Synthetic resins or natural rubbers -- part of the class 520 ser – Synthetic resins – Polymers from only ethylenic monomers or processes of...
Reexamination Certificate
2000-08-03
2002-10-08
Wu, David W. (Department: 1713)
Synthetic resins or natural rubbers -- part of the class 520 ser
Synthetic resins
Polymers from only ethylenic monomers or processes of...
C526S171000, C526S172000, C526S120000, C526S348000, C526S141000, C502S155000, C502S167000
Reexamination Certificate
active
06462155
ABSTRACT:
TECHNICAL FIELD
The present invention relates to catalysts for olefin polymerization and to a method of using the catalysts for producing olefin polymers. More precisely, the invention relates to catalysts for olefin polymerization, with which polyolefins, especially polyethylenes are efficiently produced on an industrial scale, and relates to a method of using the catalysts for producing olefin polymers.
BACKGROUND ART
At present, Ziegler catalysts and metallocene catalysts are much used for olefin polymerization, and they comprise, as the essential catalyst component, a compound of a metal element belonging to Group 4 of the Periodic Table, such as titanium, zirconium, etc.
On the other hand, recently, novel catalyst systems that differ from the above have been developed, and they comprise a complex of a metal belonging to Groups 8 to 10 of the Periodic Table, such as typically nickel or palladium. Heretofore, nickel complexes have been known as oligomerization catalysts for olefins, but it has been said that they are unsuitable to polymer production.
Regarding the catalyst systems comprising such a nickel or palladium complex, some techniques have been proposed, including, for example, (1) a method of using a catalyst with an Ni (0) complex coordinated with an adduct of quinone and a tertiary phosphine for ethylene polymerization (Japanese Patent Publication No. 1796/1993); (2) a catalyst system comprising an Ni (0) complex, an adduct of maleic anhydride and a tertiary phosphine, a phosphorylide, and an organoaluminium compound (Japanese Patent Laid-Open No.; 203106/1986); (3) a catalyst system comprising an Ni(0) or Ni(II) complex and an iminophospholane compound (Japanese Patent Laid-Open No. 115311/1991); (4) a method of using a borate complex of a metal of Groups 8 to 10 (Fe, Co, Ni, Ru, Rh, Pd, Os, Ir, Pt) coordinated with a cis-type chelate ligand for ethylene polymerization (Japanese Patent Laid-Open No. 227608/1992); (5) a catalyst system comprising an Ni (0) complex, an adduct of an imide and a tertiary phosphine, and a phosphine oxide (Japanese Patent Laid-Open No. 122721/1994); (6) a catalyst system comprising a combination of a Pd(II):BF
4
−
complex and methylaluminoxane (Japanese Patent Laid-Open No. 82314/1995); (7) a catalyst system comprising an Ni (II) complex, an iminophospholane compound and an organoaluminium compound (Japanese Patent Laid-Open No. 277610/1991); (8) a catalyst system comprising an Ni(0) or Ni(II) complex and an iminophospholane compound having a bulky substituent (Japanese Patent Laid-Open No. 25932/1995); (9) a catalyst system comprising a combination of an Ni(II):phosphorus:oxygen chelate complex and a linear or cyclic aluminium compound (Japanese Patent Laid-Open No. 14217/1989), etc.
However, the ethylene polymerization method (1) is defective in that it requires an extremely high reaction pressure (for example, 100 kg/cm
2
) and the catalyst activity to give polyethylene therein is extremely low (about 6 kg/g-Ni·hr). The catalyst system (2) is also defective in that it is for high-pressure ethylene reaction: and it is complicated as comprising many different components. In addition, its activity is extremely low (about 1 kg/g-Ni·hr or less). The catalyst system (3) could be effective even under low reaction pressure, but its activity is extremely low (about 1 kg/g-Ni·hr or less). In the ethylene polymerization method (4), the catalyst activity is extremely low (about 0.1 kg/g-Ni·hr or less). The activity of the catalyst system (5) is low (about 5 kg/g-Ni·hr). Though comprising a cationic complex, the catalyst system (6) requires expensive methylaluminoxane for expressing its activity. In addition,: its activity is low (about 3 kg/g-Ni·hr or less). The activity of the catalyst systems (7) and (8) is extremely low (about 5 kg/g-Ni·hr or less). The catalyst system (9) contains a linear or cyclic organoaluminoxane that serves as a promoter. However, the organoaluminoxane is produced through reaction of a trialkylaluminium or dialkylaluminiummonochloride with water, and only methylaluminoxane is described in the examples. No description relating to a low-molecular-weight linear or cyclic organoaluminiumoxy compound is given in the specification. In addition, the system requires expensive methylaluminoxane. Still another drawback of the system is that it requires high reaction pressure, correlating to its activity, but its activity is low (for example, about 20 kg/g-Ni·hr or less under a reaction pressure of 30 kg/cm
2
G).
