EP0416815A2
Expired / Lapsed
EP
⏱️ 0.0 years remaining
Constrained geometry addition polymerization catalysts, processes for their preparation, precursors therefor, methods of use, and novel polymers formed therewith
Assignee: Dow Chemical Co
•
Filing: 1990-08-30
•
Granted: —
•
Expires: 2010-08-30
Abstract
Abstract Metal coordination complexes comprising a metal of Group 3 (except Sc), 4-10 or the lanthanide series and a delocalized PI -bonded moiety have said moiety substituted with a constrain-inducing moiety which reduces the angle at the metal between the centroid of said PI -bonded moiety and at least one remaining substituted. Preferably, the complexes comprise a cyclopentadienyl or substituted cyclopentadienyl group forming part of a ring structure in which the metal is both bonded to an adjacent convalent moiety and held in association with the (substituted) cyclopentadienyl moiety. Complexes of said preferred structure are not necessarily constrained sufficiently to reduce the said angle. Amidosilane and amidoalkanediyl compounds are particularly preferred. The complexes of the invention form addition polymerization catalysts with activing cocatalysts such as Lewis acids, ammonium salts, oxidizing agents and, especially, aluminum compounds, particularly aluminum trialkyls. Novel polymers, including ElPE resins and pseudo-random copolymers, can be obtained using the catalysts of the invention.
Inventors
- 👤 James C. Stevens
- 👤 Francis J. Timmers
- 👤 David R. Wilson
- 👤 Gregory F. Schmidt
- 👤 Peter N. Nickias
- 👤 Robert K. Rosen
- 👤 George W. Knight
- 👤 Shih-Yaw Lai
Bibliographic Details
Application Number
—
Jurisdiction
EP
Data Source
google_patents
Last Synchronized
2026-11-03 22:53
CPC Classifications
C; C08; C08F; C08F4/00; C08F4/42; C08F4/44; C08F4/60; C08F4/62; C08F4/64; C08F10/00; C08F10/02; C07; C07F; C07F17/00; C07F7/00; C07F7/02; C07F7/08; C07F7/10; C07F9/00; C07F9/02; C07F9/28; C07F9/50; C07F9/5045; C08F210/00; C08F210/02; C08F210/16; C08L; C08L23/00; C08L23/02; C08L23/04; C08L23/08; C08L25/00; C08L25/02; C08L25/04; C08L25/06; C08F110/00; C08F110/02; C08F110/14; C08F4/659; C08F4/65908; C08F4/65912; C08F4/65916; C08F4/6592; C08L2203/00; C08L2203/14; C08L23/0807; C08L23/0838; Y; Y10; Y10S; Y10S526/00; Y10S526/943
Claims Analysis
Total Claims: 39
Claim 1
Independent Claim
122 words
A metal coordination complex comprising a metal of Group 3 (other than scandium), 4-10 or the lanthanide series of the Periodic Table of the Elements and a delocalized Π-bonded moiety substituted with a constrain-inducing moiety, said complex having a constrained geometry about the metal atom such that the angle at the metal between the centroid of the delocalized, substituted Π-bonded moiety and the center of at least one remaining substituent is less than such angle in an comparative complex differing only in that said constrain-inducing substituent is replaced by hydrogen, and provided further that for such complexes comprising more than one delocalized, substituted Π-bonded moiety, only one thereof for each metal atom of the complex is a cyclic, delocalized, substituted Π-bonded moiety.
Claim 2
Dependent Claim
122 words
A metal coordination complex comprising a metal of Group 3 (other than scandium), 4-10 or the lanthanide series of the Periodic Table of the Elements and a delocalized Π-bonded moiety substituted with a constrain-inducing moiety, said complex having a constrained geometry about the metal atom such that the angle at the metal between the centroid of the delocalized, substituted Π-bonded moiety and the center of at least one remaining substituent is less than such angle in an comparative complex differing only in that said constrain-inducing substituent is replaced by hydrogen, and provided further that for such complexes comprising more than one delocalized, substituted Π-bonded moiety, only one thereof for each metal atom of the complex is a cyclic, delocalized, substituted Π-bonded moiety.
Claim 3
Dependent Claim
25 words
A metal coordination complex as claimed in Claim 1, wherein said delocalized Π-bonded moiety is an alkene, alkenyl, alkyne, alkynyl, allyl, polyene or polyenyl moiety.
Claim 4
Dependent Claim
18 words
A metal coordination complex as claimed in Claim 1, wherein said delocalized Π-bonded moiety is a cyclic moiety.
