical, preferably a Cs-C~°-aryl radical and a C~-C$-alkyl radical. Examples of acyclic olefins are ethylene and propylene.
If desired, one or more monocyclic olefins, in particular of the formula (X111) CH CH (XIII) \
(CH2)n where n is from 2 to 10, are also used in the process of the invention.
In particular, copolymers of polycyclic olefins, preferably of thQ formulae VI
and VIII, with ethylene are prepared.
2i9277i Particularly preferred polycyclic olefins are norbornene and tetracyclododecene, with these being able to be substituted by (C~-C6)-alkyl. They are preferably copolymerized with ethylene; ethylene-norbornene copolymers are of particular importance.
In the process of the invention, the polycyclic olefin is preferably used in an amount of from 0.1 to 99.9% by weight, the monocyclic olefin in an amount of from 0 to 99.9% by weight and the acyclic olefin in an amount of from 0.1 to 99.9% by weight, in each case based on the total amount of monomers.
The concentration of the acyclic olefin used is given by its solubility in the reaction medium at a given pressure and a given temperature.
For the purposes of the present invention, polycyclic olefins, monocyclic olefins and acyclic olefins also include mixtures of two or more olefins of the respective type.
This means that, apart from polycyclic bicopolymers, it is also possible to prepare tercopolymers and multicopolymers by the process of the invention. Copolymers of monocyclic olefins and acyclic olefins can also be obtained by means of the process of the invention.
Among the monocyclic olefins, preference is given to cyclopentene which may be substituted.
The process of the invention is preferably carried out at temperatures of from -78 to 150°C, in particular from 0 to 100°C, and a presure of from 0.01 to 64 bar.
The polymerization is carried out in the liquid cycloolefin itself or in a cycloolefin solution, with the pressure advantageously being above 1 bar.
In the preparation of copolymers, the molar ratios of the polycyclic olefin to the open-chain olefin used can be varied within a wide range. Preference is given to using molar ratios of from 3:1 to 100:1 of cycloolefin to open-chain olefin.
Selection of the polymerization temperature, the concentration of the catalyst component and 2;92171 the molar ratio used or the pressure of the gaseous, open-chain olefin enables the proportion of comonomer incorporated to be controlled almost at will.
Preference is given to incorporation of between 20 and 80 mol% of the cyclic components and particular preference is given to incorporation of between 40 and 60 mol% of the cyclic components.
The polymerization can also be carried out in a plurality of stages, with block copolymers also being able to be formed (EP-A-560 090).
The mean molar mass of the polymer formed can also be controlled in a known manner by metering in hydrogen, varying the catalyst concentration or varying the temperature.
The polydispersity M~M~ of the cycloolefin copolymers is from 1.9 to 3.5 and the molecular weight distribution is therefore quite narrow. This results in a property profile which makes the cycloolefin copolymers particularly suitable for injection molding.
The process of the invention makes possible the preparation of amorphous cycloolefin copolymers which contain no partially crystalline ethylene polymers. The copolymers are transparent, hard and can be processed thermoplastically. The yield stresses (in accordance with DIN 53457) are in the range from 50 to 100 MPa, preferably between 55 and 70 MPa. Both during extrusion and during injection molding, no decomposition reactions or a drop in viscosity have been found at temperatures of 300°C.
The cycloolefin copolymers prepared according to the invention are particularly suitable for the production of shaped parts such as extruded parts (e.g.
films, hoses, tubes, rods and fibers) or injection-molded articles of any shape and size.
The films can be extruded films, calendered films, cast films, monoaxially and biaxially oriented films or multilayer films and are suitable, in particular, as food packaging films or blister packaging. They have a high barrier action against water 2?92771 and a low gas permeability. Cycloolefin copolymers prepared according to the invention are also suitable as an additive in other polymer films (in particular polyolefin films such as polypropylene films or polyethylene films), for example for the purposes of improving flow, improving the ability to apply a surface coating, influencing the modulus of elasticity and for producing opaque films.
An important property of the cycloolefin copolymers prepared according to the invention is their transparency. This makes the optical applications of the extruded or injection-molded parts produced from the cycloolefin copolymers particularly important. The index of refraction, determined using an Abbe refractometer and mixed light, of the reaction products described in the examples below is in the range between 1.520 and 1.555. Since the index of refraction is very close to that of crown glass (n = 1.51 ), the products according to the invention can be used as a substitute for glass in various applications, for example lenses, prisms, support plates and films for optical data storage, for video disks, for compact disks, as covering and focusing disks for solar cells, as covering and scattering disks for power optics, as optical waveguides in the form of fibers or films.
In impact-modified form, the cycloolefin copolymers prepared according to the invention can also be used as a structural material in various industrial fields (EP-A-566 988 ).
The cycloolefin copolymers obtained according to the invention can also be used for producing polymer alloys. The alloys can be produced in the melt or in solution. The alloys have, in each case, a property combination of the components which is favorable for certain applications. The following polymers are preferably used for alloys with the cycloolefin copolymers of the invention:
polyethylene, polypropylene, ethylene-propylene copolymers, polybutylene, poly(4-methyl-1-pentene), polyisoprene, polyisobutylene, natural rubber, poly(methyl methacrylate), further polymethacrylates, polyacrylates, acrylate-methacrylate copolymers, polystyrene, styrene-acrylonitrile copolymers, bisphenol A
polycarbonate, further polycarbonates, aromatic polyester carbonates, polyethylene terephthalate, polybutylene terephthalate, amorphous polyarylates, nylon 6, nylon 66, further polyamides, polyaramides, polyether ketones, polyoxymethylene, polyoxyethylene, polyurethanes, polysulfones, polyether sulfones, polyvinylidene fluoride.
The process of the invention proceeds with high activity and gives, in particular, transparent cycloolefin copolymers which have high tear strengths.
The glass transition temperatures Tg quoted in the following examples were determined by means of DSC (Differential Scanning Calorimetry) ~.: a heating rate of 20°C/min. The viscosity numbers quoted were determined in accordance with DIN
53728. The mechanical properties were measured in a tensile test (DIN 53457, Instron 4302).
The measure used for the catalyst activity was the yield of polymer per unit time and per mmol of metallocene:
Polymer [g]
Activity - ____________________________________________________________ _ A' Time [h] x amount of metallocene [mmol]
General procedures: Preparation and handling of organometallic compounds was carried out with exclusion of air and moisture under argon (Schlenk technique). All solvents required were freed of air and moisture before use by boiling for a number of hours over a suitable desiccant and subsequent distillation under argon.
The diketones and ketoaldehydes used as starting compounds were prepared by literature methods. Cyclopentadiene and methylcyclopentadiene were obtained by cracking of the dimers and were stored at -35°C.
The Al/CH3 ratio in the aluminoxane was determined by decomposition of the sample with HZS04 and determination of the volume of the hydrolysis gases formed _ 2~92i1~
under standard conditions and also by complexometric titration of the aluminum in the then dissolved sample using the Schwarzenbach method.
The compounds were characterized using'H-NMR, ~3C-NMR and IR spectroscopy.
The following examples illustrate the invention:
All glass apparatus was baked out in vacuo and flushed with argon. All operations were carried out with exclusion of moisture and oxygen in Schlenk vessels. The solvents used were distilled from a Na/K alloy under argon.
Toluene-soluble methylaluminoxane was used for the examples of polymerization as a 10% strength by weight toluene solution having a mean degree of oligomerization of n = 20 (Witco). The aluminum content determined was 36 mg of Allml.
Example 1 Bis(dirr~ethylamido)[n5:~5-2,2-(cyclopentadienyl)(indenyl)propylidenej-zirconium A solution of zirconium amide (416 mg, 1.55 mmol) in 25 ml of toluene is cooled to -78°C and subsequently a solution of 345 mg of the ligand in 10 ml of toluene is added dropwise. The solution is warmed to room temperature and after stirring for 12 hours is heated at 80°C for 3 hours. The solvent is removed under reduced pressure and the complex is obtained in the form of a yellow-orange solid in a yield of 99% (613 mg).
~ H-NMR (400 MHz, C6D6): b [ppm] = 1.57, 1.89 (s, 6H, C(CH3)2), 2.46, 2.81 (s, 12H, N(CH3)2), 5.29 (m, 1 H, CH in C5H4), 5.80 (m, 2H, CH in C5H4 and C9H~), 5.99 (m, 1 H, CH in CSH4), 6.08 (m, 1 H, CH in C5H4), 6.59 (d, 1 H, 3J(H,H) = 3.0 Hz, CH in C9H~), 6.69 (m, 1 H, CH in C9H~), 7.49 (m, 1 H, CH in C9H~), 7.62 (m, 1 H, CH
in C9H~).
MS (CI): m/e (%) = 708 (10) [2M+ - 2 NMe2], 398 (100) [M+], 355 (45) [M+ -NMe2], 311 (21 %) [M+ - 2 NMe2J.
._ 21927 i Example 2 Bis(dimethylamido)[r15:n5-2,2-(cyclopentadienyl)(indenyl)propylidene]- hafnium A solution of hafnium amide (833 mg, 1.55 mmol) in 25 ml of xylene is cooled to -5 78°C and subsequently a solution of 522 mg of the ligand in 10 ml of xylene is added dropwise. The solution is warmed to room temperature and after stirring for 2 hours is heated at 150°C for 8 hours. The solvent is removed under reduced pressure and the complex is recrystallized from a little pentane. The complex precipitates in the form of a yellow-orange solid (95% yield, 613 mg).
~ H-NMR (400 MHz, C6D6): b [ppm] = 1.57, 1.88 (s, 6H, C(CH3)2), 2.51, 2.85 (s, 12H, N(CH3)2), 5.29 (m, 1 H, CH in C5H4), 5.70 - 5.80 (m, 2H, CH in C5H4 and C9H~), 6.00 (m, 1 H, CH in C5H4), 6.04 (m, 1 H, CH in C5H4), 6.53 (d, 1 H, 3J(H,H) = 3.0 Hz, CH in C9H~), 6.71 (m, 1 H, CH in C9H7), 6.87 (m, 1 H, CH in C9H7), 7.49 (m, 1 H, CH
in C9H~), 7.63 (m, 1 H, CH in C9H~).
MS (CI): mle (%) = 620 (100), 600 (18), 512 (24), 497 (28), 442 (17), 399 (25), 222 (26), 207 (26), 115 (8), 107 (20).
Polymerization Examples Example A:
A 1.5 dm3 autoclave which has been thoroughly flushed beforehand with ethene is charged with 600 cm3 of an 85% strength by weight solution of norbornene in toluene. The solution was saturated with ethene by repeated pressurization with ethene (6 bar). 5 cm3 of methylaluminoxane solution in toluene (10.1 %
strength by weight solution of methylaluminoxane having a molar mass of 1300 g/mol determined by cryoscopy) were metered in countercurrent into the reactor thus prepared and the mixture was stirred for 30 minutes at 70°C. A solution of 1.5 mg of bis(dimethylamido)[~5:n5-2,2-(cyclopentadienyl)indenyl)-propylidene]zirconium (I) in 5 cm3 of a solution of methylaluminoxane in toluene was added after a preactivation 2~~~~7~
time of 15 minutes. (If hydrogen regulation is to be used, hydrogen can be injected at this point.) Polymerization was carried out for one hour at 70°C while stirring (750 rpm), with the ethene pressure being maintained at 6 bar by metering in further amounts.
At the end of the reaction time, the polymerization mixture was drained into a vessel and immediately introduced into 5 dm3 of acetone, stirred for 10 minutes and the precipitated product was subsequently filtered off. The filter cake was washed alternately with three portions of 10% strength hydrochloric acid and three portions of acetone. Finally, it was washed with water until neutral, the residue was slurried in acetone and filtered again. The polymer thus purified was dried for 15 hours at a 80 C under reduced pressure (0.2 bar).
