Organic compounds -- part of the class 532-570 series – Organic compounds – Heavy metal containing
Patent
1994-09-02
1996-07-02
Wu, David W.
Organic compounds -- part of the class 532-570 series
Organic compounds
Heavy metal containing
556 13, 556 19, 556 52, 556 7, 502155, 526126, 526170, 526 10, C07F 1700
Patent
active
055323944
DESCRIPTION:
BRIEF SUMMARY
This invention relates to addition polymerization catalysts comprising certain stabilized, reduced metal complexes. In one embodiment such catalysts additionally employ an activating cocatalyst. In another embodiment such catalysts may be employed with or without an activating cocatalyst. Finally the invention relates to an improved method for preparing the stabilized reduced metal complexes. The compositions are especially useful as catalysts for the polymerization of olefins such as ethylene for the preparation of polymers having utility as molding resins and in the formation of foamed products having cushioning and insulating applications and films that are useful as protective wrappings.
In U.S. Ser. No. 545,403, filed Jul. 3, 1990 (equivalent to EP-A-0416,845)there are disclosed and claimed certain monocyclopentadienyl metal complexes having utility as homogeneous olefin polymerization catalysts. In U.S. Pat. No. 5,064,802 (equivalent to EP-A-0418,044), cationic monocyclopentadienyl metal complexes with salts of Bronsted acids containing a non-coordinating compatible anion are disclosed and claimed. In U.S. Ser. No. 547,718, also filed on Jul. 3, 1990 now abandoned (EP-A-0468,651), an oxidative activation technique for preparing such cationic catalysts is disclosed and claimed.
In U.S. Pat. No. 4,057,565 there are disclosed Ti, Zr, or Hf derivatives of 2-dialkylaminobenzyl or 2-dialkylaminomethylphenyl all in the +4 oxidation state which are useful as components of catalysts for olefin polymerization.
In J. Am. Chem. Soc. 100, 8068-8073 (1978) there is mentioned the synthesis and characterization of Ti(+3) complexes containing cyclopentadienyl groups and 2-dialkylaminobenzyl or 2-dialkylaminomethylphenyl groups. No mention of utility as addition polymerization catalysts is given.
In U.S. Pat. No. 4,870,042, catalysts for olefin polymerizations comprising a pyrazolyl borate complex of titanium or zirconium compounds including titanium trichloride (Example 4) are disclosed.
In Organometallics; 10,3227-3237(1991) certain titanium+3 complexes containing cyclopentadienyl groups and alkyl groups are mentioned. On page 3236, the reference states: established activity for catalytic olefin polymerization has been described . . . . Apparently, the tervalent Cp*.sub.2 TiR system cannot induce sufficient positive charge at the .beta.-carbon atom of an incoming ethylene molecule to reach the polar transition state for migratory insertion."
In Journal of Organometallic Chemistry, 334 (1987) C1-C4, .eta..sup.3 -allyl(bis-.eta..sup.5 -cyclopentadienyl)titanium (III) activated with dimethylaluminum chloride was found to create a coordinated species Cp.sub.2 Ti(allyl)-(CH.sub.3).sub.2 AlCl which was found to polymerize ethylene to a small extent. Use of stronger Lewis acids so as to cause ligand abstraction thereby destroying the requisite carbon-titanium bond was to be avoided according to the reference.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is an electron spin resonance spectrogram of the product obtained in preparation ii) of Examples 1-58.
FIG. 2 is an electron spin resonance spectrogram of the product obtained in Example 59.
FIG. 3 is an electron spin resonance spectrogram of the product obtained in Example 60.
According to the present invention in its most generic description, there is provided an addition polymerization catalyst comprising: ML.sub.c, wherein:
a is 1 or 2;
b is 0 or 1;
c is 1 or 2;
the sum of a, b and c is 3;
Cp independently each occurrence is a cyclopentadienyl group .pi.-bound to M, or a hydrocarbyl, silyl, halo, halohydrocarbyl, hydrocarbylmetalloid or halohydrocarbylmetalloid substituted derivative of said cyclopentadienyl group, said Cp containing up to 50 nonhydrogen atoms, and, when a is 2, optionally both Cp groups may be joined together by a bridging group;
L independently each occurrence is hydride, halo, or a monovalent anionic ligand selected from covalently bonded hydrocarbyl, silyl, amido, phosphido, alkoxy, aryloxy, and sulfido groups optionally being further substituted wit
REFERENCES:
patent: 4057565 (1977-11-01), Manzer
patent: 4870042 (1989-09-01), Kohara et al.
patent: 5064802 (1991-11-01), Stevens et al.
patent: 5189192 (1993-02-01), LaPointe et al.
J. Am. Chem. Soc. 113, 3623-3625 (1991).
Organometallics 10, 3227-3237 (1991).
Devore David D.
Nickias Peter N.
Rosen Robert K.
Stevens James C.
Timmers Francis J.
The Dow Chemical Company
Wu David W.
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