Claim 5
Dependent Claim
19 words
A metal coordination complex as claimed in Claim 3, wherein said cyclic moiety is cyclopentadienyl or substituted cyclopentadienyl moiety.
Claim 6
Dependent Claim
42 words
A metal coordination complex as claimed in Claim 3 or Claim 4, wherein said cyclic moiety forms part of a ring structure in which said metal is both bonded to an adjacent covalent moiety and held in association with said cyclic moiety.
Claim 7
Dependent Claim
162 words
A metal coordination complex corresponding to the formula: wherein: M is a metal of Group 3 (other than scandium), 4-10, or the lanthanide series of the Periodic Table of the Elements; Cp* is a cyclopentadienyl or substituted cyclopentadienyl group bound in an η⁵ bonded mode to M; Z is a moiety comprising boron, or a member of Group 14 of the Periodic Table of the Elements and optionally sulfur or oxygen, said moiety having up to 20 non-hydrogen atoms, and optionally Cp* and Z together form a fused ring system; X each occurrence is an anionic ligand group or neutral Lewis base ligand group having up to 30 non-hydrogen atoms; n is 0, 1, 2, 3 or 4 depending on the valance of M; and Y is an anionic or nonanionic ligand group bonded to Z and M comprising nitrogen, phosphorus, oxygen or sulfur and having up to 20 non-hydrogen atoms, and optionally Y and Z together form a fused ring system.
Claim 8
Dependent Claim
162 words
A metal coordination complex corresponding to the formula: wherein: M is a metal of Group 3 (other than scandium), 4-10, or the lanthanide series of the Periodic Table of the Elements; Cp* is a cyclopentadienyl or substituted cyclopentadienyl group bound in an η⁵ bonded mode to M; Z is a moiety comprising boron, or a member of Group 14 of the Periodic Table of the Elements and optionally sulfur or oxygen, said moiety having up to 20 non-hydrogen atoms, and optionally Cp* and Z together form a fused ring system; X each occurrence is an anionic ligand group or neutral Lewis base ligand group having up to 30 non-hydrogen atoms; n is 0, 1, 2, 3 or 4 depending on the valance of M; and Y is an anionic or nonanionic ligand group bonded to Z and M comprising nitrogen, phosphorus, oxygen or sulfur and having up to 20 non-hydrogen atoms, and optionally Y and Z together form a fused ring system.
Claim 9
Dependent Claim
39 words
A metal coordination complex as claimed in Claim 6, wherein the substituted cyclopentadienyl group is cyclopentadienyl substituted by one or more C₁₋₂₀ hydrocarbyl, C₁₋₂₀ halohydrocarbyl, halogen or C₁₋₂₀ hydrocarbyl-substituted Group 14 metalloid or is indenyl, tetrahydroindenyl, fluorenyl or octahydrofluorenyl.
Claim 10
Dependent Claim
33 words
A metal coordiantion complex as claimed in Claim 6 or Claim 7, wherein each X is hydride, halo, alkyl, sily, germyl, aryl, amide, aryloxy, alkoxy, siloxy, phosphide, sulfide, acyl, cyanide, azide or acetylacetonate.
Claim 11
Dependent Claim
179 words
A metal coordination complex as claimed in Claim 6 corresponding to the formula: whrein R′ each occurrence is hydrogen or a moiety selected from alkyl, aryl, silyl, germyl, cyano, halo, or a combination thereof having up to 20 non-hydrogen atoms or an adjacent pair of R′ groups form a hydrocarbyl ring fused to the cyclopentadienyl moiety; X each occurrence is hydride or a moiety selected from halo, alkyl, silyl, germyl, aryl, amide, aryloxy, alkoxy, siloxy and combinations thereof having up to 20 non-hydrogen atoms and neutral Lewis base ligands having up to 20 non-hydrogen atoms; Y is -O-, -S-, -NR*-, -PR*-, or a neutral two electron donor ligand selected from of OR*, SR*, NR*₂, or PR*₂; M is as previously defined; and Z is SiR*₂, CR*₂, SiR*₂SiR*₂, CR*₂CR*₂, CR*=CR*, Cr*₂SiR*₂, GeR*₂, BR*, BR*₂; R* each occurrence is hydrogen or a moiety selected from alkyl, aryl, silyl, halogenated alkyl, halogenated aryl groups, and combinations thereof having up to 20 non-hydrogen atoms or two or more R* groups from Y, Z, or both Y and 2 form a fused ring system.