Drying gave 44 g of colorless polymer which had a glass transition temperature of 193°C, a viscosity number of 69 cm3/g, a yield stress of 64 MPa and an elongation at break of 3.3%. The activity A was 10842 g of polymer/h x mmol.
Example B:
Example A was repeated at an ethylene pressure of 18 bar and a polymerization temperature of 90°C. The yield of purified and dried polymer was 152 g.
The polymer had a glass transition temperature of 150°C, a viscosity number of 70 cm3lg, a yield stress of 62 MPa and an elongation at break of 3.5%. The activity A
was 56182 g of polymer/h x mmol.
Example C:
The procedure of Example B was repeated, but the metallocene used was 0.5 mg of isopropylidenebis(1-indenyl)bis(N,N-dimethylamido)zirconium (II). This gave g of purified and dried polymer having a glass transition temperature of 143°C, a viscosity number of 152 cm3/g.
~~92771 Example D:
The procedure of Example A was repeated, but the metallocene used was 0.1 mg of dimethylsilanediyl(9-(2,7-di-tert-butyl)fluorenyl)cyclopentadienyl-bis(N,N-dimethylamido)zirconium (III). This gave 17 g of purified and dried polymer having a glass transition temperature of 143°C and a viscosity number of 267 cm3/g.
Example E:
The procedure of Example A was repeated, but the metallocene used was 0.2 mg of isopropylidene(9-fluorenyl)cyclopentadienyl-bis(N,N-dimethylamido)zirconium (IV).
This gave 64 g of purified and dried polymer having a glass transition temperature of 151 °C and a viscosity number of 147 cm3/g.
L L L L L
_ _ _ _ _ O C O C O C O C O C
L O O ~ O ~ O ~ O ~ O
' ::.~ ~. ' ~.W . w :..
N p i p i p n p V~ 7 N p o ~ o N o U o N o~
N
O V M O M M
o O
O
O N
U
U a7 ~ tp ~ ~ C~O
v r r.
O C
C ~ ~ N
N ~ ~ ~ l~
p E ~ O O O
E
a C
a ~ ~ m ~ ~ ~o m L O
w a a O ~ ~ O O
H
p c a~
O C
U
.L O - -cv O
_N
Q
a m v o w x w ~n o
Metallocene compounds of the 4th transition group of the Periodic Table of the Elements are, in combination with methylaluminoxane (MAO), active catalysts for the polymerization of olefins. The literature discloses the preparation of polyolefins using soluble metallocene compounds in combination with aluminoxanes or other cocatalysts which, owing to their Lewis acidity, can convert the neutral metallocene into a ration and stabilize it (EP-A-129 368).
Metallocene and semisandwich complexes are of great interest not only in respect of the polymerization or oligomerization of olefins. They can also be used as hydrogenation, epoxidation, isomerization and C-C coupling catalysts CChem.
Rev.
1992, 92, 965-994).
It is known from the literature that CpH can be reacted with zirconium or hafnium dimethyltetraamide, directly and without addition of a base, to give metallocenes of the type described in EP-A-595 390 and EP-A-283 164 (J. Chem. Soc. (A), 1968, 1940-1945). Furthermore, it is known that cycloolefi~n copolymers can be prepared in the presence of bridged metallocenes (EP-A-283 164, EP-A-407 870). It is an object of the invention to provide an economical process for preparing cycloolefin copolymers. This object is achieved by the present invention.
The present invention accordingly provides a process for preparing a cycloolefin copolymer by polymerization of at least one cyclic olefin and at least one acyclic olefin in the presence of a catalyst comprising at least one metallocene compound of the formula I, ~i92~71 T ~M~ (I) L, ~ ~ NR3R4 m where L is a n-ligand, L' is a n-ligand, T is a bridge between L and L', M is a tetravalent transition metal, m is 1 or 2 and R~, R2, R3 and R4 are, independently of one another, identical or different and are each a hydrogen atom or a C~-C2o-hydrocarbon radical.
M is preferably titanium, zirconium, hafnium, vanadium, niobium, tantalum, scandium, yttrium or a rare earth metal, particularly preferably titanium, zirconium or hafnium. L is preferably a substituted or unsubstituted cyclopentadienyl group. L' is preferably a substituted or unsubstituted cyclopentadienyl group. When m = 1, T is preferably [RSRsX]~, where X are, independently of one another, identical or different and are carbon, silicon, germanium or tin, the radicals R5 and Rs are, independently of one another, identical or different and are each a hydrogen atom or a C~-C3o- hydrocarbon radical such as C~-C2o-alkyl or Cs-C2o-aryl and n is 1, 2, 3 or 4, preferably 1 or 2. When m = 2, T is preferably carbon, silicon, germanium or tin.
R~ and R3 are, independently of one another, identical or different and are each a hydrogen atom or a C~-C2o-hydrocarbon radical, preferably a C~-C2o-hydrocarbon radical such as C~-CZO-alkyl or C6-C~4-aryl, in particular methyl.
R2 and R4 are, independently of one another, identical or different and are preferably each a C~-CZO-hydrocarbon radical such as C~-C2o-alkyl or Cs-C~4-aryl, in particular methyl.
~192~71 The radicals R~, R2, R3 and R4 are, independently of one another, identical or different. Preferably, the radicals R~, R2, R3 and R4 are identical and are C~-C2o-alkyl or Cs-C~4-aryl, in particular methyl.
Examples of substituted cyclopentadienyl groups L or L' are:
tetramethylcyclopentadienyl, methylcyclopentadienyl, methyl-tert-butylcyclopentadienyl, tert-butylcyclopentadienyl, isopropylcyclopentadienyl, dimethylcyclopentadienyl, trimethylcyclopentadienyl, trimethylethylcyclopentadienyl, phenylcyclopentadienyl, diphenylcyclopentadienyl, indenyl, 2-methylir,~enyl, 2-ethylindenyl, 3-methylindenyl, 3-tert-butylindenyl, 3-trimethylsilylindenyl, 2-methyl-4-phenylindenyl, 2-ethyl-4-phenylindenyl, 2-methyl-4-naphthylindenyl, 2-methyl-4-isopropylindenyl, 4,5-benzoindenyl, 2-methyl-4,5-benzoindenyl, 2-methyl-a-acenaphthindenyl, 2-methyl-4,6-diisopropylindenyl, fluorenyl, 4-methylfluorenyl or 2,7-di-tert-butylfluorenyl.
Examples of bridges T are:
dimethylsilanediyl, methylphenylsilanediyl, diphenylsilanediyl, dimethylgermanediyl, 1,2-tetramethyldisilanediyl, 1,2-ethylidene, 1,2-propylidene, 1,2-butylidene, 1,3-propylidene, 1,4-butylidene or 2,2-propylidene.
Examples of metallocene compounds of the formula I are:
bis(dimethylamido)[r~5: n5-2,2-(cyclopentadienyl)(indenyl)propylidene)]-zirconium bis(dimethylamido)[r)5:n5-2,2-(cyclopentadienyl)(indenyl)propylidene)]-hafnium bis(dimethylamido)[05:05-2,2-(cyclopentadienyl)(fluorenyl)propylidene)]-zirconium bis(dimethylamido)[~S:rIS-2,2-(cyclopentadienyl)(fluorenyl)propylidene)]-hafnium bis(dimethylamido)[rt5: rt5-2,2-(fluorenyl)(indenyl)propylidene)]zirconium bis(dimethylamido)[rt5: r~5-2,2-(fluorenyl)(indenyl)propylidene)]hafnium bis(dimethylamido)[r)5:~5-2,2-(methylcyclopentadienyl)(indenyl)propyli-dene)]zirconium bis(dimethylamido)[~5: ~5-2,2-(methylcyclopentadienyl)(fluorenyl)propyli-dene)]-zirconium 2192~1~
bis(dimethylamido)(n5: n5-2,2-(fluorenyl)(2-methylindenyl)propylidene)]-zirconium bis(dimethylamido)[~5: n5-2,2-(tetramethylcyclopentadienyl)(indenyl)-propylidene)]zirconium bis(dimethylamido)[~5: n5-2,2-(tetramethylcyclopentadienyl)(fluorenyl)-propylidene)]zirconium bis(dimethylamido)(n5: n5-2,2-(fluorenyl)(2-ethylindenyl)propylidene)]-zirconium bis(dimethylamido)[n5: n5-2,2-(cyclopentadienyl)(2-methylindenyl)-propylidene)]zirconium bis(dimethylamido)[ns: ~5-2,2-(cyclopentadienyl)(2-ethylindenyl)-propylidene)]zirconium bis(dimethylamido)[ris: ~5-2,2-(cyclopentadienyt)(3-trimethylsilylindenyl)-propylidene)]zirconium bis(dimethylamido)[rt5: ~5-2,2-(methylcyclopentadienyl)(2-methylindenyl)-propylidene)]zirconium bis(dimethylamido)[ri5:n5-2,2-(methylcyclopentadienyl)(2-ethylindenyl)-propylidene)]zirconium bis(dimethylamido)[~5: ~5-2,2-(methylcyclopentadienyl)(3-trimethylsilyl-indenyl)propylidene)]zirconium bis(dimethylamido)[dimethylsilanediyl(rts: ~5-(cyclopentadienyl)(indenyl)]-zirconium bis(dimethylamido)(dimethylsilanediyl(~S:r)5-(cyclopentadienyl)(indenyl)]-zirconium bis(dimethylamido)[dimethylsilanediyl(rt5: rt5-(fluorenyl)(indenyl)]zirconium bis(dimethylamido)[dimethylsilanediyl(~5: ~s-2,2-(methylcyclopentadienyl)-(indenyl))]zirconium bis(dimethylamido)[dimethylsilanediyl(n5: n5-2,2-(methylcyclopentadienyl)-(fluorenyl))]zirconium bis(dimethylamido)[dimethylsilanediyl(~5: n5-2,2-(fluorenyl)(2-methyl-indenyl))]zirconium bis(dimethylamido)[dimethylsilanediyl(n5: r~5_2,2-(tetramethylcyclopenta-dienyl)(indenyl))]zirconium bis(dimethylamido)[dimethylsilanediyl(n5:r~5_2,2_(tetramethylcyclopenta-dienyl)(fluorenyl))]zirconium bis(dimethylamido)[dimethylsilanediyl(r~5: n5-2,2-(fluorenyl)(2-ethylindenyl))]-zirconiu m 2I92~7~
bis(dimethylamido)[dimethylsilanediyl(~5:~5-2,2-(cyclopentadienyl)(2-methylindenyl)))zirconium bis(dimethylamido)[dimethylsilanediyl(~5:n5-2,2-(cyclopentadienyl)(2-ethyl-indenyl))]zirconium 5 bis(dimethylamido)[dimethylsilanediyl(~5:rt5-2,2-(cyclopentadieny1)(3-trimethylsilylindenyl))]zirconium bis(dimethylamido)[dimethylsilanediyl(n5: ~5-2,2-(methylcyclopentadienyl)-(2-methylindenyl))Jzirconium bis(dimethylamido)[dimethylsilanediyl(rt5: n5-2,2-(methylcyclopentadienyl)-(2-ethylindenyl))]zirconium bis(dimethylamido)[dimethylsilanediyl(n5: ~5-2,2-(methylcyclopentadienyl)-(3-trimethylsilylindenyl))]zirconium stanntetraylbis[(rt5: n5-bis(cyclopentadienyl)bis(dimethylamido)zirconium].