Recently, a catalyst system that comprises a combination of a complex of a metal of Groups 8 to 10, typically such as nickel or palladium, coordinated with a nitrogen-containing ligand such as a diimine or the like, and an organoaluminium compound such as methylaluminoxane (MAO) or the like, or comprises the nitrogen-containing ligand complex combined with an anion species of BF
4
−
, PF
6
−
, SbF
6
−
or BAF
−
[tetrakis(3,5-bistrifluoromethylphenyl)borate] has been disclosed (International Patent Laid-Open No. 96/23010). For example, disclosed is a catalyst system comprising a compound of a formula [1]:
wherein: R
10
and R
13
each independently represent an aliphatic hydrocarbon group having from 1 to 20 carbon atoms, or an aromatic group having from 7 to 20 carbon atoms in total and having a hydrocarbon group on its ring; R
11
and R
12
each independently represent a hydrogen atom, or a hydrocarbon group having from 1 to 20 carbon atoms; R
11
and R
12
may be bonded to each other to form a ring; X and Y each independently represent a hydrogen atom, or a hydrocarbon group having from 1 to 20 carbon atoms; M represents a transition metal of Groups 8 to 10 of the Periodic Table.
The catalyst system has the advantage of extremely high activity in ethylene polymerization, as compared with the catalyst systems mentioned above, but can be used only at low temperatures. In addition, the molecular weight of the polymers produced with it is low. Therefore, the catalyst system is not as yet practicable.
Further recently, a catalyst system comprising a nitrogen-containing tridentate ligand complex with iron or cobalt has been disclosed (Brookhart et al., J. Am. Chem. Soc., 1998, 4049; Gibson et al., Chem. Commun., 1998, 849). For example, it includes a compound of a formula [2]:
wherein X and Y each independently represent a hydrogen atom, a halogen atom, or a hydrocarbon group having from 1 to 20 carbon atoms; M represents a transition metal of Groups 8 to 10 of the Periodic Table.
The catalyst system has the advantage of extremely high activity in ethylene polymerization (about 400 kg/g-Ni·hr), as compared with the conventional Group 8 to 10 transition metal catalysts mentioned above. However, in order to fully express its activity, it requires a large amount of an aluminoxane, especially methylaluminoxane. Methylaluminoxane is expensive, and, in addition, it is difficult to handle, its storage stability is poor, and it is extremely dangerous. Aluminoxanes must be produced through reaction of a trialkylaluminium or dialkylaluminiummonochloride with water, and the reaction efficiency for producing them is low.
The present invention relates to catalysts for olefin polymerization and to a method of using the catalysts for producing olefin polymers. More precisely, its object is to provide catalysts for olefin polymerization and a method of using the catalysts for producing olefin polymers, of which the advantages are that the catalysts do not require methylaluminoxane which is expensive and difficult to handle, and of which storage stability is poor, and is extremely dangerous, and olefin polymers, especially polyethylenes are efficiently produced on an industrial scale.
DISCLOSURE OF THE INVENTION
We, the present inventors have assiduously studied so as to attain the object as above, and, as. a result, have found that the object can be attained by polymerizing olefins, especially ethylene, in the presence of a catalyst which comprises a transition metal compound
Choi Ling-Siu
Idemitsu Petrochemical Co. Ltd.
Wu David W.
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