Claim 12
Dependent Claim
31 words
A metal coordination complex as claimed in Claim 9, wherein Y is an amido or phosphido group corresponding to the formula -N‴- or -PR‴-, wherein R‴ is C₁₋₁₀ alkyl or aryl.
Claim 13
Dependent Claim
99 words
A metal coordination complex as claimed in Claim 10 which is an amidosilane or amidoalkanediyl compound corresponding to the formula: wherein: M is titanium, zirconium or hafnium, bound in an η⁵ bonding mode to the cyclopentadienyl group; R′ each occurrence is hydrogen or a moiety selected from silyl, alkyl, aryl, or combinations thereof having up to 10 carbon or silicon atoms; E is silicon or carbon; X each occurrence is hydride, halo, alkyl, aryl, aryloxy, or alkoxy of up to 10 carbons; m is 1 or 2; and n is 1 or 3 depending on the valence of M.
Claim 14
Dependent Claim
49 words
A metal coordination complex as claimed in Claim 11, wherein each R′ is hydrogen, C₁₋₆ alkyl, norbornyl, benzyl or phenyl or R′ on the cyclopentadienyl moiety form with said moiety an indenyl, tetrahydroindenyl, fluorenyl or octahydrofluorenyl group; and X is chloro, bromo, iodo, C₁₋₆ alkyl, norbornyl, benzyl or phenyl.
Claim 15
Dependent Claim
27 words
A metal coordination complex as claimed in any one of Claims 1-5, wherein said angle is decreased by at least 5 percent compared with said comparative complex.
Claim 16
Dependent Claim
18 words
A metal coordination complex as claimed in Claim 13, wherein said angle decrease is at least 7.5 percent.
Claim 17
Dependent Claim
31 words
A metal coordination complex as claimed in Claim 13 or Claim 14, wherein said metal is a metal of Group 4 or lanthanide metal and said angle is less than 115°.
Claim 18
Dependent Claim
16 words
A metal coordiantion complex as claimed in Claim 15, wherein said angle is less than 105°.
Claim 19
Dependent Claim
28 words
A metal coordination complex as claimed in any one of Claims 1 to 10 and 13 to 16, wherein said metal is of Group 4 or lanthanide metal.
Claim 20
Dependent Claim
17 words
A metal coordination catalyst as claimed in Claim 17, wherein said metal is titanium, zirconium or hafnium.
Claim 21
Dependent Claim
27 words
A metal coordination complex selected from (tert-butylamido) (tetramethyl-η⁵-cyclopentadienyl)-1,2-ethanediylzirconium dichloride, (tert-butylamido)-(tetramethyl-η⁵-cyclopentadienyl)-1,2-ethanediyltitanium dichloride, (methylamido)-(tetramethyl-η⁵-cyclopentadienyl)-1,2-ethanediyl-zirconium dichloride, (methylamido)(tetramethyl-η⁵-cyclopentadienyl)-1,2-ethanediyltitanium dichloride, (ethylamido)(tetramethyl-η⁵-cyclopentadienyl)-methylenetitanium dichloride, (tert-butylamido)dimethyl-(tetramethyl-η⁵-cyclopentadienyl)silanetitanium dichloride, (tert-butylamido)dimethyl(tetramethyl-η⁵-cyclopentadienyl)silanezirconium dibenzyl, (benzylamido)dimethyl(tetramethyl-η⁵- cyclopentadienyl)silanetitanium dichloride, and (phenylphosphido)dimethyl(tetramethyl-η⁵-cyclopentadienyl)silanezirconium dibenzyl.
Claim 22
Dependent Claim
27 words
A metal coordination complex selected from (tert-butylamido) (tetramethyl-η⁵-cyclopentadienyl)-1,2-ethanediylzirconium dichloride, (tert-butylamido)-(tetramethyl-η⁵-cyclopentadienyl)-1,2-ethanediyltitanium dichloride, (methylamido)-(tetramethyl-η⁵-cyclopentadienyl)-1,2-ethanediyl-zirconium dichloride, (methylamido)(tetramethyl-η⁵-cyclopentadienyl)-1,2-ethanediyltitanium dichloride, (ethylamido)(tetramethyl-η⁵-cyclopentadienyl)-methylenetitanium dichloride, (tert-butylamido)dimethyl-(tetramethyl-η⁵-cyclopentadienyl)silanetitanium dichloride, (tert-butylamido)dimethyl(tetramethyl-η⁵-cyclopentadienyl)silanezirconium dibenzyl, (benzylamido)dimethyl(tetramethyl-η⁵- cyclopentadienyl)silanetitanium dichloride, and (phenylphosphido)dimethyl(tetramethyl-η⁵-cyclopentadienyl)silanezirconium dibenzyl.