The preferred form of metallocene compound of the formula (I) used in the process of the invention is a metallocene compound of the formula (II) 5 6 Ind~ /NR1R2 R R C /M~ 3 4 k 1 Cp NR R
m where Cp is an unsubstituted or substituted cyclopentadienyl group, Ind is unsubstituted or substituted indenyl, M is a tetravalent transition metal, R~, R2, R3 and R4 are, independently of one another, identical or different and are each a hydrogen atom or a C~-C2o-hydrocarbon radical, R5 and R6 are, independently of one another, identical or different and are each a hydrogen atom or a C~-C3o-hydrocarbon radical, m is 1 or 2 and k and I are 1 when m is 1 and k and I are zero when m is 2.
In formula II, M is preferably titanium, zirconium, hafnium, vanadium, niobium, tantalam, scandium, yttrium or a rare earth metal, particularly preferably titanium, zirconium or hafnium.
Cp is an unsubstituted or substituted cyclopentadienyl group.
Examples of substituted cyclopentadienyl groups Cp are:
tetramethylcyclopentadienyl, methylcyclopentadienyl, methyl-tert-butylcyclopentadienyl, tert-butylcyclopentadienyl, isopropylcyclopentadienyl, dimethylcyclopentadienyl, trimethylcyclopentadienyl, trimethylethylcyclopentadienyl, phenylcyclopentadienyl, diphenylcyclopentadienyl, indenyl, 2-methylindenyl, 2-ethylindenyl, 3-methylindenyl, 3-tert-butylindenyl, 3-trimethylsilylindenyl, 2-Methyl-4-phenylindenyl, 2-ethyl-4-phenylindenyl, 2-methyl-4-naphthylindenyl, 2-methyl-4-isopropylindenyl, 4,5-benzoindenyl, 2-methyl-4,5-benzoindenyl, 2-methyl-a-acena~hthindenyl, 2-methyl-4,6-diisopropylindenyl, fluorenyl, 4-methylfluorenyl or 2,7-di-tert-butylfluorenyl.
Ind is unsubstituted or substituted indenyl. Examples of substituted indenyl are:
2-methylindenyl, 2-ethylindenyl, 3-methylindenyl, 3-tert-butylindenyl, 3-trimethylsilylindenyl, 2-methyl-4-phenylindenyl, 2-ethyl-4-phenylindenyl, 2-methyl-4-naphthylindenyl, 2-methyl-4-isopropylindenyl, 4,5-benzoindenyl, 2-methyl-4,5-benzoindenyl, 2-methyl-a-acenaphthindenyl, 2-methyl-4,6-diisopropylindenyl. Ind is preferably unsubstituted indenyl.
The radicals R5 and Rs are, independently of one another, identical or different, preferably identical, and are each a hydrogen atom or a C~-C3o-hydrocarbon radical such as C~-CZO-alkyl or Cs-C2o-aryl. Preferably, R5 and R6 are methyl or phenyl, in particular methyl.
R~ and R3 are, independently of one another, identical or different and are each a h dro en atom or a C -C h drocarbon radical, preferabl a C -C -h drocarbon Y 9 ~ 20- Y Y ~ 2o Y
radical such as C~-C2o-alkyl or C6-C~4-aryl, in particular methyl.
R2 and R4 are, independently of one another, identical or different and are preferably a C~-C2o-hydrocarbon radical such as C~-C2o-alkyl or C6-C~4-aryl, in particular methyl.
2?9277?
The radicals R~, R2, R3 and R4 are, independently of one another, identical or different. Preferably, the radicals R~, R2, R3 and R4 are identical and are each a C~-C2o-hydrocarbon radical such as C~-CZO-alkyl or C6-C~4-aryl, in particular methyl.
Examples of metallocene compounds of the formula II are:
bis(dimethylamido)[n5: rt5-2,2-(cyclopentadienyl)(indenyl)propylidene)]-zirconium bis(dimethylamido)(ns: r15-2,2-(cyclopentadienyl)(indenyl)propylidene)]-hafnium bis(dimethylamido)[n5: rt5-2,2-(fluorenyl)(indenyl)propylidene]zirconium bis(dimethylamido)[~5: ~5-2,2-(fluorenyl)(indenyl)propylidene)]hafnium bis(dimethylamido)[~5: rt5-2,2-(methylcyclopentadienyl)(indenyl)-propylidene)]zirconium bis(dimethylamido)[05:rt5-2,2-(fluorenyl)(2-methylindenyl)propylidene)]-zirconium bis(dimethylamido)[O5: rl5-2,2-(tetramethylcyclopentadienyl)(indenyl)-propylidene)]zirconium bis(dimethylamido)[n5: ~5-2,2-(fluorenyl)(2-ethylindenyl)propylidene)]-zirconium bis(dimethylamido)[r~5: rt5-2,2-(cyclopentadienyl)(2-methylindenyl)-propylidene)]zirconium bis(dimethylamido)[rt5: ~5-2,2-(cyclopentadienyl)(2-ethylindenyl)-propylidene)]zirconium bis(dimethylamido)[rt5: n5-2,2-(cyclopentadienyl)(3-trimethylsilylindenyl)-propylidene)]zirconium bis(dimethylamido)[~5: n5-2,2-(methylcyclopentadienyl)(2-methylindenyl)-propylidene)]zirconium bis(dimethylamido)[rt5:~5-2,2-(methylcyclopentadienyl)(2-ethylindenyl)-propylidene)]zirconium bis(dimethylamido)[rt5: ~5-2,2-(methylcyclopentadienyl)(3-trimethylsilyl-indenyl)propylidene)]zirconium bis(dimethylamido)[n5:~5-2,2-(2-methylindenyl)(indenyl)-propylidene)]zirconium bis(dimethylamido)(n5:n5-2,2-bis(indenyl)propylidene)]zirconium.
The metallocene compound of the formula I or II can be prepared by reacting a compound of the formula III, where L is a rr-ligand, L' is a n-ligand, T is a bridge and 2~9277i s m is 1 or 2, with a compound of the formula IV, where M is a tetravalent metal and R~, R2, R3 and R4 are, independently of one another, identical or different and are each a hydrogen atom or a C~-C2o-hydrocarbon radical LH
T M(NR12NR22NR32NR42) ~L'H
m (III) ( The reaction is preferably carried out in an aprotic solvent such as toluene or hexane. The temperature can be between -78 and 140°C, preferably from 0°C to 110°C. The compound of the formula III can be used in excess;
preference is given to using 1 equivalent of the compound of the formula III and 1 equivalent of the metal tetramide of the formula IV.
Methods of preparing compounds of the formula III are known CChem. Ber. 1990, 123, 1649-1651 ). Methods of preparing compounds of the formula IV are likewise known (J. Chem. Soc. 1960, 3857-3861 ).
In the process of the invention, preference is given to using a catalyst which comprises at least one metallocene compound of the formula I and at least one cocatalyst. It is also possible to use mixtures of two or more metallocene compounds, in particular for preparing reactor blends or cycloolefin copolymers having a broad or multimodal molecular weight distribution.
A suitable cocatalyst in the process of the invention is in principle any compound which, owing to its Lewis acidity, cari convert the neutral metallocene compound into a ration and stabilize the latter ("labile coordination"). In addition, the cocatalyst or the anion formed therefrom should undergo no further reactions with the ration formed (EP-A-427 697). As cocatalyst, preference is given to using an aluminum compound and/or a boron compound.
The boron compound preferably has the formula RaXNH4_XBRb4, RaXPH4_xBRb4, Ra3CBRb~ or BRb3, where x is from 1 to 4, preferably 3, the radicals Ra are identical or different, preferably identical, and are C~-Coo-alkyl or Cs-C~8-aryl, or two radicals Ra together with the atoms connecting them form a ring, and the radicals Rb are identical or different, preferably identical, and are Cs-C~8-aryl which may be substituted by alkyl, haloalkyl or fluorine. In particular, Ra is ethyl, propyl, butyl or phenyl and Rb is phenyl, pentafluorophenyl, 3,5-bis(trifluoromethyl)phenyl, mesityl, xylyl or tolyl (EP-A-277 003, EP-A-277 004 and EP-A-426 638).
The cocatalyst used is preferably an aluminum compound such as aluminoxane and/or an aluminum alkyl.
The cocatalyst used is particularly preferably an aluminoxane, in particular of the formula Va for the linear type and/or the formula Vb for the cyclic type, Rc Rc R
A1 O A1O A1 ~ (Va) R~ p Rc Rc '- -' p+2 (Vb) where, in the formulae Va and Vb, the radicals R~ are identical or different and are each hydrogen or a C~-C2o-hydrocarbon group such as a C~-C~8-alkyl group, a C6-C~$-aryl group or benzyl and p is an integer from 2 to 50, preferably from 10 to 35.
The radicals R~ are preferably identical and are hydrogen, methyl, isobutyl, phenyl or benzyl, particularly preferably methyl.
~i~2~~~
If the radicals R~ are different, then they are preferably methyl and hydrogen or alternatively methyl and isobutyl, with hydrogen or isobutyl preferably being present in a proportion of from 0.01 to 40% by number (of the radicals R°).
5 The methods of preparing the aluminoxanes are known. The exact spatial structure of the aluminoxanes is not known (J. Am. Chem. Soc. (1993) 115, 4971 ). For example, it is conceivable that chains and rings can join to form larger two-dimensional or three-dimensional structures.
10 Regardless of the method of preparation, all aluminoxane solutions';ave in common a varying content of unreacted aluminum starting compound, which is present in free form or as adduct.
It is possible to preactivate the metallocene compound with~a cocatalyst, in particular an aluminoxane, before use in the polymerization reaction. This significantly increases the polymerization activity. The preactivation of the metallocene compound is preferably carried out in solution. The metallocene compound is preferably dissolved in a solution of the aluminoxane in an inert hydrocarbon. Suitable inert hydrocarbons are aliphatic or aromatic hydrocarbons.
Preference is given to using toluene.
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, in each case based on the total amount of solution. The metallocene compound can be used in the same concentration, but it is preferably used in an amount of from 10~ to 1 mol per mol of aluminoxane. The preactivation time is from 5 minutes to 60 hours, preferably from 5 to 60 minutes. The preactivation is carried out at a temperature of from -78 to 150°C, preferably from 0 to 80°C.
The metallocene compound is preferably employed in a concentration, based on the transition metal, of from 10-3 to 10-$ mol, preferably from 10~ to 10-7 mol, of transition metal per dm3 of solvent or per dm3 of reactor volume. The aluminoxane is preferably used in a concentration of from 10~ to 10-~ mol, preferably from 10-5 to 2?92771 10-2 mol, per dm3 of solvent or per dm3 of reactor volume. The other cocatalysts mentioned are used in approximately equimolar amounts to the metallocene compound. However, higher concentrations are also possible in principle.
The aluminoxane can be prepared in various ways by known methods. One of the methods is, for example, reacting an aluminum hydrocarbon compound and/or a hydridoaluminum hydrocarbon compound with water (gaseous, solid, liquid or bound - for example as water of crystallization) in an inert solvent such as toluene. To prepare an aluminoxane having different radicals R°, for example, two or more different trialkylaluminums corresponding to the desired composition are reacted with water (S. Pazynkiewicz, Polyhedron 9 (1990) 429, EP-A 302 424).
To remove catalyst poisons present in the olefin, purification using an aluminum compound, preferably an aluminum alkyl such as trimethylaluminum or triethylaluminum, is advantageous. This purification can be carried out either in the polymerization system itself or the olefin is brought into contact with the aluminum compound and subsequently separated off again before addition to the polymerization system.
In the process of the invention, the metallocene compound is preferably reacted with the cocatalyst outside the polymerization reactor in a separate step using a suitable solvent. Application to a support can be carried out during this step.
If solvent is added to the reaction mixture, this is a customary inert solvent such as an aliphatic or cycloaliphatic hydrocarbon, a petroleum or hydrogenated diesel oil fraction or toluene.
