US5646084A
Expired / Lapsed
US
⏱️ 0.0 years remaining
Polymerization process using diene containing catalysts
Assignee: Dow Chemical Co
•
Filing: 1995-05-22
•
Granted: 1997-07-08
•
Expires: 2015-05-22
Abstract
Abstract Compositions comprising Group 4 metal complexes containing a diene moiety and activating cocatalysts are used as catalysts for polymerizing olefins, diolefins and/or acetylenically unsaturated monomers. Vinylidene aromatic monomers, particularly styrene are polymerized to form highly syndiotactic polymers.
Inventors
- 👤 Jasson Todd Patton
- 👤 David D. Devore
- 👤 Franis J. Timmers
- 👤 Jorge Soto
- 👤 Gregory F. Schmidt
- 👤 David R. Wilson
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-10-23 23:15
CPC Classifications
C; C08; C08F; C08F10/00; C08F4/00; C08F4/42; C08F4/44; C08F4/60; C08F4/62; C08F4/64; C08F4/659; C08F4/65908; C08F4/65912; C08F4/65916; C08F4/6592
Claims Analysis
Total Claims: 11
Claim 1
Independent Claim
171 words
A composition of matter comprising: 1) at least one metal complex corresponding to the formula: L.sub.m MD.sub.d X.sub.p X'.sub.q wherein: M is titanium in the +2 formal oxidation state; L is an anionic group containing an aromatic π-system through which the group is bound to M; D is a C 4-40 conjugated diene selected from the group consisting of 1,3-pentadiene, 1,4-diphenyl-1,3-butadiene, 3-methyl-1,3-pentadiene, 1,4-dibenzyl-1,3-butadiene, 2,4-hexadiene, 1,4-ditolyl-1,3-butadiene, and 1,4-bis(trimethylsilyl)-1,3-butadiene; X is an anionic ligand group having up to 40 atoms exclusive of the class of ligands defined by L; X' independently each occurrence is a neutral ligating compound having up to 20 atoms, with the proviso that X' is not π-bound to M through an arene group; d is 1 or 2; m is 0 or 1; p is 0, 1, or 2; q is 0, 1 or 2; and 2) an activating cocatalyst, the molar ratio of 1) to 2) being from 1:10,000 to 100:1, or the reaction product formed by converting 1) to an active catalyst by use of bulk electrolysis.
Claim 2
Dependent Claim
171 words
A composition of matter comprising: 1) at least one metal complex corresponding to the formula: L.sub.m MD.sub.d X.sub.p X'.sub.q wherein: M is titanium in the +2 formal oxidation state; L is an anionic group containing an aromatic π-system through which the group is bound to M; D is a C 4-40 conjugated diene selected from the group consisting of 1,3-pentadiene, 1,4-diphenyl-1,3-butadiene, 3-methyl-1,3-pentadiene, 1,4-dibenzyl-1,3-butadiene, 2,4-hexadiene, 1,4-ditolyl-1,3-butadiene, and 1,4-bis(trimethylsilyl)-1,3-butadiene; X is an anionic ligand group having up to 40 atoms exclusive of the class of ligands defined by L; X' independently each occurrence is a neutral ligating compound having up to 20 atoms, with the proviso that X' is not π-bound to M through an arene group; d is 1 or 2; m is 0 or 1; p is 0, 1, or 2; q is 0, 1 or 2; and 2) an activating cocatalyst, the molar ratio of 1) to 2) being from 1:10,000 to 100:1, or the reaction product formed by converting 1) to an active catalyst by use of bulk electrolysis.
Claim 3
Dependent Claim
124 words
A composition according to claim 1 wherein the metal complex corresponds to the formula: ##STR12## wherein: M is titanium in the +2 formal oxidation state; R' in each occurrence is independently selected from the group consisting of hydrogen, alkyl, aryl, aralkyl, silyl, germyl, cyano, halo and combinations thereof said R' having up to 20 non-hydrogen atoms, or adjacent R' groups (when R' is not hydrogen, cyano or halo) together form a hydrocarbylene group connected to adjacent positions of the cyclopentadienyl ring D is a neutral, η 4 -bonded, C 5-30 conjugated diene group selected from the group consisting of 1,3-pentadiene, 1,4-diphenyl-1,3-butadiene, 3-methyl-1,3-pentadiene, 1,4-dibenzyl- 1,3-butadiene, 2,4-hexadiene, 1,4-ditolyl- 1,3-butadiene, and 1,4-bis(trimethylsilyl)-1,3-butadiene; and X is chloride, allyl, methyl substituted allyl, pentadienyl or C 1-6 hydrocarbyl substituted pentadienyl.
