Organic compounds -- part of the class 532-570 series – Organic compounds – Heavy metal containing
Reexamination Certificate
2001-05-10
2004-10-05
Bell, Mark L. (Department: 1755)
Organic compounds -- part of the class 532-570 series
Organic compounds
Heavy metal containing
C556S034000, C556S138000, C502S159000, C502S167000, C526S172000, C526S352000
Reexamination Certificate
active
06800774
ABSTRACT:
FIELD OF THE INVENTION
The present invention relates to a catalyst used for olefine polymerization and the preparation thereof. The present invention also relates to a method of polymerizing olefines by using the catalyst of the present invention.
BACKGROUND OF THE INVENTION
Polyolefine is a very important category of polymeric materials. Half of the plastics are polyolefine. They are widely used in industry, agriculture, national defense, communication, transportation and human daily life. Olefines can be polymerized to form macromolecular compounds called polyolefines by using a catalyst. Therefore, catalyst is a key to the development of polyolefine industry which plays a very important role in controlling the structures and properties of polyolefines.
Although the conventional Ziegler-Natta catalysts are still widely used in the industrial production of polyolefines, they are not good catalysts for the manufacture of linear low-density polyethylenes (LLDPE). Recently, it was found that zirconocene, a representative of the metallocene catalysts, possesses very high catalytic activity to copolymerize olefines and can be used for the production of LLDPE. However, an &agr;-olefine (such as butene-1, hexene-1, octene-1, and the like) as the second monomer is required by using metallocene to catalyze the polymerization of olefine for the production of LLDPE, which complicated the process of polymerization. In 1996, Johnson in Du Pont Co. disclosed that &agr;-diimino nickel(II) could be used as an olefine polymerization catalyst (WO 96/23010). With the action of a co-catalyst of methyl aluminoxane (MAO) or modified methyl aluminoxane (MMAO), it is possible to homopolymerize ethylene. By controlling the polymerization conditions, it is possible to obtain polyethylene (PE) including LLDPE with high molecular weight, low density and desired degree of branching.
DISCLOSURE OF THE INVENTION
It is an object of the present invention to provide a catalyst used for olefine polymerization which is a polynuclear &agr;-diimino Ni(II). The precursor of this catalyst is a polynuclear &agr;-diimino Ni(II) complex. The polynuclear &agr;-diimine Ni(II) complex can be activated by a neutral Lewis acids such as MAO, MMAO, which then catalyze the polymerization of ethylene into high molecular weight branched polymeric materials.
The polynuclear &agr;-diimino Ni(II) complex of the present invention has the following structure:
wherein M is Ni; X is Cl or Br, and preferably X is Br; m and n is dependently an integer from 0 to 100, and preferably m is from 1 to 20 and n is from 0 to 30 or m is from 0 to 20 and n is from 1 to 30, more preferably m is from 1 to 10 and n is from 0 to 20 or m is from 0 to 10 and n is from 1 to 20; R
1
and R
2
may be same or different, and is dependently H, methyl, ethyl, isopropyl or tert-butyl, preferably R
1
is isopropyl and R
2
is methyl or isopropyl; Y is CR
3
R
4
, wherein R
3
and R
4
may be same or different, and is dependently H, methyl, ethyl, propyl, butyl or phenyl, preferably R
3
and R
4
are the same, and are H or methyl, or R
3
and R
4
forming a cyclohexyl group; R
5
and R
6
may be same or different, and is dependently methyl, ethyl or heterocyclic group (such as 2-pyridyl group), preferably R
5
and R
6
are the same, and are methyl; Q is a divalent residual represent by the following formula or a mixture thereof:
preferably Q is a divalent residual of the following formula:
The polynuclear &agr;-diimino Ni(II) complex of the present invention can be prepared by a method comprising the following steps:
(a) condensing an &agr;-diketone represented by the formula or a mixture thereof,
wherein, Q, R
5
and R
6
are as defined above,
a substituted aromatic diamine represented by the formula
wherein, R
1
, R
2
and Y are as defined above,
and a substituted aromatic amine represented by the formula
wherein, R
1
and R
2
are as defined above, in a medium of alcohol, aromatic hydrocarbon, alcohol-ether mixture, or alcohol-halogenated hydrocarbon mixture and under the catalytic action of HCOOH, CF
3
COOH or HX, wherein X is F, Cl, Br, or I;
thereby obtaining an oligomer of substituted &agr;-diimine of the formula
wherein, R
1
, R
2
, R
5
, R
6
, Q, Y, m and n have the same definition of above;
(b) carrying out coordination reaction of the oligomer of step (a) with NiX
2
, wherein X is Cl or Br, in the absence of water and oxygen, thereby obtaining a polynuclear &agr;-diimino Ni(II) complex of the following formula:
wherein, R
1
, R
2
, R
5
, R
6
, Q, Y, M, X, m and n have the same definition of above.
The reaction process can be represent by the following scheme:
wherein, R
1
, R
2
, R
5
, R
6
, Q, Y, M, X, m and n have the same definition of above.
The polynuclear &agr;-diimino Ni(II) complex of the present invention is capable of catalyzing the polymerization of ethylene under the action of neutral Lewis acid such as MAO or MMAO and the like. Thus, polyethylene with high molecular weight can be obtained.
REFERENCES:
patent: 3624000 (1971-11-01), Throckmorton
patent: 3668146 (1972-06-01), Ruhle
patent: 6232259 (2001-05-01), Ittel et al.
US 2002/0082162 A1, US Pre-Grant publication to Li et al., published Jun. 27, 2002, US class 502/167.
Dai Ke
Li Yuesheng
Liu Jingyu
Zheng Yi
Bell Mark L.
Changchun Institute of Applied Chemistry Chinese Academy of Scie
Dickstein Shapiro Morin & Oshinsky LLP.
Pasterczyk J.
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