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
2002-07-09
2004-01-13
Choi, Ling-Siu (Department: 1713)
Catalyst, solid sorbent, or support therefor: product or process
Catalyst or precursor therefor
Plural component system comprising a - group i to iv metal...
C502S126000, C502S104000, C502S115000, C502S125000, C526S124300, C526S169200, C526S116000, C526S129000, C526S123100, C526S348000
Reexamination Certificate
active
06677266
ABSTRACT:
FIELD OF THE INVENTION
This invention relates to a process for preparing a catalyst component that is useful for olefin polymerization or interpolymerization. In particular the catalyst component comprises magnesium, titanium, vanadium compounds and an electron donor.
BACKGROUND OF THE INVENTION
Many catalysts are known for producing polyolefins having desired properties. Mixed metal catalysts of varying transition metals are used in producing polyolefins. In particular the use of mixed metal catalysts containing vanadium and titanium catalysts have been described in patents for such purpose. For example such patents include U.S. Pat. Nos. 6,084,042; 5,691,264; 5,442,018; 5,420,090; 5,231,151; 5,227,354; 5,106,805; 5,075,271; 5,059,570; 5,034,483; 5,013,701; 5,006,618; 5,006,499; 4,912,074; 4,831,000; 4,814,314; 4,612,300; 4,537,869; 4,506,029; and 4,471,066. The patents describe various types of catalysts and use of the catalysts for preparing polyolefins having various properties.
SUMMARY OF THE INVENTION
A process for preparing a catalyst component comprising titanium, vanadium, magnesium chloride and at least one electron donor (ED), both supported and unsupported. The process for preparing the catalyst component comprises contacting magnesium chloride with a vanadium compound containing at least one electron donor thereby yielding a product that is thereafter contacted with a titanium compound, wherein the amounts of the magnesium, titanium and vanadium are specifically defined. The resulting catalyst component, with a cocatalyst, provides a catalyst system suitable for the polymerization or interpolymerization of olefins.
DETAILED DESCRIPTION OF THE INVENTION
A process for preparing a catalyst component comprising titanium, vanadium, magnesium chloride and at least one electron donor (ED), both supported and unsupported. The process for preparing the catalyst component comprises contacting magnesium chloride with a vanadium compound containing at least one electron donor thereby yielding a product that is thereafter contacted with a titanium compound, wherein the amounts of the magnesium, titanium and vanadium are specifically defined. The resulting catalyst component, with a cocatalyst, provides a catalyst system suitable for the polymerization or interpolymerization of olefins.
All mention herein to elements of Groups of the Periodic Table are made in reference to the Periodic Table of the Elements, as published in “Chemical and Engineering News”, 63(5), 27, 1985. In this format, the Groups are numbered 1 to 18.
In the process for preparing the catalyst component, any magnesium chloride may be used. It has been found that the magnesium chloride may be utilized in the form of magnesium chloride supported on silica such as Sylopol 5550 support obtainable from Grace-Davison. Sylopol 5550 support is described as magnesium chloride supported on silica, containing 3.53 wt % magnesium and a molar ratio of chlorine to magnesium of 2.02.
In the present process there is used a vanadium compound containing at least one electron donor. The vanadium compounds that are usable herein are selected from OVX
m
(OR)
3−m
(ED)
s
; OVX
m
(NR
2
)
3−m
(ED)
s
; VX
n
(OR)
4−n
(ED)
s
; VX
n
(NR
2
)
4−n
(ED)
s
; [V
3
O(RCO
2
)
6
]
2
.[V
2
O
2
X
6
(ED)
s
]; [V(CO)
3
(ED)
s
].[V(CO)
6
]; M[V(bipy)
2
].(ED)
s
; M
3
[V(C
2
O
4
)
3
].(ED)
s
; M[VOX
4
].(ED)
s
; V
3
O(RCO
2
)
6
(ED)
s
; O
3−p
VR′
p
(ED)
S
; VX
m
R′
3−m
(ED)
s
; VX
2
.(ED)
s
; OVX
q
R′
r
(ED)
S
wherein m is 0 to 3, n is 0 to 4, p is 1 to 3, q is 0 to 2, r is 0 to 2, q is not equal to r, s is greater than 0, preferably s is from about 0.1 to about 3, X is independently fluorine, chlorine, bromine or iodine, R is independently a C
1
-C
18
acyclic or cyclic hydrocarbon radical, ED is an electron donor, M is a cation of lithium, sodium, potassium or cesium (Li
+
, Na
+
, K
+
or Cs
+
), bipy is 2,2′-bipyridine and R′ is a monoanionic bidentate ligand.