The metallocene compound of the formula I is preferably used in the form of its racemate. The metallocene compound is preferably employed in a concentration, based on the transition metal, of from 10-3 to 10-8 mol, preferably from 10~
to 10-~
mol, of transition metal per dm3 of reactor volume. The aluminoxane is used in a concentration of from 10 4 to 10-~ mol, preferably from 10~ to 2 * 10-2 mol, per dm3 of reactor volume, based on the aluminum content. However, higher concentrations are also possible in principle.
In the process of the invention, at least one cyclic, preferably polycyclic, olefin is polymerized together with at least one acyclic olefin. Polycyclic olefins preferably have the formulae VI, VII, VIII, IX, X or XI
R~
/CH\
HC/ \CH
R 9 - C - R 1 0 ( V I ) HC ~ CH
CH
/cH\ cH2 HC
i (VII) HC ~ H
~CH~~CH
R~
/CH CH
HC ~~ \CH~
R9-C-R10 R11-C-R12 (VIII) HC ~ ~ H CH
CH ~ ~ g CH R
2;92171 /CH ~ CH CH
HC / ~ \CH' \CH ~ R
R9-C-R10 R11_C_R12 ( R13_C_R14 (IX) HC ~ ~ H 'C /CH\
g CH CH CH R
/C H ~ /C H
HC / CH / CH
R9_C_R10 (X) HC\ ~ ~CH~ /CH
CH CH CH R~
HC~ \CH \CH \CH
R9_C_R110 R13_C_R14 (XI).
HC~ /CH\ /CH\ /CH\
\CH CH CH \R8 where R~, R8, R9, R~°, R~~, R~2, R~3 and R~4 are identical or different and are each a hydrogen atom or a C~-C2°-hydrocarbon radical such as C~-C8-alkyl or Cs-C~°-aryl, or two or more radicals R7-R~~ together form a C4-C4°-ring system, where identical radicals R~-R~~ in the various formulae can have a different meaning.
Particular preference is given to cycloolefins of the formulae VI or VIII, where R7, R8, R9, R~°, R~~, R~2, R~3 and R~4 are identical or different and are each a hydrogen atom or a C~-C2°-hydrocarbon radical, in particular a C6-C~°-aryl radical or a C~-C8-alkyl radical, where identical radicals R~-R~4 in the various formulae VI -XI can have a different meaning.
Acyclic olefins are preferably 1-olefins having from 1 to 40, preferably 1 -20, carbon atoms. Particular preference is given to 1-olefins of the formula (X11) C\ (XII) R1~ R18 where R~ 5, R~s, R~ ~ and R~ 8 are identical or different and are each a hydrogen atom or a C~-C2°-hydrocarbon radical, preferably a Cs-C~°-aryl radical and a C~-C$-alkyl radical. Examples of acyclic olefins are ethylene and propylene.
If desired, one or more monocyclic olefins, in particular of the formula (X111) CH CH (XIII) \
(CH2)n where n is from 2 to 10, are also used in the process of the invention.
In particular, copolymers of polycyclic olefins, preferably of thQ formulae VI
and VIII, with ethylene are prepared.
2i9277i Particularly preferred polycyclic olefins are norbornene and tetracyclododecene, with these being able to be substituted by (C~-C6)-alkyl. They are preferably copolymerized with ethylene; ethylene-norbornene copolymers are of particular importance.
In the process of the invention, the polycyclic olefin is preferably used in an amount of from 0.1 to 99.9% by weight, the monocyclic olefin in an amount of from 0 to 99.9% by weight and the acyclic olefin in an amount of from 0.1 to 99.9% by weight, in each case based on the total amount of monomers.
The concentration of the acyclic olefin used is given by its solubility in the reaction medium at a given pressure and a given temperature.
For the purposes of the present invention, polycyclic olefins, monocyclic olefins and acyclic olefins also include mixtures of two or more olefins of the respective type.
This means that, apart from polycyclic bicopolymers, it is also possible to prepare tercopolymers and multicopolymers by the process of the invention. Copolymers of monocyclic olefins and acyclic olefins can also be obtained by means of the process of the invention.
Among the monocyclic olefins, preference is given to cyclopentene which may be substituted.
The process of the invention is preferably carried out at temperatures of from -78 to 150°C, in particular from 0 to 100°C, and a presure of from 0.01 to 64 bar.
The polymerization is carried out in the liquid cycloolefin itself or in a cycloolefin solution, with the pressure advantageously being above 1 bar.
In the preparation of copolymers, the molar ratios of the polycyclic olefin to the open-chain olefin used can be varied within a wide range. Preference is given to using molar ratios of from 3:1 to 100:1 of cycloolefin to open-chain olefin.
Selection of the polymerization temperature, the concentration of the catalyst component and 2;92171 the molar ratio used or the pressure of the gaseous, open-chain olefin enables the proportion of comonomer incorporated to be controlled almost at will.
Preference is given to incorporation of between 20 and 80 mol% of the cyclic components and particular preference is given to incorporation of between 40 and 60 mol% of the cyclic components.
The polymerization can also be carried out in a plurality of stages, with block copolymers also being able to be formed (EP-A-560 090).
The mean molar mass of the polymer formed can also be controlled in a known manner by metering in hydrogen, varying the catalyst concentration or varying the temperature.
The polydispersity M~M~ of the cycloolefin copolymers is from 1.9 to 3.5 and the molecular weight distribution is therefore quite narrow. This results in a property profile which makes the cycloolefin copolymers particularly suitable for injection molding.
The process of the invention makes possible the preparation of amorphous cycloolefin copolymers which contain no partially crystalline ethylene polymers. The copolymers are transparent, hard and can be processed thermoplastically. The yield stresses (in accordance with DIN 53457) are in the range from 50 to 100 MPa, preferably between 55 and 70 MPa. Both during extrusion and during injection molding, no decomposition reactions or a drop in viscosity have been found at temperatures of 300°C.
The cycloolefin copolymers prepared according to the invention are particularly suitable for the production of shaped parts such as extruded parts (e.g.
films, hoses, tubes, rods and fibers) or injection-molded articles of any shape and size.
The films can be extruded films, calendered films, cast films, monoaxially and biaxially oriented films or multilayer films and are suitable, in particular, as food packaging films or blister packaging. They have a high barrier action against water 2?92771 and a low gas permeability. Cycloolefin copolymers prepared according to the invention are also suitable as an additive in other polymer films (in particular polyolefin films such as polypropylene films or polyethylene films), for example for the purposes of improving flow, improving the ability to apply a surface coating, influencing the modulus of elasticity and for producing opaque films.
An important property of the cycloolefin copolymers prepared according to the invention is their transparency. This makes the optical applications of the extruded or injection-molded parts produced from the cycloolefin copolymers particularly important. The index of refraction, determined using an Abbe refractometer and mixed light, of the reaction products described in the examples below is in the range between 1.520 and 1.555. Since the index of refraction is very close to that of crown glass (n = 1.51 ), the products according to the invention can be used as a substitute for glass in various applications, for example lenses, prisms, support plates and films for optical data storage, for video disks, for compact disks, as covering and focusing disks for solar cells, as covering and scattering disks for power optics, as optical waveguides in the form of fibers or films.
In impact-modified form, the cycloolefin copolymers prepared according to the invention can also be used as a structural material in various industrial fields (EP-A-566 988 ).
The cycloolefin copolymers obtained according to the invention can also be used for producing polymer alloys. The alloys can be produced in the melt or in solution. The alloys have, in each case, a property combination of the components which is favorable for certain applications. The following polymers are preferably used for alloys with the cycloolefin copolymers of the invention:
polyethylene, polypropylene, ethylene-propylene copolymers, polybutylene, poly(4-methyl-1-pentene), polyisoprene, polyisobutylene, natural rubber, poly(methyl methacrylate), further polymethacrylates, polyacrylates, acrylate-methacrylate copolymers, polystyrene, styrene-acrylonitrile copolymers, bisphenol A
polycarbonate, further polycarbonates, aromatic polyester carbonates, polyethylene terephthalate, polybutylene terephthalate, amorphous polyarylates, nylon 6, nylon 66, further polyamides, polyaramides, polyether ketones, polyoxymethylene, polyoxyethylene, polyurethanes, polysulfones, polyether sulfones, polyvinylidene fluoride.
The process of the invention proceeds with high activity and gives, in particular, transparent cycloolefin copolymers which have high tear strengths.
The glass transition temperatures Tg quoted in the following examples were determined by means of DSC (Differential Scanning Calorimetry) ~.: a heating rate of 20°C/min. The viscosity numbers quoted were determined in accordance with DIN
53728. The mechanical properties were measured in a tensile test (DIN 53457, Instron 4302).
The measure used for the catalyst activity was the yield of polymer per unit time and per mmol of metallocene:
Polymer [g]
Activity - ____________________________________________________________ _ A' Time [h] x amount of metallocene [mmol]
General procedures: Preparation and handling of organometallic compounds was carried out with exclusion of air and moisture under argon (Schlenk technique). All solvents required were freed of air and moisture before use by boiling for a number of hours over a suitable desiccant and subsequent distillation under argon.
The diketones and ketoaldehydes used as starting compounds were prepared by literature methods. Cyclopentadiene and methylcyclopentadiene were obtained by cracking of the dimers and were stored at -35°C.
The Al/CH3 ratio in the aluminoxane was determined by decomposition of the sample with HZS04 and determination of the volume of the hydrolysis gases formed _ 2~92i1~
under standard conditions and also by complexometric titration of the aluminum in the then dissolved sample using the Schwarzenbach method.
The compounds were characterized using'H-NMR, ~3C-NMR and IR spectroscopy.
The following examples illustrate the invention:
All glass apparatus was baked out in vacuo and flushed with argon. All operations were carried out with exclusion of moisture and oxygen in Schlenk vessels. The solvents used were distilled from a Na/K alloy under argon.
Toluene-soluble methylaluminoxane was used for the examples of polymerization as a 10% strength by weight toluene solution having a mean degree of oligomerization of n = 20 (Witco). The aluminum content determined was 36 mg of Allml.
Example 1 Bis(dirr~ethylamido)[n5:~5-2,2-(cyclopentadienyl)(indenyl)propylidenej-zirconium A solution of zirconium amide (416 mg, 1.55 mmol) in 25 ml of toluene is cooled to -78°C and subsequently a solution of 345 mg of the ligand in 10 ml of toluene is added dropwise. The solution is warmed to room temperature and after stirring for 12 hours is heated at 80°C for 3 hours. The solvent is removed under reduced pressure and the complex is obtained in the form of a yellow-orange solid in a yield of 99% (613 mg).
~ H-NMR (400 MHz, C6D6): b [ppm] = 1.57, 1.89 (s, 6H, C(CH3)2), 2.46, 2.81 (s, 12H, N(CH3)2), 5.29 (m, 1 H, CH in C5H4), 5.80 (m, 2H, CH in C5H4 and C9H~), 5.99 (m, 1 H, CH in CSH4), 6.08 (m, 1 H, CH in C5H4), 6.59 (d, 1 H, 3J(H,H) = 3.0 Hz, CH in C9H~), 6.69 (m, 1 H, CH in C9H~), 7.49 (m, 1 H, CH in C9H~), 7.62 (m, 1 H, CH
in C9H~).
MS (CI): m/e (%) = 708 (10) [2M+ - 2 NMe2], 398 (100) [M+], 355 (45) [M+ -NMe2], 311 (21 %) [M+ - 2 NMe2J.
._ 21927 i Example 2 Bis(dimethylamido)[r15:n5-2,2-(cyclopentadienyl)(indenyl)propylidene]- hafnium A solution of hafnium amide (833 mg, 1.55 mmol) in 25 ml of xylene is cooled to -5 78°C and subsequently a solution of 522 mg of the ligand in 10 ml of xylene is added dropwise. The solution is warmed to room temperature and after stirring for 2 hours is heated at 150°C for 8 hours. The solvent is removed under reduced pressure and the complex is recrystallized from a little pentane. The complex precipitates in the form of a yellow-orange solid (95% yield, 613 mg).