Claim 4
Dependent Claim
21 words
A composition according to claim 1 wherein X independently each occurrence is methoxide, isopropoxide, t-butoxide, phenoxide, dimethylamide, allyl, 1-methylallyl, or pentadienyl.
Claim 5
Dependent Claim
26 words
A composition according to claim 1 wherein L is selected from the group consisting of cyclopentadienyl, methylcyclopentadienyl, tetrammethylcyclopentadienyl, pentamethylcyclopentadienyl, t-butylcyclopentadienyl, indenyl, tetramethylindenyl, fluorenyl, tetrahydrofluorenyl and octahydrofluorenyl.
Claim 6
Dependent Claim
16 words
A composition according to claim 1 wherein the metal complex is pentamethylcyclopentadienyltitanium(1,4-diphenyl-1,3-butadiene)t-butoxide, pentamethylcyclopentadienyltitanium(1,4-diphenyl-1,3-butadiene)isopropoxide; pentamethylcyclopentadienyltitanium(1,4-diphenyl-1,3-butadiene)chloride, or pentamethylcyclopentadienyltitanium(1,4-diphenyl-1,3-butadiene)phenoxide.
Claim 7
Dependent Claim
60 words
A composition according to claim 1 wherein the activating cocatalyst is selected from the group consisting of polymeric or oligomeric alumoxanes; hydrocarbyl substituted Group 13 compounds containing from 1 to 10 carbons in each hydrocarbyl group; halogenated trihydrocarbylboron compounds containing from 1 to 10 carbons in each halogenated hydrocarbyl group; nonpolymeric, inert, compatible, noncoordinating, ion forming compounds; and combinations thereof.
Claim 8
Dependent Claim
27 words
A composition according to claim 1 wherein the activating cocatalyst is methylalumoxane, a C 1-30 trialkylaluminum compound, a C 1-10 trihydrocarbylammonium tetrakis(pentafluorophenyl)borate compound or a mixture thereof.
Claim 9
Dependent Claim
29 words
A composition according to claim 1 wherein the activating cocatalyst comprises a cation which is a Bronsted acid capable of donating a proton, and a noncoordinating, compatible, inert anion.
Claim 10
Dependent Claim
48 words
A composition according to claim 8 wherein the activating cocatalyst comprises a compound represented by the formula: (L*-H).sup.+.sub.f (A.sup.f-) wherein: L* is a neutral Lewis base; (L*-H) + is a Bronsted acid; A f- is a noncoordinating, compatible anion, and f is an integer from 1 to 3.
Claim 11
Dependent Claim
13 words
A composition according to claim 8 wherein the noncoordinating, compatible anion is tetrakis(pentafluorophenyl)borate.
References Cited (Backward Citations)
US3242099A
Cited
US5153157A
Cited
EP0277003A1
Cited
US5198401A
Cited
US4774301A
Cited
US4808680A
Cited
US5045517A
Cited
US5064802A
Cited
US5064918A
Cited
EP0468651A1
Cited
EP0520732A1
Cited
US5278272A
Cited
WO1993023412A1
Cited
US5470993A
Cited
USPTO Annuity & Maintenance Windows
| Annuity Stage | Window Opens | Payment Deadline | Surcharge Period Until | Estimated Fee | Status |
|---|---|---|---|---|---|
| 3.5 Years (Year 4) | 2000-07-07 | 2001-01-06 | 2001-07-08 | $2000.00 | Window Closed / Lapsed |
| 7.5 Years (Year 8) | 2004-07-07 | 2005-01-06 | 2005-07-08 | $3760.00 | Window Closed / Lapsed |
| 11.5 Years (Year 12) | 2008-07-07 | 2009-01-06 | 2009-07-08 | $7700.00 | Window Closed / Lapsed |