With respect to the above described vanadium compounds containing at least one electron donor, suitable for use as acyclic or cyclic radicals (R) are C
1-18
alkyl, C
2-18
alkenyl, C
4-18
dienyl, C
3-18
cycloalkyl, C
3-18
cycloalkenyl, C
4-18
cyclodienyl, C
6-18
aryl, C
7-18
aralkyl, and C
7-18
alkaryl.
Further with respect to the above described vanadium compounds containing at least one electron donor, the electron donors suitable for use herein include carboxylic acid esters, anhydrides, acid halides, ethers, alcohols, thiols, thioethers, aldehydes, ketones, imines, amines, amides; nitrites, isonitriles, cyanates, isocyanates, thiocyanates, isothiocyanates, thioesters, dithioesters, carbonic esters, hydrocarbyl carbamates, hydrocarbyl thiocarbamates, urethanes, sulfoxides, sulfones, sulfonamides, organosilicon compounds containing at least one oxygen atom, and nitrogen, phosphorous, arsenic or antimony compounds connected to an organic group through a carbon or oxygen atom. More preferred as electron donors are compounds containing from 1 to 50 carbon atoms and from 1 to 30 heteroatoms of an element, or mixtures thereof, selected from Groups 14, 15, 16 and 17 of the Periodic Table of Elements. Most preferred for use is an ether such as tetrahydrofuran.
Further with respect to the above described vanadium compounds containing at least one electron donor, suitable for use herein as the monoanionic bidentate ligand (R′) are the Lewis bases of the following compounds which contain acidic hydrogen; carboxylic acids, carboxylic acid amides, carboxylic acid phosphides, thiocarboxylic acids, dithiocarboxylic acids, thiocarboxylic acid amides, thiocarboxylic acid phosphides, carbonic acid, carbamamic acids, ureas, thiocarbonic acid, thioureas, thiocarbamamic acids, dithiocarbamic acids, hydroxycarboxylic esters, hydroxycarboxylic acid amides, amino acid esters, hydroxythiocarboxylic esters, hydroxydithiocarboxylic esters, hydroxythiocaboxylic acid amides, hydroxycarboxylic thioesters, hydroythiocarboxylic thioesters, hydroxydithiocarboxylic thioesters, mercaptocarboxylic esters, mercaptocarboxylic acid amides, mercaptothiocarboxylic esters, mercaptodithiocarboxylic esters, mercaptothiocarboxylic acid amides, mercaptocarboxylic thioesters, mercaptothiocarboxylic thioesters, mercaptodithiocarboxylic thioesters, hydroxyketones, hydroxyaldehydes, hydroxyimines, mercaptoketones, mercaptoaldehydes, mereaptoimines, hydroxythioketones, hydroxythioaldehydes, mercaptothioketones, mercaptothioaldehydes, 2-hydroxybenzaldehydes, 2-mercaptobenzaldehydes, 2-aminobenzaldehydes, 2-hydroxybenzthioaldehydes, 2-hydroxybenzoate esters, 2-hydroxybenzamides, 2-hydroxybenzoate thioesters, 2-hydroxythiobenzoate esters, 2-hydroxythiobenzamides, 2-hydroxybenzthioaldehydes, 2-mercaptobenzthioaldhydes, 2-aminobenzthioaldehydes, 2-hydroxyarylketones, 2-mercaptoarylketones, 2-aminoarylketones, 2-hydroxyarylimines, 2-mercaptoarylimines, 2-aminoarylimines, 2-hydroxyarylthioketones, 2-mercaptoarylthioketones, 2-aminoarylthioketones, benzoins, 2-pyrrolecarboxaldehydes, 2-pyrrolethiocarboxyaldehydes, 2-pyrrolecarboxaldimines, hydrocarbyl 2-pyrrolyl ketones, hydrocarbyl 2-pyrrolylimines, hydrocarbyl 2-pyrrolyl thioketones, 2-indolecarboxaldehydes, 2-indolethiocarboxaldehydes, 2-indolecarboxaldimines, hydrocarbyl 2-indolyl ketones, hydrocarbyl 2-indolyl imines, hydrocarbyl 2-indolyl thioketones, hydroxyquinolines, tropolones, aminotropolones, aminotropone imines, and the like.
Preferred for use herein as the vanadium compound containing an electron donor are VCl
3
.zTHF (z=2-3), VOCl
3
.THF, and VOF
3
.THF.
The vanadium compounds containing at least one electron donor may be prepared by any method known in the art. For example, a vanadium compound may be dissolved in excess electron donor and the excess electron donor subsequently removed.
In the present process the titanium compound is selected from TiX
a
(OR)
4
−
a
; TiX
a
(NR
2
)
4
−
a
; Ti(NR
2
Choi Ling-Siu
Eastman Chemical Company
Graves, Jr. Bernard J.
Richard Charles R.
Wood Jonathan D.
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