~ H-NMR (400 MHz, C6D6): b [ppm] = 1.57, 1.88 (s, 6H, C(CH3)2), 2.51, 2.85 (s, 12H, N(CH3)2), 5.29 (m, 1 H, CH in C5H4), 5.70 - 5.80 (m, 2H, CH in C5H4 and C9H~), 6.00 (m, 1 H, CH in C5H4), 6.04 (m, 1 H, CH in C5H4), 6.53 (d, 1 H, 3J(H,H) = 3.0 Hz, CH in C9H~), 6.71 (m, 1 H, CH in C9H7), 6.87 (m, 1 H, CH in C9H7), 7.49 (m, 1 H, CH
in C9H~), 7.63 (m, 1 H, CH in C9H~).
MS (CI): mle (%) = 620 (100), 600 (18), 512 (24), 497 (28), 442 (17), 399 (25), 222 (26), 207 (26), 115 (8), 107 (20).
Polymerization Examples Example A:
A 1.5 dm3 autoclave which has been thoroughly flushed beforehand with ethene is charged with 600 cm3 of an 85% strength by weight solution of norbornene in toluene. The solution was saturated with ethene by repeated pressurization with ethene (6 bar). 5 cm3 of methylaluminoxane solution in toluene (10.1 %
strength by weight solution of methylaluminoxane having a molar mass of 1300 g/mol determined by cryoscopy) were metered in countercurrent into the reactor thus prepared and the mixture was stirred for 30 minutes at 70°C. A solution of 1.5 mg of bis(dimethylamido)[~5:n5-2,2-(cyclopentadienyl)indenyl)-propylidene]zirconium (I) in 5 cm3 of a solution of methylaluminoxane in toluene was added after a preactivation 2~~~~7~
time of 15 minutes. (If hydrogen regulation is to be used, hydrogen can be injected at this point.) Polymerization was carried out for one hour at 70°C while stirring (750 rpm), with the ethene pressure being maintained at 6 bar by metering in further amounts.
At the end of the reaction time, the polymerization mixture was drained into a vessel and immediately introduced into 5 dm3 of acetone, stirred for 10 minutes and the precipitated product was subsequently filtered off. The filter cake was washed alternately with three portions of 10% strength hydrochloric acid and three portions of acetone. Finally, it was washed with water until neutral, the residue was slurried in acetone and filtered again. The polymer thus purified was dried for 15 hours at a 80 C under reduced pressure (0.2 bar).
Drying gave 44 g of colorless polymer which had a glass transition temperature of 193°C, a viscosity number of 69 cm3/g, a yield stress of 64 MPa and an elongation at break of 3.3%. The activity A was 10842 g of polymer/h x mmol.
Example B:
Example A was repeated at an ethylene pressure of 18 bar and a polymerization temperature of 90°C. The yield of purified and dried polymer was 152 g.
The polymer had a glass transition temperature of 150°C, a viscosity number of 70 cm3lg, a yield stress of 62 MPa and an elongation at break of 3.5%. The activity A
was 56182 g of polymer/h x mmol.
Example C:
The procedure of Example B was repeated, but the metallocene used was 0.5 mg of isopropylidenebis(1-indenyl)bis(N,N-dimethylamido)zirconium (II). This gave g of purified and dried polymer having a glass transition temperature of 143°C, a viscosity number of 152 cm3/g.
~~92771 Example D:
The procedure of Example A was repeated, but the metallocene used was 0.1 mg of dimethylsilanediyl(9-(2,7-di-tert-butyl)fluorenyl)cyclopentadienyl-bis(N,N-dimethylamido)zirconium (III). This gave 17 g of purified and dried polymer having a glass transition temperature of 143°C and a viscosity number of 267 cm3/g.
Example E:
The procedure of Example A was repeated, but the metallocene used was 0.2 mg of isopropylidene(9-fluorenyl)cyclopentadienyl-bis(N,N-dimethylamido)zirconium (IV).
This gave 64 g of purified and dried polymer having a glass transition temperature of 151 °C and a viscosity number of 147 cm3/g.
L L L L L
_ _ _ _ _ O C O C O C O C O C
L O O ~ O ~ O ~ O ~ O
' ::.~ ~. ' ~.W . w :..
N p i p i p n p V~ 7 N p o ~ o N o U o N o~
N
O V M O M M
o O
O
O N
U
U a7 ~ tp ~ ~ C~O
v r r.
O C
C ~ ~ N
N ~ ~ ~ l~
p E ~ O O O
E
a C
a ~ ~ m ~ ~ ~o m L O
w a a O ~ ~ O O
H
p c a~
O C
U
.L O - -cv O
_N
Q
a m v o w x w ~n o
Claims (21)
1. A process for preparing a cycloolefin copolymer by polymerization of at least one cyclic olefin and at least one acyclic olefin in the presence of a catalyst comprising at least one metallocene compound of the formula (I), where L and L' are each a substituted or unsubstituted cyclopentadienyl group, T is a bridge between L and L' and is [R5R6X]n, where X are each, independently of one another, carbon, silicon, germanium or tin, the radicals R5 and R6 are each, independently of one another, a hydrogen atom or a C1-C30-hydrocarbon radical and n is 1, 2, 3 or 4, M is a tetravalent transition metal and R1, R2, R3 and R4 are identical or different and are each, independently of one another, a hydrogen atom or a C1-C20-hydrocarbon radical.
2. The process according to claim 1, wherein the radicals R5 and R6 are each a hydrogen atom, C1-C20-alkyl or C6-C20-aryl.
3. The process according to claim 1 or 2, wherein the bridge T is a radical selected from the group consisting of dimethylsilanediyl, methylphenylsilanediyl, diphenylsilanediyl, dimethylgermanediyl, 1,2-tetramethyldisilanediyl, 1,2-ethylidene, 1,2-propylidene, 1,2-butylidene, 1,3-propylidene, 1,4-butylidene and 2,2-propylidene.
4. The process according to any one of claims 1 to 3, wherein L and L' are each, independently of one another, cyclopentadienyl, tetramethylcyclopentadienyl, methylcyclopentadienyl, methyl-tert-butylcyclopentadienyl, tertbutylcyclopentadienyl, isopropylcyclopentadienyl, dimethylcyclopentadienyl, trimethylcyclopentadienyl, trimethylethylcyclopentadienyl, phenylcyclopentadienyl, diphenylcyclopentadienyl, indenyl, 2-methylindenyl, 2-ethylindenyl, 3-methylindenyl, 3-tert-butylindenyl, 3-trimethylsilylindenyl, 2-methyl-4-phenylindenyl, 2-ethyl-4-phenylindenyl, 2-methyl-4-naphthylindenyl, 2-methyl-4-isopropylindenyl, 4,5-benzoindenyl, 2-methyl-4,5-benzoindenyl, 2-methyl-.alpha.-acenaphthindenyl, 2-methyl-4,6-diisopropylindenyl, fluorenyl, 4-methylfluorenyl or 2,7-di-tert-butylfluorenyl.
5. A process for preparing a cycloolefin copolymer by polymerization of at least one cyclic olefin and at least one acyclic olefin in the presence of a catalyst comprising at least one metallocene compound of the formula (II), where Cp is an unsubstituted or substituted cyclopentadiene group, Ind is an unsubstituted or substituted indenyl, the radicals R5 and R6 are identical or different and are each, independently of one another, a hydrogen atom or a C1-C30-hydrocarbon radical and n is 1, 2, 3 or 4, M
is a tetravalent transition metal and R1, R2, R3 and R4 are identical or different and are each, independently of one another, a hydrogen atom or a C1-C20-hydrocarbon radical.
is a tetravalent transition metal and R1, R2, R3 and R4 are identical or different and are each, independently of one another, a hydrogen atom or a C1-C20-hydrocarbon radical.
6. The process according to claim 5, wherein Cp is the radical cyclopentadienyl, tetramethylcyclopentadienyl, methylcyclopentadienyl,methyl-tert-butylcyclopentadienyl, tert-butylcyclopentadienyl, isopropylcyclopentadienyl, dimethylcyclopentadienyl, trimethylcyclopentadienyl, trimethylethylcyclopentadienyl, phenylcyclopentadienyl, diphenylcyclopentadienyl, indenyl, 2-methylindenyl, 2-ethylindenyl, 3-methylindenyl, 3-tert-butylindenyl, 3-trimethylsilylindenyl, 2-methyl-4-phenylindenyl, 2-ethyl-4-phenylindenyl, 2-methyl-4-naphthylindenyl, 2-methyl-4-isopropylindenyl, 4,5-benzoindenyl, 2-methyl-4,5-benzoindenyl, 2-methyl-alpha-acenaphthindenyl, 2-methyl-4,6-diisopropylindenyl, fluorenyl, 4-methylfluorenyl or 2,7-di-tert-butylfluorenyl and Ind is the radical, indenyl, 2-methylindenyl, 2-ethylindenyl, 3-methylindenyl, 3-tert-butylindenyl, 3-trimethylsilylindenyl, 2-methyl-4-phenylindenyl, 2-ethyl-4-phenylindenyl, 2-methyl-4-naphthylindenyl, 2-methyl-4-isopropylindenyl, 4,5-benzoindenyl, 2-methyl-4,5-benzoindenyl, 2-methyl-alpha-acenaphthindenyl or 2-methyl-4,6-diisopropylindenyl.
7. The process according to any one of claims 1 to 6, wherein the catalyst further comprises at least one cocatalyst.
8. The process according to claim 7, wherein the cocatalyst is an aluminium compound and/or a boron compound.
9. The process according to claim 8, wherein the cocatalyst is an aluminoxane.
10. The process according to any one of claims 1 to 9, wherein M is titanium, zirconium or hafnium.
11. The process according to any one of claims 1 to 10, wherein R1, R2, R3 and R4 are identical and are, each C1-C20-alkyl or C6-C14-aryl.
