Imidochromium compounds contained in catalyst systems for...

Details Imidochromium compounds contained in catalyst systems for... Imidochromium compounds contained in catalyst systems for...

2002-04-12

2004-08-31

Lu, Caixia (Department: 1713)

Synthetic resins or natural rubbers -- part of the class 520 ser

Synthetic resins

Polymers from only ethylenic monomers or processes of...

C502S103000, C502S167000, C526S159000, C526S165000, C526S161000, C526S169000

Reexamination Certificate

active

06784261

ABSTRACT:

DESCRIPTION
The subject matter of the present invention is catalyst systems containing imidochromium compounds, new imidochromium complexes, a process for the polymerization of olefins as well as a process for the production of imidochromium complexes.
Many of the catalysts employed for the polymerization of &agr;-olefins are based on immobilized chromium oxides (see, for example, Kirk-Othmer, “Encyclopedia of Chemical Technology”, 1981, Volume 16, page 402). Such catalysts generally yield ethylene homopolymers and ethylene copolymers having high molecular weights although they are relatively insensitive to hydrogen, as a result of which they do not allow a simple control of the molecular weight. In contrast, the use of bis(cyclopentadienyl)chromium (U.S. Pat. No. 3,709,853), bis(indenyl)chromium or bis(fluorenyl)chromium (U.S. Pat. No. 4,015,059), which is applied onto an inorganic, oxidic support, makes it possible to easily regulate the molecular weight of polyethylene through the addition of hydrogen.
As is the case with Ziegler-Natta systems, chemists have recently sought for catalyst systems having a uniformly defined, active center, the so-called single-site catalysts, also for chromium compounds. The systematic variation of the ligand skeleton is supposed to make it easy to change the activity, the copolymerization behavior of the catalyst and the properties of the polymers thus obtained.
The preparation of bis(tert.-butylimido)bis(trimethylsiloxy)chromium by means of the reaction of dioxochromium dichloride with tert.-butyl(trimethylsilyl)amine was described by W. Nugent et al. in Inorg. Chem. 1980, 19, pages 777 to 779. Diaryl derivatives of this compound, namely, bis(tert.-butylimido)di(aryl)chromium were prepared by G. Wilkinson et al. as presented in J. Chem. Soc. Dalt. Trans. 1988, pages 53 to 60. The corresponding dialkyl complexes were described for the first time by C. Schaverien et al. (Organomet. 9 (1990), pages 774 to 782). They were also able to isolate a monoimidochromium compound tert.-butylimido(oxo)chromium dichloride by reacting tert.-butyl-imido-bis(trimethylsilanolato)oxochromium with phosphorus pentachloride (W. Nugent in Inorg. Chem. 1983, 22, pages 965 to 969).
EP-A 0,641,804 describes the use of bis(alkylimido)chromium(VI) and bis(arylimido)chromium(VI) complexes for the polymerization of olefins. In EP-A 0,816,384, these bis(imido)chromium(VI) complexes are supported on polyaminostyrene for the polymerization of ethylene and copolymerization of ethylene with higher &agr;-olefins. In this context, the preparation of bis(arylimido)chromium dichloride is a three-stage synthesis route since the reaction of dioxochromium dichloride with N-trimethyl-silylanilines does not yield bis(arylimido)chromium dichloride.
G. Wilkinson et al., were able to prepare tert.-butylimidochromium(V)trichloride and its donor-coordinated derivatives (J. Chem. Soc. Dalt. Trans. 1991, pages 2051 to 2061).
The objective of the present invention was to find new catalyst systems that can be easily modified and that are suitable for the polymerization of &agr;-olefins.
Moreover, the objective was to find an improved synthesis route for the preparation of bis(imido)chromium(VI) compounds.
Accordingly, catalyst systems have been found, containing
(A) at least one imidochromium compound, which can be obtained by a process encompassing the following process steps:
(a) contacting a dioxochromium compound with an N-sulfinyl compound R
1
—N═S═O or R
2
—N═S═O, wherein the variables have the following meaning:
R
1
stands for C
1
-C
20
-alkyl, C
2
-C
20
-alkanyl, C
6
-C
20
-aryl, alkylaryl having 1 to 10 carbon atoms in the alkyl radical and 6 to 20 carbon atoms in the aryl radical, whereby the organic radical R
