Catalyst – solid sorbent – or support therefor: product or process – Catalyst or precursor therefor – Plural component system comprising a - group i to iv metal...
Reexamination Certificate
1998-12-21
2002-09-03
Wood, Elizabeth D. (Department: 1755)
Catalyst, solid sorbent, or support therefor: product or process
Catalyst or precursor therefor
Plural component system comprising a - group i to iv metal...
C502S118000, C502S122000, C502S123000, C502S125000, C502S126000, C502S127000, C502S128000, C502S152000, C502S167000, C502S172000
Reexamination Certificate
active
06444603
ABSTRACT:
FIELD OF THE INVENTION
The present invention relates to a catalyst component capable of providing a highly active catalyst for ethylenically unsaturated monomer polymerization when used in combination with a transition metal compound such as a metallocene compound. The invention also relates to a catalyst for ethylenically unsaturated monomer polymerization which comprises said catalyst component and a transition metal compound such as a metallocene compound and to a process for ethylenically unsaturated monomer polymerization using said catalyst.
BACKGROUND OF THE INVENTION
Titanium catalysts comprising a titanium compound and an organoaluminum compound and vanadium catalysts comprising a vanadium compound and an organoaluminum compound have conventionally been known as catalysts for producing (co)polymers of ethylenically unsaturated monomers (sometimes referred to as “ethylenically unsaturated monomer (co)polymers” hereinafter), such as polyethylene, polypropylene, poly-4-methyl-1-pentene, ethylene/propylene copolymer, ethylene/styrene copolymer and ethylene/propylene/butene terpolymer.
Ziegler catalysts comprising a metallocene compound such as zirconocene and an organoaluminum oxy-compound (aluminoxane) or a boron compound such as tris(pentafluorophenyl)borane have been known as catalysts capable of producing olefin polymers with high activities.
Further, catalysts comprising a nickel compound or a palladium compound and a co-catalyst such as an aluminoxane or an ionic compound have been proposed (J. Am. Chem. Soc., 1995, 117, 6414-6415).
Because of their excellent mechanical properties, ethylenically unsaturated monomer (co)polymers such as polyolefins have been used in various fields such as for molded products. In recent years, there have been diverse demands for physical properties of the ethylenically unsaturated monomer (co)polymers, so that such polymers showing various properties have been desired.
Under such circumstances as mentioned above, there has been desired development of a novel co-catalyst component exhibiting an excellent polymerization activity and capable of producing ethylenically unsaturated monomer (co)polymers of excellent properties.
OBJECT OF THE INVENTION
The present invention has been made in view of the prior art as described above. It is an object of the invention to provide a novel catalyst component capable of exhibiting a high ethylenically unsaturated monomer polymerization activity when used in combination with a transition metal compound such as a metallocene compound.
It is another object of the invention to provide a highly active catalyst which comprises said catalyst component and capable of producing polymers of high molecular weight.
It is a further object of the invention to provide a process for ethylenically unsaturated monomer polymerization using said catalyst.
SUMMARY OF THE INVENTION
The catalyst component for ethylenically unsaturated monomer polymerization according to the invention comprises a compound obtained by the reaction of the following compounds (i), (ii), (iii) and optionally (iv) in any order:
(i) a compound comprising a metal of Group 13 of the periodic table:
(ii) a compound capable of reacting with the compound (i) to be bonded to two or more of the Group 13 metal;
(iii) a compound capable of reacting with a compound comprising a metal of Group 13 of the periodic table to form an ionizing ionic compound; and
(iv) at least one compound selected from a hydrocarbon compound, a halogenated hydrocarbon compound, a hydroxyhydrocarbon compound, a silanol compound, a boronic acid compound, an organic carboxylic acid compound, an organic sulfonic acid compound, a hydroxylamine compound, a sufonamide compound, a ketoimide compound, an amide compound, an oxime compound, an amine compound, an imide compound, a diimine compound, an imine compound, a diketone compound, and metallic salts thereof.