12. The process according to any one of claims 1 to 11, wherein R1, R2, R3 and R4 are each methyl.
13. The process according to any one of claims 1 to 4 and 7 to 9, wherein the metallocene compound of the formula I is one of the following compounds:
bis(dimethylamido)[.eta.5:.eta.5-2,2-(cyclopentadienyl)(indenyl)propylidene)]zirconium bis(dimethylamido)[.eta.5:.eta.5-2,2-(cyclopentadienyl)(indenyl)propylidene)]hafnium bis(dimethylamido)[.eta.5:.eta.5-2,2-(cyclopentadienyl)(fluorenyl)propylidene)]zirconium bis(dimethylamido)[.eta.5:.eta.5-2,2-(cyclopentadienyl)(fluorenyl)propylidene)]hafnium bis (dimethylamido)[.eta.5:.eta.5-2,2-(fluorenyl)(indenyl)propylidene)]zirconium bis(dimethylamido)[.eta.5:.eta.5-2,2-(fluorenyl)(indenyl)propylidene)]hafnium bis (dimethylamido)[.eta.5:.eta.5-2,2-(methylcyclopentadienyl)(indenyl)propylidene)]zirconium bis(dimethylamido)[.eta.5:.eta.5-2,2-(methylcyclopentadienyl)(fluorenyl)propylidene)]zirconium bis(dimethylamido)[.eta.5:.eta.5-2,2-(fluorenyl)(2-methylindenyl)(propylidene)]zirconium bis(dimethylamido)[.eta.5:.eta.5-2,2-(tetramethylcyclopentadienyl)(indenyl)propylidene)]zirconium bis(dimethylamido)[.eta.5:.eta.5-2,2-(tetramethylcyclopentadienyl)(fluorenyl)propylidene)]zirconium bis(dimethylamido)[.eta.5:.eta.5-2,2-(fluorenyl)(2-ethylindenyl)propylidene)]zirconium bis(dimethylamido)[.eta.5:.eta.5-2,2-(cyclopentadienyl)-(2-methylindenyl)propylidene)]zirconium bis(dimethylamido)[.eta.5:.eta.5-2,2-(cyclopentadienyl)-(2-ethylindenyl)propylidene)]zirconium bis(dimethylamido)[.eta.5:.eta.5-2,2-(cyclopentadienyl)-(3-trimethylsilyl)propylidene)]zirconium bis(dimethylamido)[.eta.5:.eta.5-2,2-(methylcyclopentadienyl)(2-methylindenyl)propylidene)]zirconium bis(dimethylamido)[.eta.5:.eta.5-2,2--(methylcyclopentadienyl)(2-ethylindenyl)propylidene)]zirconium bis(dimethylamido)[.eta.5:.eta.5-2,2-(methylcyclopentadienyl)(3-trimethylsilylindenyl)propylidene)]zirconium bis(dimethylamido)[dimethylsilanediyl(.eta.5:.eta.5-(cyclopentadienyl)(indenyl)]zirconium bis(dimethylamido)[dimethylsilanediyl(.eta.5:.eta.5-(fluorenyl)(indenyl)]zirconium bis(dimethylamido)[dimethylsilanediyl(.eta.5:.eta.5-(methylcyclopentadienyl)(indenyl)]zirconium bis(dimethylamido)[dimethylsilanediyl(.eta.5:.eta.5-(methylcyclopentadienyl)(fluorenyl)]zirconium bis(dimethylamido)[dimethylsilanediyl(.eta.5:.eta.5-2,2-(fluorenyl)(2-methylindenyl)]zirconium bis(dimethylamido)[dimethylsilanediyl(.eta.5:.eta.5-2,2-(tetramethylcycfopentadienyl)(indenyl))]zirconium bis(dimethylamido)[dimethylsilanediyl(.eta.5:.eta.5-2,2-(tetramethylcyclopentadienyl)(fluorenyl)]zirconium bis(dimethylamido)[dimethylsilanediyl(.eta.5:.eta.5-2,2(fluorenyl)(2-ethylindenyl)]zirconium bis(dimethylamido)[dimethylsilanediyl(.eta.5:.eta.5-2,2(cyclopentadienyl)(2-methylindenyl)]zirconium bis(dimethylamido)[dimethylsilanediyl(.eta.5:.eta.5-2,2-(cyclopentadienyl)(2-ethylindenyl)]zirconium bis(dimethylamido)[dimethylsilanediyl(.eta.5:.eta.5-2,2-(cyclopentadienyl)(trimethylsilylindenyl))]zirconnium bis(dimethylamido)[dimethylsilanediyl(.eta.5:.eta.5-2,2-(methylcyclopentadienyl)(2-methylindenyl))]zirconnium bis(dimethylamido)[dimethylsilanediyl(.eta.5:.eta.5-2,2-(methylcyclopentadienyl)(2-ethylindenyl))]zirconnium bis(dimethylamido)[dimethylsilanediyl(.eta.5:.eta.5-2,2-(methylcyclopentadienyl)(3-trimethylsilylindenyl))]zirconium stanntetraylbis(.eta.5:.eta.5-bis(cyclopentadienyl)-bis-(dimethylamido)zirconium]
bis(dimethylamido)[.eta.5:.eta.5-2,2-(cyclopentadienyl)(indenyl)propylidene)]zirconium bis(dimethylamido)[.eta.5:.eta.5-2,2-(cyclopentadienyl)(indenyl)propylidene)]hafnium bis(dimethylamido)[.eta.:.eta.5-2,2-(fluorenyl)(indenyl)propylidene]zirconium bis (dimethylamido)[.eta.5:.eta.5-2,2-(fluorenyl)(indenyl)propylidene)]hafnium bis(dimethylamido)[.eta.5:.eta.5-2,2-(methylcyclopentadienyl)(indenyl)propylidene)]zirconium bis(dimethylamido)[.eta.5:.eta.5-2,2-(fluorenyl)(2-methylindenyl)propylidene)]zirconium bis(dimethylamido)[.eta.5:.eta.5-2,2-(tetramethylcyclopentadienyl)(indenyl)propylidene)]zirconium bis(dimethylamido)[.eta.5:.eta.5-2,2-(fluorenyl)(2-ethylindenyl)propylidene)]zirconium bis(dimethylamido)[.eta.5:.eta.5-2,2-(cyclopentadienyl)(2-methylindenyl)propylidene)]zirconium bis(dimethylamido)[.eta.5:.eta.5-2,2-(cyclopentadienyl)(2-ethylindenyl)propylidene)]zirconium bis(dimethylamido)[.eta.5:.eta.5-2,2-(cyclopentadienyl)(3-trimethylsilylindenyl)propylidene]zirconium bis(dimethylamido)[.eta.5:.eta.5-2,2-(methylcyclopentadienyl)(2-methylindenyl)propylidene)zirconium bis(dimethylamido)[.eta.5:.eta.5-2,2-(methylcyclopentadienyl)(2-ethylindenyl)propylidene]zirconium bis (dimethylamido)[.eta.5:.eta.5-2,2-(methylcyclopentadienyl)(3-trimethylsilylindenyl)propylidene]zirconium bis (dimethylamido)[.eta.5:.eta.5-2,2-(2-methylindenyl)-(indenyl)propylidene]zirconium bis(dimethylamido)[.eta.5:.eta.5-2,2-bis(indenyl)propylidene)]zirconium.
bis(dimethylamido)[.eta.5:.eta.5-2,2-(cyclopentadienyl)(indenyl)propylidene)]zirconium bis(dimethylamido)[.eta.5:.eta.5-2,2-(cyclopentadienyl)(indenyl)propylidene)]hafnium bis(dimethylamido)[.eta.5:.eta.5-2,2-(cyclopentadienyl)(fluorenyl)propylidene)]zirconium bis(dimethylamido)[.eta.5:.eta.5-2,2-(cyclopentadienyl)(fluorenyl)propylidene)]hafnium bis (dimethylamido)[.eta.5:.eta.5-2,2-(fluorenyl)(indenyl)propylidene)]zirconium bis(dimethylamido)[.eta.5:.eta.5-2,2-(fluorenyl)(indenyl)propylidene)]hafnium bis (dimethylamido)[.eta.5:.eta.5-2,2-(methylcyclopentadienyl)(indenyl)propylidene)]zirconium bis(dimethylamido)[.eta.5:.eta.5-2,2-(methylcyclopentadienyl)(fluorenyl)propylidene)]zirconium bis(dimethylamido)[.eta.5:.eta.5-2,2-(fluorenyl)(2-methylindenyl)(propylidene)]zirconium bis(dimethylamido)[.eta.5:.eta.5-2,2-(tetramethylcyclopentadienyl)(indenyl)propylidene)]zirconium bis(dimethylamido)[.eta.5:.eta.5-2,2-(tetramethylcyclopentadienyl)(fluorenyl)propylidene)]zirconium bis(dimethylamido)[.eta.5:.eta.5-2,2-(fluorenyl)(2-ethylindenyl)propylidene)]zirconium bis(dimethylamido)[.eta.5:.eta.5-2,2-(cyclopentadienyl)-(2-methylindenyl)propylidene)]zirconium bis(dimethylamido)[.eta.5:.eta.5-2,2-(cyclopentadienyl)-(2-ethylindenyl)propylidene)]zirconium bis(dimethylamido)[.eta.5:.eta.5-2,2-(cyclopentadienyl)-(3-trimethylsilyl)propylidene)]zirconium bis(dimethylamido)[.eta.5:.eta.5-2,2-(methylcyclopentadienyl)(2-methylindenyl)propylidene)]zirconium bis(dimethylamido)[.eta.5:.eta.5-2,2--(methylcyclopentadienyl)(2-ethylindenyl)propylidene)]zirconium bis(dimethylamido)[.eta.5:.eta.5-2,2-(methylcyclopentadienyl)(3-trimethylsilylindenyl)propylidene)]zirconium bis(dimethylamido)[dimethylsilanediyl(.eta.5:.eta.5-(cyclopentadienyl)(indenyl)]zirconium bis(dimethylamido)[dimethylsilanediyl(.eta.5:.eta.5-(fluorenyl)(indenyl)]zirconium bis(dimethylamido)[dimethylsilanediyl(.eta.5:.eta.5-(methylcyclopentadienyl)(indenyl)]zirconium bis(dimethylamido)[dimethylsilanediyl(.eta.5:.eta.5-(methylcyclopentadienyl)(fluorenyl)]zirconium bis(dimethylamido)[dimethylsilanediyl(.eta.5:.eta.5-2,2-(fluorenyl)(2-methylindenyl)]zirconium bis(dimethylamido)[dimethylsilanediyl(.eta.5:.eta.5-2,2-(tetramethylcycfopentadienyl)(indenyl))]zirconium bis(dimethylamido)[dimethylsilanediyl(.eta.5:.eta.5-2,2-(tetramethylcyclopentadienyl)(fluorenyl)]zirconium bis(dimethylamido)[dimethylsilanediyl(.eta.5:.eta.5-2,2(fluorenyl)(2-ethylindenyl)]zirconium bis(dimethylamido)[dimethylsilanediyl(.eta.5:.eta.5-2,2(cyclopentadienyl)(2-methylindenyl)]zirconium bis(dimethylamido)[dimethylsilanediyl(.eta.5:.eta.5-2,2-(cyclopentadienyl)(2-ethylindenyl)]zirconium bis(dimethylamido)[dimethylsilanediyl(.eta.5:.eta.5-2,2-(cyclopentadienyl)(trimethylsilylindenyl))]zirconnium bis(dimethylamido)[dimethylsilanediyl(.eta.5:.eta.5-2,2-(methylcyclopentadienyl)(2-methylindenyl))]zirconnium bis(dimethylamido)[dimethylsilanediyl(.eta.5:.eta.5-2,2-(methylcyclopentadienyl)(2-ethylindenyl))]zirconnium bis(dimethylamido)[dimethylsilanediyl(.eta.5:.eta.5-2,2-(methylcyclopentadienyl)(3-trimethylsilylindenyl))]zirconium stanntetraylbis(.eta.5:.eta.5-bis(cyclopentadienyl)-bis-(dimethylamido)zirconium]
bis(dimethylamido)[.eta.5:.eta.5-2,2-(cyclopentadienyl)(indenyl)propylidene)]zirconium bis(dimethylamido)[.eta.5:.eta.5-2,2-(cyclopentadienyl)(indenyl)propylidene)]hafnium bis(dimethylamido)[.eta.:.eta.5-2,2-(fluorenyl)(indenyl)propylidene]zirconium bis (dimethylamido)[.eta.5:.eta.5-2,2-(fluorenyl)(indenyl)propylidene)]hafnium bis(dimethylamido)[.eta.5:.eta.5-2,2-(methylcyclopentadienyl)(indenyl)propylidene)]zirconium bis(dimethylamido)[.eta.5:.eta.5-2,2-(fluorenyl)(2-methylindenyl)propylidene)]zirconium bis(dimethylamido)[.eta.5:.eta.5-2,2-(tetramethylcyclopentadienyl)(indenyl)propylidene)]zirconium bis(dimethylamido)[.eta.5:.eta.5-2,2-(fluorenyl)(2-ethylindenyl)propylidene)]zirconium bis(dimethylamido)[.eta.5:.eta.5-2,2-(cyclopentadienyl)(2-methylindenyl)propylidene)]zirconium bis(dimethylamido)[.eta.5:.eta.5-2,2-(cyclopentadienyl)(2-ethylindenyl)propylidene)]zirconium bis(dimethylamido)[.eta.5:.eta.5-2,2-(cyclopentadienyl)(3-trimethylsilylindenyl)propylidene]zirconium bis(dimethylamido)[.eta.5:.eta.5-2,2-(methylcyclopentadienyl)(2-methylindenyl)propylidene)zirconium bis(dimethylamido)[.eta.5:.eta.5-2,2-(methylcyclopentadienyl)(2-ethylindenyl)propylidene]zirconium bis (dimethylamido)[.eta.5:.eta.5-2,2-(methylcyclopentadienyl)(3-trimethylsilylindenyl)propylidene]zirconium bis (dimethylamido)[.eta.5:.eta.5-2,2-(2-methylindenyl)-(indenyl)propylidene]zirconium bis(dimethylamido)[.eta.5:.eta.5-2,2-bis(indenyl)propylidene)]zirconium.
