Manufacture of alpha-olefins

Details Manufacture of alpha-olefins Manufacture of alpha-olefins

2002-09-05

2004-05-25

Harlan, Robert Deshon (Department: 1713)

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

Synthetic resins

Polymers from only ethylenic monomers or processes of...

C526S171000, C556S138000, C502S155000, C502S167000

Reexamination Certificate

active

06740715

ABSTRACT:

FIELD OF THE INVENTION
Alpha-olefins may be manufactured in high yield and with very high selectivity by contacting ethylene with an iron complex of a selected 2,6-pyridinedicarboxaldehyde bisimine or a selected 2,6-diacylpyridine bisimine, and usually a selected activator compound.
TECHNICAL BACKGROUND
Alpha-olefins, especially those containing about 6 to about 20 carbon atoms, are important items of commerce, with about 1.5 million tons reportedly being produced in 1992. The &agr;-olefins are used as intermediates in the manufacture of detergents, as monomers (especially in linear low density polyethylene), and as intermediates for many other types of products. As a consequence, improved methods of making these compounds are of interest.
Most commercially produced &agr;-olefins are made by the oligomerization of ethylene, catalyzed by various types of compounds, see for instance B. Elvers, et al., Ed. Ullmann's Encyclopedia of Industrial Chemistry, Vol. A13, VCH Verlagsgesellschaft mbH, Weinheim, 1989, p. 243-247 and 275-276, and B. Cornils, et al., Ed., Applied Homogeneous Catalysis with Organometallic Compounds, A Comprehensive Handbook, Vol. 1, VCH Verlagsgesellschaft mbH, Weinheim, 1996, p. 245-258. The major types of commercially used catalysts are alkylaluminum compounds, certain nickel-phosphine complexes, and a titanium halide with a Lewis acid such as AlCl
3
. In all of these processes significant amounts of branched and/or internal olefins and/or diolefins, are produced. Since in most instances these are undesired, and often difficult to separate from the desired linear &agr;-olefins, minimization of these byproducts is sought.
SUMMARY OF THE INVENTION
This invention concerns a first process for the production of &agr;-olefins, comprising, contacting, at a temperature of about −100° C. to about +300° C., a compound of the formula
with ethylene and:
(a) a first compound W, which is a neutral Lewis acid capable of abstracting X
−
an alkyl group or a hydride group from Fe to form WX
−
, (WR
20
)
−
or WH
−
and which is also capable of transferring an alkyl group or a hydride to Fe, provided that WX
−
is a weakly coordinating anion; or
(b) a combination of second compound which is capable of transferring an alkyl or hydride group to Fe and a third compound which is a neutral Lewis acid which is capable of abstracting X
−
, a hydride or an alkyl group from Fe to form a weakly coordinating anion;
wherein:
each X is an anion;
n is 1, 2 or 3 so that the total number of negative charges on said anion or anions is equal to the oxidation state of an Fe atom present in (I);
R
1
, R
2
and R
3
are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl, or an inert functional group;
R
4
and R
5
are each independently hydrogen, hydrocarbyl, an inert functional group or substituted hydrocarbyl;
R
9
, R
10
, R
11
, R
14
, R
15
and R
16
are each independently hydrogen, hydrocarbyl, an inert functional group or substituted hydrocarbyl;
R
8
is a primary carbon group, a secondary carbon group or a tertiary carbon group; and
R
20
is alkyl;
and provided that:
when R
8
is a primary carbon group none, one or two of R
12
, R
13
and R
17
are primary carbon groups, and the remainder of R
12
, R
13
and R
17
are hydrogen;
when R
8
is a secondary carbon group, none or one of R
12
, R
13
and R
17
is a primary carbon group or a secondary carbon group and the remainder of R
12
, R
13
, and R
17
are hydrogen;
when R
8
is a tertiary carbon group all of R
12
, R
13
and R
14
are hydrogen; and
any two of R
8
, R
9
, R
10
, R
11
, R
12
, R
13
, R
14
, R
15
, R
16
and R
17
vicinal to one another, taken together may form a ring.
Also disclosed herein is a compound of the formula
wherein:
each X is an anion;
