US 7,253,133 B2 · Catalyst for polymerization or copolymerization of olefins, preparation and use of the same

Abstract

Catalysts and catalyst systems useful for the olefin polymerization and copolymerization, and their synthesis procedure and usage are disclosed. These catalyst are a kind of novel complexes formed by transition metal from Group III to Group XI and multidentate ligand having the following formula:

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Claims29

Dependent claims

A catalytic system for olefin polymerization or copolymerization comprising a catalyst having the following formula:

wherein:
A, B, D, E, G, and connecting bonds comprise a tridentate ligand;
and wherein
A represents a metal-coordinating moiety selected from the group consisting of an oxygen atom-containing moiety, a sulfur atom-containing moiety, a selenium atom-containing moiety, a nitrogen atom-containing moiety, and a phosphorus atom-containing moiety;
B represents a chemically inert moiety selected from the group consisting of a nitrogen atom-containing moiety, a phosphorus atom-containing moiety, and a substituted or unsubstituted hydrocarbyl moiety;
D represents O, S, Se, or a metal-coordinating moiety selected from the group consisting of an oxygen atom-containing moiety, a nitrogen atom-containing moiety, a sulfur atom-containing moiety, and a selenium atom-containing moiety;
E represents a metal-coordinating moiety selected from the group consisting of an oxygen atom-containing moiety, a sulfur atom-containing moiety, a selenium atom-containing moiety, a nitrogen atom-containing moiety, and a phosphorus atom-containing moiety;
G represents a chemically inert substituted or unsubstituted phenylene group bridging D and E through
R1, R2, and R3 each individually represents hydrogen or a chemically inert substituted or unsubstituted hydrocarbyl moiety, R1 and R2 being optionally linked to form a ring;
R18, R19, R20, R21, each independently represents hydrogen, halogen, a chemically inert substituted or unsubstituted hydrocarbyl moiety;
M represents a transition metal selected from Group III to Group XI, M being linked to each of A, D, and E by a covalent or a coordinate covalent bond;
X represents a weakly coordinating monovalent ligand;
d is 1;
q is 0 or 1;
m is 1, 2 or 3;
and
n is 1, 2, 3 or 4 as needed to balance the charge on M.

14 more elements

Dependencies are inferred from the claim text.

Description11,479 words

Summary655 words

#This invention provides a new class of catalysts (catalyst systems) used for olefin polymerization and copolymerization, their synthesis and utility as homogeneous catalysts (used directly without support) or as heterogeneous catalysts (used after supported on the solids materials such as macromolecular materials, silica, alumina, magnesium chloride etc. or used as catalyst supported on polymer). The catalyst is based on the Group III to Group XI transition metal complexes of multidentate ligands.

#Since the discovery of the Ziegle-Natta catalyst in 1950s, highly active MgCl2-supported Ti catalysts prove to have excellent properties. (N. Kashiwa etc., U.S. Pat. No. 3,642,746, 1968) and are used for the manufacture of HDPE, LLDPE and i-PP. However, these catalysts are difficult to control the structure and physical properties of the polymer by changing the steric hindrance and electronic effect of the catalyst effectively. The metallocene single-site is found to be excellent for the controllable synthesis of the bulk materials (W. Kaminsky etc., Angew. Chem. Int. Ed. Engl. 1980, 19, 390; H. H. Brintzinger etc. Angew. Chem. Int. Ed. Engl. 1995, 34, 1143; Ishiha, Takeshi, JP 07268029; Exxon Co. Int., WO 9600243, WO 9611960, WO 9400500, WO 9506071). Several single-site non-metallocene catalysts with ligands having N, O, P atom etc. have also been developed since 1995 (M. S. Brookhart etc., WO 9623010, WO 98/30612, WO 99/02472; V. C. Gibson etc., WO 99/12981, WO 98/27124; D. H. McConville etc., WO 2000/069922; R. H. Grubbs etc., WO 98/42664, WO 98/42665; Terunori Fujita etc., WO 99/54364). Selected catalysts are showed as follows:

#To date, few reports appeared on the polymerization of olefins by non-metallocene titanium (IV) trichloride and zirconium (IV) trichloride complexes based on the single anion ligands. Nagy S. group reported the synthesis of 8-hydroxyl Quinoline titanium (IV) complex, which showed high activity in ethylene polymerization (Nagy S. etc. WO 9634021). A. Otero group reported the catalyst h was highly active in ethylene polymerization and gave high molecular weight PE and broad molecular weight dispersity (Organometallics, 2001, 20, 2428-2430).

Brief description of the drawings1 figure

#FIG. 1 shows an X-ray diffraction of compound J-1.

Detailed description10,815 words

#The present invention provides a new class of olefin polymerization and copolymerization catalyst (catalyst systems) and its preparation and usage in catalyzing the homopolymerization (including the oligomerization and copolymerization) of ethylene, α-olefin, and olefins containing functional group. It also provides the usage and the condition of polymerization about the catalysts. The catalysts provided in this invention are Group III to Group XI transition metal complexes of multidentate ligands.

#The olefin polymerization and copolymerization catalysts provided in this invention are the transition metal complexes showed below (formula I):

#A detailed representation of the catalyst is showed as formula IA and IB:

Facts

Application

10/761,827Filed 21 Jan 2004 · continuation in part

Priority

CN 01 1 2632323 Jul 2001

Published

US 2005/0004331 A16 Jan 2005

Granted

7 Aug 2007

Term ended

19 Dec 2022

Estimated · how

20 years from earliest known nonprovisional domestic filing plus recorded patent term adjustment, including 185 days of adjustment. Maintenance-fee lapses, terminal disclaimers and statutory extensions have not been checked. The continuity chain may be incomplete; this is not an enforceability determination.

Classification3 codes

C08F 10/00
Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double
C08F 210/16
Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond: copolymers of ethene with alpha-alkenes, e.g. EP…
C08F
Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds

Timeline

23 Jul 2001Priority claimedCN 01 1 26323
21 Jan 2004Application filedUS 10/761,827
13 Aug 2004Assigned to Shanghai Institute of Organic Chemistry, Chinese Academy of Sciencesassignment of assignor's interest
6 Jan 2005PublishedUS 2005/0004331 A1
7 Aug 2007GrantedUS 7,253,133 B2
19 Dec 2022Term endedEstimated, includes 185 days of adjustment

Catalyst for polymerization or copolymerization of olefins, preparation and use of the same

Life of this patent

Catalyst for polymerization or copolymerization of olefins, preparation and use of the same

Life of this patent

Life of this patent

Abstract

Drawings

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Claims29

Description11,479 words

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Classification3 codes

Life of this patent

Description11,479 words