14. The process according to any one of claims 1 to 13, wherein the cyclic olefin is a polycyclic olefin having one of the formulae VI to XI, where R7, R8, R9, R10, R11, R12, R13 and R14 are identical or different and are each a hydrogen atom or a C1-C20-hydrocarbon radical.
15. The process according to claim 14, wherein R7, R8, R9, R10, R11, R12, R13 and R14 are identical or different and are each a hydrogen atom or a C1-C8-alkyl or C6-C10-aryl or two or more radicals R7-R14 together form a C4-C40 ring system, where the same radicals R7-R14 in the various formulae can have different meanings.
16. The process according to any one of claims 1 to 15, wherein the acyclic olefin is a 1-olefin having 1-20 carbon atoms.
17. The process according to any one of claims 1 to 16, wherein the acyclic olefin is a 1-olefin of the formula XII, where R15, R16, R17 and R18 are identical or different and are each a hydrogen atom or a C1-C20-hydrocarbon radical.
18. The process according to any one of claims 1 to 17, wherein the cyclic olefin is an olefin of the formula VI or VIII
wherein R7, R8, R9, R10, R11 and R12 are as defined in claim 14 and the acyclic olefin is ethylene.
wherein R7, R8, R9, R10, R11 and R12 are as defined in claim 14 and the acyclic olefin is ethylene.
19. The process according to any one of claims 1 to 18, wherein the cyclic olefin is norbornene.
20. The process according any one of claims 1 to 19, wherein one or more monocyclic olefins of the formula XIII
where n is from 2 to 10, are additionally used.
where n is from 2 to 10, are additionally used.
21. The process according to claim 20, wherein the monocyclic olefin is cyclopentene, which may be substituted.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19546500A DE19546500A1 (en) | 1995-12-13 | 1995-12-13 | Production of cyclo-olefin copolymers e.g. for pipes |
| DE19546500.8 | 1995-12-13 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CA2192771A1 CA2192771A1 (en) | 1997-06-14 |
| CA2192771C true CA2192771C (en) | 2007-03-27 |
Family
ID=7779982
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002192771A Expired - Lifetime CA2192771C (en) | 1995-12-13 | 1996-12-12 | Process for preparing a cycloolefin copolymer |
Country Status (8)
| Country | Link |
|---|---|
| US (2) | US5869586A (en) |
| EP (1) | EP0779306B1 (en) |
| JP (1) | JPH09176223A (en) |
| KR (1) | KR100480532B1 (en) |
| CN (1) | CN1089771C (en) |
| CA (1) | CA2192771C (en) |
| DE (2) | DE19546500A1 (en) |
| TW (1) | TW356473B (en) |
Families Citing this family (74)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6169152B1 (en) * | 1996-07-05 | 2001-01-02 | Jsr Corporation | Olefin polymerization catalyst comprising transition metal compound containing a cyclic ligand having at least two nitrogen atoms in its main chain skeleton |
| JP3566819B2 (en) * | 1996-10-04 | 2004-09-15 | 関東化学株式会社 | New organic transition metal compounds |
| DE19652340A1 (en) * | 1996-12-17 | 1998-06-18 | Hoechst Ag | Process for the preparation of cycloolefin copolymers |
| US6517781B1 (en) * | 1997-06-02 | 2003-02-11 | Aurora Biosciences Corporation | Low fluorescence assay platforms and related methods for drug discovery |
| US5986024A (en) * | 1997-10-17 | 1999-11-16 | Sri International | Preparation of multimodal polymer compositions using multinuclear metallocene catalysts |
| US6096677A (en) * | 1997-10-17 | 2000-08-01 | Sri International | Supported metallocene catalysts |
| US5892079A (en) * | 1997-10-17 | 1999-04-06 | Sri International | Metallocene catalysts and associated methods of preparation and use |
| JPH11281351A (en) * | 1998-01-28 | 1999-10-15 | Fuji Electric Co Ltd | Distance measuring apparatus |
| EP0933383A1 (en) * | 1998-01-29 | 1999-08-04 | Union Carbide Chemicals & Plastics Technology Corporation | Catalyst composition for the polymerization of olefins |
| US6861035B2 (en) * | 1998-02-24 | 2005-03-01 | Aurora Discovery, Inc. | Multi-well platforms, caddies, lids and combinations thereof |
| DE59913218D1 (en) | 1998-06-16 | 2006-05-11 | Ticona Gmbh | Impact-resistant cycloolefin copolymer alloy |
| US6228790B1 (en) * | 1998-06-29 | 2001-05-08 | Industrial Technology Research Institute | Dinuclear metallocene catalyst for preparing high molecular weight olefin polymer |
| US6455458B1 (en) | 1998-07-10 | 2002-09-24 | Exxonmobil Chemical Patents Inc. | Tethered monocyclopentadienyl polymerization catalysts |
| EP0985677A1 (en) * | 1998-09-07 | 2000-03-15 | Industrial Technology Research Institute | Dinuclear metallocene catalyst for olefin polymerization |
| GB9826874D0 (en) * | 1998-12-07 | 1999-01-27 | Borealis As | Process |
| US6339035B1 (en) * | 1999-02-22 | 2002-01-15 | Phillips Petroleum Company | Catalyst and process for polymerizing olefins |
| DE19929809A1 (en) | 1999-06-30 | 2001-01-04 | Ticona Gmbh | Continuous process for the production of an amorphous polyolefin with a broad molar mass distribution and uniform glass temperature |
| DE19932384A1 (en) * | 1999-07-14 | 2001-01-18 | Mitsubishi Polyester Film Gmbh | White, biaxially oriented polyester film with cycloolefin copolymer (COC), process for its production and its use |
| US6544919B1 (en) | 1999-10-06 | 2003-04-08 | Sri International | Multinuclear transition metal catalysts for preparation of multimodal polymer compositions |
| KR100416470B1 (en) * | 1999-12-20 | 2004-01-31 | 삼성아토피나주식회사 | Ethylene-Aromatic Vinyl Compound-Vinyl Norbonene Terpolymer |
| US7151143B2 (en) * | 2000-01-21 | 2006-12-19 | Cyclics Corporation | Blends containing macrocyclic polyester oligomer and high molecular weight polymer |
| US6906147B2 (en) * | 2002-03-20 | 2005-06-14 | Cyclics Corporation | Catalytic systems |
| US7256241B2 (en) * | 2000-01-21 | 2007-08-14 | Cyclics Corporation | Methods for polymerizing macrocyclic polyester oligomers using catalyst promoters |
| US6960626B2 (en) * | 2000-01-21 | 2005-11-01 | Cyclics Corporation | Intimate physical mixtures containing macrocyclic polyester oligomer and filler |
| US20050282952A1 (en) * | 2000-01-21 | 2005-12-22 | Cyclics Corporation | Graphite-polyester composites made from macrocyclic polyester oligomers |
| US6420047B2 (en) * | 2000-01-21 | 2002-07-16 | Cyclics Corporation | Macrocyclic polyester oligomers and processes for polymerizing the same |
| DE10003934A1 (en) * | 2000-01-29 | 2001-08-09 | Daimler Chrysler Ag | Light guide, comprises at least one optical fiber made of cycloolefin copolymer with impeded crystallization |
| US6497676B1 (en) * | 2000-02-10 | 2002-12-24 | Baxter International | Method and apparatus for monitoring and controlling peritoneal dialysis therapy |
| DE10009286A1 (en) * | 2000-02-28 | 2001-08-30 | Mitsubishi Polyester Film Gmbh | White, biaxially-oriented, fire-resistant, UV-stabilised polyester film, used e.g. for packaging light- or air-sensitive food, has at least one layer containing cyclo-olefin copolymer, UV stabiliser and fire retardant |
| DE10011652A1 (en) * | 2000-03-10 | 2001-09-13 | Mitsubishi Polyester Film Gmbh | Biaxially oriented polyester film with high whiteness, process for its production and its use |
| US6875719B2 (en) * | 2000-04-27 | 2005-04-05 | Industrial Technology Research Institute | Catalyst composition for preparing olefin polymers |
| US20020147104A1 (en) * | 2000-04-27 | 2002-10-10 | Industrial Technology Research Institute | Catalyst composition for preparing olefin polymers |
| DE10026177A1 (en) * | 2000-05-26 | 2001-11-29 | Mitsubishi Polyester Film Gmbh | White, high-gloss polyester film containing cycloolefin copolymer (COC), process for its production and its use |
| DE10030235A1 (en) * | 2000-06-20 | 2002-01-03 | Mitsubishi Polyester Film Gmbh | White, sealable, thermoformable, biaxially oriented and coextruded polyester film with cycloolefin copolymer, process for its production and its use |
| EP1179554A1 (en) * | 2000-08-08 | 2002-02-13 | Industrial Technology Research Institute | Catalyst composition for preparing olefin polymers |
| JP2004507599A (en) * | 2000-09-01 | 2004-03-11 | サイクリクス コーポレイション | Method for converting linear polyester into macrocyclic oligoester composition and macrocyclic oligoester |
| US7767781B2 (en) * | 2000-09-01 | 2010-08-03 | Cyclics Corporation | Preparation of low-acid polyalkylene terephthalate and preparation of macrocyclic polyester oligomer therefrom |
| US7750109B2 (en) | 2000-09-01 | 2010-07-06 | Cyclics Corporation | Use of a residual oligomer recyclate in the production of macrocyclic polyester oligomer |
| US6372848B1 (en) | 2000-10-10 | 2002-04-16 | Baxter International Inc. | Blend of ethylene and α-olefin copolymers obtained using a metallocene catalyst for fabricating medical films and tubings |
| KR100417037B1 (en) * | 2000-12-22 | 2004-02-05 | 이동호 | Method for preparing cycloolefin copolymer having desirable material properties |
| US6670423B2 (en) | 2001-02-20 | 2003-12-30 | E. I. Du Pont De Nemours And Company | Polar ethylene-based polymer, cycloolefin polymer blends |
| US6696524B2 (en) | 2001-02-20 | 2004-02-24 | E. I. Du Pont De Nemours And Company | Low Tg ethylene-based polymer, cycloolefin polymer blends |
| JP2002338617A (en) * | 2001-05-22 | 2002-11-27 | Sumitomo Chem Co Ltd | Catalyst component for vinyl compound polymerization, vinyl compound polymerization catalyst, production method for vinyl compound polymer, and using method for transition metal compound |
| US7304123B2 (en) * | 2001-06-27 | 2007-12-04 | Cyclics Corporation | Processes for shaping macrocyclic oligoesters |
| US7071291B2 (en) * | 2001-06-27 | 2006-07-04 | Cyclics Corporation | Isolation, formulation and shaping of macrocyclic oligoesters |
| US20030077466A1 (en) * | 2001-10-19 | 2003-04-24 | Smith Sidney T. | Multilayered polymer structure |