1
can also have inert substituents, for SiR
3
3
;
R
2
stands for R
3
C═NR
4
, R
2
C═O, R
3
C═O(OR
4
), R
3
C═S, (R
3
)
2
P═O, (OR
3
)
2
P═O, SO
2
R
3
, R
5
R
4
C═N, NR
5
R
4
or BR
5
R
4
;
R
3
, R
4
independent of each other, stand for C
1
-C
20
-alkyl, C
2
-C
30
-alkenyl, C
4
-C
30
-aryl, alkylaryl having 1 to 10 carbon atoms in the alkyl radical and 6 to 20 carbon atoms in the aryl radical, for hydrogen if the latter is bonded to a carbon atom, whereby the organic radicals R
3
and R
4
can also have inert substituents;
(b) contacting the reaction product thus obtained with chlorine if a sulfinyl compound R
1
—N═S═O was used and, in case an N-sulfinyl compound R
2
—N═S═O was used, with chloride or sulfurylchloride or with no other reagent;
(B) at least one activator compound
and
(C) optionally, one or more additional catalysts commonly employed for the polymerization of olefins.
Furthermore, imidochromium compounds having the general formula II,
were found, wherein the variables have the following meaning:
R
2
stands for R
3
C═NR
4
, R
3
C═O, R
3
C═O(OR
4
), R
3
C═S, (R
3
)
2
P═O, (OR
3
)
2
P═O, SO
2
R
2
, R
3
R
4
C═N, NR
3
R
4
or BR
3
R
4
;
X independent of each other, strands for fluorine, chlorine, bromine, iodine, NR
5
R
6
, NP(R
5
)
3
, OR
5
, OSi(R
5
)
2
, SO
3
R
5
, OC(O)R
5
, &bgr;-diketonate, sulfate, dicarboxylates, dialcoholates, BF
4
−
, PF
6
−
, or bulky weakly on non-coordinating anions;
R
3
-R
6
independent of each other, stand for C
1
-C
20
-alkyl, C
2
-C
20
-alkenyl, C
6
-C
20
-aryl, alkylaryl, having 1 to 10 carbon atoms in the alkyl radical and 6 to 20 carbon atoms in the aryl radical, for hydrogen if the latter is bonded to a carbon atom, whereby the organic radicals R
3
and R
4
can also have insert substituents;
m is 1 for dianionic X, 2 for monoanionic X.
Imidochromium compounds having the general formula III,
were likewise found, wherein the variables have the following meaning:
R
2
stands for R
3
C═NR
4
, R
3
C═O, R
3
C═O(OR
4
), R
3
C═S, (R
3
)
2
P═O, (OR
3
)
2
P═O, SO
2
R
3
, R
3
R
4
C═N, NR
3
R
4
or BR
3
R
4
;
X independent of each other, stands for fluorine, chlorine, bromine, iodine, NR
5
R
6
, NP(R
5
)
3
, OR
5
, OSi(R
5
)
3
, SO
3
R
5
, OC(O)R
5
, &bgr;-diketonate, sulfate, dicarboxylates, dialcoholates, BF
4
−
, PF
6
−
, or bulky weakly or non-coordinating anions;
R
5
-R
6
independent of each other, stand for C
1
-C
20
-alkyl, C
2
-C
20
-alkenyl, C
6
-C
20
-aryl, alkylaryl having 1 to 10 carbon atoms in the alkyl radical and 6 to 20 carbon atoms in the aryl radical, for hydrogen if the latter is bonded to a carbon atom, whereby the organic radicals R
3
to R
6
can also have insert substituents;
m is 1 for dianionic X, 2 for monoanionic X;
L is a neutral donor;
n is 0 to 3;
Furthermore, a process was found for the production of an imidochromium compound having the general formula IV,
wherein the variables have the following meaning:
R
1
stands for C
1
-C
20
-alkyl, C
2
-C
20
-alkenyl, C
0
-C
20
-aryl, alkylaryl having 1 to 10 carbon atoms in the alkyl radical and 6 to 20 carbon atoms in the aryl radical, whereby the organic radical R
1
can also have inert substituents, or SiR
3
3
;
Z independent of each other, stands for C
1
-C
20
-alkyl, C
2
-C
20
-alkenyl, C
6
-C
20
-aryl, alkylaryl having 1 to 10 carbon atoms in the alkyl radical and 6 to 20 carbon atoms in the aryl radical, for fluorine, chlorine, bromine, iodine, NR
5
R
6
, NP(R
5
)
3
, OR
5
, OSi(R
5
)
3
, SO
3
R
5
, OC(O)R
5
, &bgr;-diketonate, sulfate, dicarboxylates, dialcoholates, BF
4
−
, PF
6
−
, or bulky weakly or non-coordinating anions;
R
3
, R
5
, R
6
independent of each other, stand for C
1
-C
20
-alkyl, C
2
-C
20
-alkenyl, C
6
-C
20
-aryl, alkylaryl having 1 to 10 carbon atoms in the alkyl radical and 6 to 20 carbon atoms in the aryl radical, for hydrogen if the latter is bonded to a carbon atom, whereby the organic radicals R
3
, R
5
and R
6
can also have inert substituents;
p is 1 for dianionic Z, 2 for monoanionic Z;
characterized in that a dioxochromium compound is reacted with an N-sulfinyl compound R
1
—NSO.
A process for the production of an imidochromium compound having t

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