n is 1, 2 or 3 so that the total number of negative charges on said anion or anions is equal to the oxidation sate of a Fe atom present in (I);
R
1
, R
2
and R
3
are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl, or an inert functional group;
R
4
and R
5
are each independently hydrogen, hydrocarbyl, an inert functional group or substituted hydrocarbyl; and
R
9
, R
10
, R
11
, R
14
, R
15
and R
16
are each independently hydrogen, hydrocarbyl, an inert functional group or substituted hydrocarbyl; R
8
is a primary carbon group, a secondary carbon group or a tertiary carbon group;
and provided that:
when R
8
is a primary carbon group none, one or two of R
12
, R
13
and R
17
are primary carbon groups, and the remainder of R
12
, R
13
and R
17
are hydrogen;
when R
8
is a secondary carbon group, none or one of R
12
, R
13
and R
17
is a primary carbon group or a secondary carbon group and the remainder of R
12
, R
13
, and R
17
are hydrogen; and
when R
8
is a tertiary carbon group all of R
12
, R
13
and R
14
are hydrogen; any two of R
8
, R
9
, R
10
, R
11
, R
12
, R
13
, R
14
, R
15
, R
16
and R
17
vicinal to one another, taken together may form a ring.
This invention includes a compound of the formula
wherein:
R
1
, R
2
and R
3
are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl, or an inert functional group;
R
4
and R
5
are each independently hydrogen, hydrocarbyl, an inert functional group or substituted hydrocarbyl; and
R
9
, R
10
, R
11
, R
14
, R
15
and R
16
are each independently hydrogen, hydrocarbyl, an inert functional group or substituted hydrocarbyl; R
8
is a primary carbon group, a secondary carbon group or a tertiary carbon group;
and provided that:
when R
8
is a primary carbon group none, one or two of R
12
, R
13
and R
17
are primary carbon groups, and the remainder of R
12
, R
13
and R
17
are hydrogen;
when R
8
is a secondary carbon group, none or one of R
12
, R
13
and R
17
is a primary carbon group or a secondary carbon group and the remainder of R
12
, R
13
, and R
17
are hydrogen;
when R
8
is a tertiary carbon group all of R
12
, R
13
and R
14
are hydrogen; and
any two of R
8
, R
9
, R
10
, R
11
, R
12
, R
13
, R
14
, R
15
, R
16
and R
17
vicinal to one another, taken together may form a ring.
This invention also concerns a second process for the production of &agr;-olefins, comprising contacting, at a temperature of about −100° C. to about +300° C., a Fe[II] or Fe[III] complex of a tridentate ligand of the formula
with ethylene, wherein:
R
1
, R
2
and R
3
are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl, or an inert functional group;
R
4
and R
5
are each independently hydrogen, hydrocarbyl, an inert functional group or substituted hydrocarbyl;
R
9
, R
10
, R
11
, R
14
, R
15
and R
16
are each independently hydrogen, hydrocarbyl, an inert functional group or substituted hydrocarbyl;
R
8
is a primary carbon group, a secondary carbon group or a tertiary carbon group;
and provided that:
when R
8
is a primary carbon group none, one or two of R
12
, R
13
and R
17
are primary carbon groups, and the remainder of R
12
, R
13
and R
17
are hydrogen;
when R
8
is a secondary carbon group, none or one of R
12
, R
13
and R
17
is a primary carbon group or a secondary carbon group and the remainder of R
12
, R
13
, and R
17
are hydrogen;
when R
8
is a tertiary carbon group all of R
12
, R
13
and R
14
are hydrogen;
any two of R
8
, R
9
, R
10
, R
11
, R
12
, R
13
, R
14
, R
15
, R
16
and R
17
vicinal to one another, taken together may form a ring;
an Fe[II] or Fe[III] atom also has bonded to it an empty coordination site or a ligand that may be displaced by said ethylene, and a ligand that may add to said ethylene.
This invention also includes a compound of the formula
wherein:
R
1
, R
2
and R
3
are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl, or an inert functional group;
R
4
and R
5
are each independently hydrogen, hydrocarbyl, an inert functional group or substituted hydrocarbyl,
R
9
, R
10
, R
11
, R
14
, R
15
and R
16
are each independently hydrogen, hydrocarbyl, an inert functional group or substituted hydrocarb

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