| JP4704682B2 (en) * | 2001-12-21 | 2011-06-15 | イー・アイ・デュポン・ドウ・ヌムール・アンド・カンパニー | Multilayer film |
| US20030125662A1 (en) * | 2002-01-03 | 2003-07-03 | Tuan Bui | Method and apparatus for providing medical treatment therapy based on calculated demand |
| US7238164B2 (en) | 2002-07-19 | 2007-07-03 | Baxter International Inc. | Systems, methods and apparatuses for pumping cassette-based therapies |
| US6831188B1 (en) | 2002-07-31 | 2004-12-14 | Albemarle Corporation | Dihydrocarbylamino metal compounds |
| WO2004024739A1 (en) * | 2002-09-12 | 2004-03-25 | Dow Global Technologies Inc. | Preparation of metal amide complexes |
| DE60308885T2 (en) * | 2002-09-12 | 2007-04-12 | Dow Global Technologies, Inc., Midland | PREPARATION OF METAL COMPLEXES |
| KR100576971B1 (en) * | 2002-09-13 | 2006-05-10 | 금호석유화학 주식회사 | A method for producing dinuclear transition metal complexes as olefin polymerization catalyst |
| US20060004157A1 (en) * | 2002-09-17 | 2006-01-05 | Arriola Daniel J | Process for manufacture of polymers |
| US7037989B2 (en) * | 2003-05-27 | 2006-05-02 | Exxonmobil Chemical Patents Inc. | Copolymers of ethylene and/or α-olefins and vicinally disubstituted olefins |
| ES2349641T3 (en) * | 2003-09-26 | 2011-01-07 | Lubrizol Advanced Materials, Inc. | TRANSPARENT THERMOPLASTIC MIXTURE OF A CYCLOLEFINE COPOLYMER AND A THERMOPLASTIC POLYURETHANE. |
| TWI356073B (en) * | 2003-09-26 | 2012-01-11 | Lubrizol Advanced Mat Inc | A transparent thermoplastic blend of a cycloolefin |
| DE602004025971D1 (en) * | 2003-12-19 | 2010-04-22 | Cyclics Corp | METHOD OF DISPERSING A PUNCHING MODULE IN A MACROCYCLIC POLYESTEROLIGOMER |
| US20050209563A1 (en) * | 2004-03-19 | 2005-09-22 | Peter Hopping | Cassette-based dialysis medical fluid therapy systems, apparatuses and methods |
| CN101142273B (en) * | 2005-03-18 | 2011-05-11 | 三井化学株式会社 | Resin composition for solar cell package |
| JP4830800B2 (en) * | 2006-11-09 | 2011-12-07 | Ｊｓｒ株式会社 | Manufacturing method of thin optical lens molding |
| US8361023B2 (en) * | 2007-02-15 | 2013-01-29 | Baxter International Inc. | Dialysis system with efficient battery back-up |
| US7731689B2 (en) | 2007-02-15 | 2010-06-08 | Baxter International Inc. | Dialysis system having inductive heating |
| US7998115B2 (en) * | 2007-02-15 | 2011-08-16 | Baxter International Inc. | Dialysis system having optical flowrate detection |
| US8870812B2 (en) | 2007-02-15 | 2014-10-28 | Baxter International Inc. | Dialysis system having video display with ambient light adjustment |
| US8558964B2 (en) | 2007-02-15 | 2013-10-15 | Baxter International Inc. | Dialysis system having display with electromagnetic compliance (“EMC”) seal |
| US7863210B2 (en) | 2007-12-28 | 2011-01-04 | Chevron Phillips Chemical Company Lp | Nano-linked metallocene catalyst compositions and their polymer products |
| US8080681B2 (en) * | 2007-12-28 | 2011-12-20 | Chevron Phillips Chemical Company Lp | Nano-linked metallocene catalyst compositions and their polymer products |
| US8012900B2 (en) * | 2007-12-28 | 2011-09-06 | Chevron Phillips Chemical Company, L.P. | Nano-linked metallocene catalyst compositions and their polymer products |
| US8163948B2 (en) | 2008-02-29 | 2012-04-24 | Albemarle Corporation | Processes for producing transition metal amido and imido compounds |
| US7919639B2 (en) * | 2009-06-23 | 2011-04-05 | Chevron Phillips Chemical Company Lp | Nano-linked heteronuclear metallocene catalyst compositions and their polymer products |
| JP6230127B2 (en) | 2012-01-31 | 2017-11-15 | イー・アイ・デュポン・ドウ・ヌムール・アンド・カンパニーＥ．Ｉ．Ｄｕ Ｐｏｎｔ Ｄｅ Ｎｅｍｏｕｒｓ Ａｎｄ Ｃｏｍｐａｎｙ | Multilayer film containing cyclic olefin copolymer |
| US10844217B2 (en) | 2016-05-12 | 2020-11-24 | Sabic Global Technologies B.V. | Capacitor films with high temperature performance, methods of manufacture, and articles thereof |
| US11179516B2 (en) | 2017-06-22 | 2021-11-23 | Baxter International Inc. | Systems and methods for incorporating patient pressure into medical fluid delivery |
Family Cites Families (21)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| ZA844157B (en) | 1983-06-06 | 1986-01-29 | Exxon Research Engineering Co | Process and catalyst for polyolefin density and molecular weight control |
| US5324800A (en) * | 1983-06-06 | 1994-06-28 | Exxon Chemical Patents Inc. | Process and catalyst for polyolefin density and molecular weight control |
| IL85097A (en) | 1987-01-30 | 1992-02-16 | Exxon Chemical Patents Inc | Catalysts based on derivatives of a bis(cyclopentadienyl)group ivb metal compound,their preparation and their use in polymerization processes |
| PL276385A1 (en) | 1987-01-30 | 1989-07-24 | Exxon Chemical Patents Inc | Method for polymerization of olefines,diolefins and acetylene unsaturated compounds |
| US5003019A (en) | 1987-03-02 | 1991-03-26 | Mitsui Petrochemical Industries, Ltd. | Cyclo-olefinic random copolymer, olefinic random copolymer, and process for producing cyclo-olefinic random copolymers |
| DE3726067A1 (en) | 1987-08-06 | 1989-02-16 | Hoechst Ag | METHOD FOR PRODUCING 1-OLEFIN POLYMERS |
| DE3922546A1 (en) | 1989-07-08 | 1991-01-17 | Hoechst Ag | METHOD FOR THE PRODUCTION OF CYCLOOLEFINPOLYMERS |
| CA2027145C (en) | 1989-10-10 | 2002-12-10 | Michael J. Elder | Metallocene catalysts with lewis acids and aluminum alkyls |
| DE69026679T3 (en) | 1989-10-30 | 2005-10-06 | Fina Technology, Inc., Houston | Addition of alkylaluminum to improve a metallocene catalyst |
| US5371158A (en) * | 1990-07-05 | 1994-12-06 | Hoechst Aktiengesellschaft | Bulk polymerization using specific metallocene catalysts for the preparation of cycloolefin polymers |
| ES2116301T3 (en) * | 1991-03-09 | 1998-07-16 | Targor Gmbh | PROCEDURE FOR THE OBTAINING OF CYCLOOLEFIN COPOLYMERS HOMOGENEOUS CHEMICALLY. |
| TW312695B (en) | 1992-02-22 | 1997-08-11 | Hoechst Ag | |
| TW286324B (en) | 1992-04-22 | 1996-09-21 | Hoechst Ag | |
| IT1256603B (en) | 1992-10-30 | 1995-12-12 | Enichem Polimeri | CATALYST AND PROCEDURE FOR (CO) POLYMERIZING ALPHA-OLEFINS |
| DE4304311C2 (en) * | 1993-02-12 | 1998-08-06 | Hoechst Ag | Cycloolefin copolymers for extrusion and injection molding articles and process for the preparation of a cycloolefin copolymer |
| DE4304291A1 (en) * | 1993-02-12 | 1994-08-18 | Hoechst Ag | Cycloolefin copolymers with low melt viscosity and low optical attenuation |
| EP0610851B1 (en) * | 1993-02-12 | 1997-05-07 | Hoechst Aktiengesellschaft | Process for preparing cyclo-olefin copolymers |
| DE59408260D1 (en) * | 1993-02-12 | 1999-06-24 | Ticona Gmbh | Process for the preparation of cycloolefin polymers |
| FI945959A (en) * | 1993-12-21 | 1995-06-22 | Hoechst Ag | Metallocenes and their use as catalysts |
| US5597935A (en) * | 1994-06-01 | 1997-01-28 | University Of Iowa Research Foundation | Synthesis of ansa-metallocene catalysts |
| DE4422157A1 (en) * | 1994-06-24 | 1996-01-04 | Hoechst Ag | Process for the preparation of cycloolefin copolymers |
-
1995
- 1995-12-13 DE DE19546500A patent/DE19546500A1/en not_active Withdrawn
-
1996
- 1996-12-10 EP EP96119751A patent/EP0779306B1/en not_active Expired - Lifetime
- 1996-12-10 DE DE59610845T patent/DE59610845D1/en not_active Expired - Lifetime
- 1996-12-11 TW TW085115303A patent/TW356473B/en not_active IP Right Cessation
- 1996-12-12 CN CN96121528A patent/CN1089771C/en not_active Expired - Lifetime
- 1996-12-12 CA CA002192771A patent/CA2192771C/en not_active Expired - Lifetime
- 1996-12-12 KR KR1019960064752A patent/KR100480532B1/en not_active IP Right Cessation
- 1996-12-13 JP JP8333458A patent/JPH09176223A/en active Pending
- 1996-12-13 US US08/766,622 patent/US5869586A/en not_active Expired - Lifetime
-
1998
- 1998-06-04 US US09/090,855 patent/US6020444A/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| CN1089771C (en) | 2002-08-28 |
| DE59610845D1 (en) | 2004-01-15 |
| KR100480532B1 (en) | 2005-07-07 |
| DE19546500A1 (en) | 1997-06-19 |
| EP0779306A3 (en) | 1999-03-03 |
| EP0779306A2 (en) | 1997-06-18 |
| US6020444A (en) | 2000-02-01 |
| CN1151995A (en) | 1997-06-18 |
| EP0779306B1 (en) | 2003-12-03 |
| CA2192771A1 (en) | 1997-06-14 |
| JPH09176223A (en) | 1997-07-08 |
| US5869586A (en) | 1999-02-09 |
| KR970042568A (en) | 1997-07-24 |
| TW356473B (en) | 1999-04-21 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CA2192771C (en) | Process for preparing a cycloolefin copolymer | |
| JP3334106B2 (en) | Catalyst for producing cycloolefin-based polymer | |
| JP3493387B2 (en) | Metallocenes and their use as catalysts | |
| JP3416243B2 (en) | Method for producing cycloolefin polymer | |
| CA2152552C (en) | Process for preparing cycloolefin copolymers | |
| CA2055397C (en) | Bulk polymerization using specific metallocene catalysts for the preparation of cycloolefin polymers | |
| CA2062201C (en) | Process for the preparation of chemically homogeneous cycloolefin copolymers | |
| AU649520B2 (en) | Cycloolefin (co)polymers with a narrow molecular weight distribution and a process for the preparation thereof | |
| CA2275430C (en) | Method for producing cycloolefin polymers | |
| CA2186232A1 (en) | Metallocene compounds, process for their prepration, and their use in catalysts for the polymerization of olefins | |
| JPH06271628A (en) | Production of cycloolefin copolymer | |
| CA2069603A1 (en) | Process for the preparation of syndiotactic polyolefins having a broad molecular weight distribution | |
| US6365686B1 (en) | Method for producing a cycloolefin copolymer | |
| JPH093117A (en) | Preparation of cycloolefin copolymer | |
| JPH06271626A (en) | Production of cycloolefin polymer | |
| JPH11171918A (en) | Production of norbornene-based random copolymer |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| EEER | Examination request | ||
| MKEX | Expiry |
Effective date: 20161212 |