Claim 23
Dependent Claim
26 words
A catalyst useful in addition polymerizations comprising a) a metal coordination complex as claimed in any one of the preceding claims, and b) an activating cocatlyst.
Claim 24
Dependent Claim
15 words
A catalyst as claimed in Claim 20, wherein said activing cocatalyst comprises an aluminum compound.
Claim 25
Dependent Claim
21 words
A catalyst as claimed in Claim 21, wherein said aluminum compound is an alkylaluminoxane, aluminum alkyl, aluminum halide, or aluminum alkylhalide.
Claim 26
Dependent Claim
21 words
A catalyst as claimed in Claim 20, wherein said activating cocatalyst comprises a Lewis acid, ammonium salt, or noninterfering oxidizing agent.
Claim 27
Dependent Claim
44 words
A catalyst as claimed in Claim 21, wherein the activating cocatalyst is selected from alkylaluminoxanes, and compounds corresponding to the formula: ALR n X˝ 3-n wherein: R is each occurrence C₁₋₁₀ alkyl or aralkyl; X˝ is halogen; and n is 1, 2 or 3.
Claim 28
Dependent Claim
136 words
A process for preparing a metal coordination complex as claimed in Claim 6 comprising. (a) contacting a metal compound of the formula MX n+2 or MX n+1 , or a coordinated adduct thereof with a dianionic salt compound corresponding to the formula: (L+x)y(Cp*-Z-Y)⁻² or (LX˝)+x)y(Cp*-Z-Y)⁻² wherein: n, Cp*, M, X, Y, and Z are as defined in Claim 6; L is a metal of Group 1 or 2 of the Periodic Table of the Elements, x and y are either 1 or 2 and the product of x and y equals 2, and X˝ is fluoro, bromo, chloro or iodo, in an inert aprotic solvent, and, when the metal compound is of the formula MX n+1 ; (b) contacting the product of (a) with a noninterfering oxidizing agent to raise the oxidation state of the metal.
Claim 29
Dependent Claim
27 words
A process for preparing a catalyst as claimed in Claim 20, comprising contacting a complex as defined in Claim 1 or Claim 6 with an activating cocatalyst.
Claim 30
Dependent Claim
39 words
An addition polymerization process for preparing a polymer by contacting one or more addition polymerizable monomers with a catalyst under addition polymerization conditions characterized in that the catalyst is as defined in any one of Claims 20 to 24.
Claim 31
Dependent Claim
35 words
A process as claimed in Claim 27, wherein the addition polymerizable monomers are selected from ethylenically unsaturated monomers, acetylenic compounds, conjugated or nonconjugated dienes, and polyenes having from 2 to 20 carbons, and carbon monoxide.
Claim 32
Dependent Claim
22 words
A process as claimed in Claim 27, wherein an alpha olefin is copolymerized with a vinylidene aromatic or hindered aliphatic vinyl monomers.
Claim 33
Dependent Claim
17 words
A process as claimed in Claim 29, wherein ethylene is copolymerized with a styrene or a vinylcyclohexene.
Claim 34
Dependent Claim
42 words
A copolymer comprising ethylene and an olefin other than ethylene obtainable by a process as defined in Claim 27 and having a melt index less than 200 ((I₂), ASTM D-1238 Procedure A, condition E) and an elastic modulus greater than 1000 dyne/cm².
Claim 35
Dependent Claim
21 words
A copolymers as claimed in Claim 31, wherein the olefin other than ethylene is propylene, isobutylene, 1-butene, 1-hexane, 4-methyl-1-pentene or 1-octene.
Claim 36
Dependent Claim
24 words
A pseudo-random polymer comprising an interpolymer of an olefin and a vinylidene aromatic monomer and obtainable by a process as defined in Claim 27.
Claim 37
Dependent Claim
12 words
A polymer as claimed in Claim 33, comprising ethylene and a styrene.
Claim 38
Dependent Claim
24 words
A pseudo-random polymer comprising an interpolymer of hindered aliphatic vinylidene compound and an alph-olefin and obtainable by a process as claimed in Claim 27.
Claim 39
Dependent Claim
12 words
A polymer as claimed in Claim 35, comprising ethylene and a vinylcyclohexane.
References Cited (Backward Citations)
No citation records indexed.
USPTO Annuity & Maintenance Windows
Maintenance schedule is calculated for granted US utility patents.