The catalyst component for ethylenically unsaturated monomer polymerization according to another aspect of the invention comprises a compound obtained by the reaction of the following compounds (i), (ii) and optionally (iv) in any order, and then further the following compound (iii):
(i) a compound represented by the following formula:
MR
1
R
2
R
3
wherein M is an atom of Group 13 of the periodic table; R
1
, R
2
and R
3
nay be the same or different and are each a halogen atom, a hydrogen, atom, a hydroxy group or an organic group; and two groups of R
1
, R
2
and R
3
may be bonded to form a ring;
(ii) a compound capable of reacting with the compound (i) to be bonded to two or more M;
(iii) a compound capable of reacting with a compound comprising a metal of Group 13 of the periodic table, preferably with the reactor. product obtained by reacting the compound (i), the compound (ii) and optionally the compound (iv) in any order, to form an ionizing ionic compound;
(iv) at least one compound selected from a hydrocarbon compound, a halogenated hydrocarbon compound, a hydroxyhydrocarbon compound, a silanol compound, a boronic acid compound, an organic carboxylic acid compound, an organic sulfonic acid compound, a hydroxylamine compound, a sufonamide compound, a ketoimide compound, an amide compound, an oxime compound, an amine compound, an imide compound, a diimine compound, an imine compound, a diketone compound, and metallic salts thereof.
The compound (i) is, for example, an aluminum compound represented by the following formula:
R
a
m
Al(OR
b
)
n
X
p
wherein R
a
and R
b
may be the same or different and are each a hydrocarbon group of 1 to 15 carbon atoms; X is a halogen atom; and m, n and p are numbers satisfying the conditions of 0≦m≦3, 0≦n≦3, 0≦p≦3 and m+n+p=3.
The compound (ii) is, for example, at least one compound selected from the group consisting of H
2
O, H
2
S and compounds represented by the following formulae:
wherein R
4
is a hydrogen atom, a hydrocarbon group, a halogenated hydrocarbon group, a silicon-containing group, a germanium-containing group, a tin-containing group or an oxygen-containing group; R
5
is a divalent hydrocarbon group, a divalent halogenated hydrocarbon group, a divalent silicon-containing group, a divalent germanium-containing group, a divalent tin-containing group, a divalent boron-containing group or a single bond; R
6
and R
7
may be the same or different and are each a hydrogen atom, a hydrocarbon group, a halogenated hydrocarbon group, a silicon-containing group, a germanium-containing group, a tin-containing group or an oxygen-containing group; each of R
6
and R
7
may be bonded to a carbon atom for constituting R
5
to form a ring; and R
8
and R
9
may be the same or different and are each a hydrogen atom, a hydrocarbon group or a halogenated hydrocarbon group.
The compound (iii) is, for example, a compound capable of forming an ionizing ionic compound having a carbonium cation, an oxonium cation, an ammonium cation, a phosphonium cation, a cycloheptyltrienyl cation or a ferrocenium cation.
The compound (iv) is, for example, at least one compound selected from compounds represented by the following formulae:
R
10
X,
R
10
H,
R
10
OH,
R
10
R
11
NH,
R
10
COOH,
R
10
SO
3
H,
R
10
R
11
CNOH,
R
10
R
11
NOH,
R
10
CONHR
11
,
R
10
SO
2
NHR
11
,
R
10
COCH
2
COR
11
, and
R
10
C(═NH)CH
2
COR
11
wherein R
10
is a hydrocarbon group, a halogenated hydrocarbon group, a silicon-containing group, a germanium-containing group, a tin-containing group or a boron-containing group; R
11
is a hydrogen atom, an alkoxy group, or any of a hydrocarbon group, a halogenated hydrocarbon group, a silicon-containing group, a germanium-containing group, a tin-containing group and a boron-containing group each of which is the same as or different from R
10
; and X is a halogen atom.
The other catalyst component for ethylenically unsaturated monomer polymerization according to the invention is represented by the following formula:
wherein each M may be the same or different and is an atom of Group 13 of the periodic table; n is an integer of 0 or more; Y is a diva
Fujita Terunori
Makio Haruyuki
Tohi Yasushi
Tsutsui Toshiyuki
Birch & Stewart Kolasch & Birch, LLP
Mitsui Chemicals Inc.
Wood Elizabeth D.
LandOfFree
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