Polymerization of olefins

Details Polymerization of olefins Polymerization of olefins

1999-10-13

2001-10-23

Wu, David W. (Department: 1713)

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

Synthetic resins

Polymers from only ethylenic monomers or processes of...

C526S172000, C526S348600, C526S352000, C502S155000

Reexamination Certificate

active

06306986

ABSTRACT:

FIELD OF THE INVENTION
Olefins such as ethylene may be polymerized using polymerization catalysts containing transition metals complexed to neutral bidentate ligands and using as cocatalysts “alkylhaloaluminoxanes”. These cocatalysts often give high polymer yields, even at relatively low ratios of aluminum containing cocatalyst to transition metal. Haloalkylaluminum compounds also give good yields of polyethylene at relatively low ratios of aluminum containing cocatalyst to transition metal.
TECHNICAL BACKGROUND
Recently it has been found that certain complexes of late transition metals, such as Ni, Pd, Fe, and others are effective catalysts for the polymerization of various olefins, such as ethylene, propylene, higher &agr;-olefins, norbornenes, cyclopentenes, and others, and copolymers thereof. In some instances olefins containing polar groups such as esters may also be copolymerized. Descriptions of many of these polymerizations will be found in World Patent Application 96/23010, and U.S. Pat. No. 5,714,556.
While some of these complexes may by themselves be able to polymerize such olefins, more commonly a cocatalyst, particularly an alkylaluminum compound, is also added to the polymerization to form an active polymerization system. Typically these cocatalysts have been alkylaluminoxanes (especially methylaluminoxanes), dialkylaluminum chlorides, and trialkylaluminum compounds. Sometimes, and particularly with trialkylaluminum compounds a second cocatalyst, such as another Lewis acid, is also added. While alkylaluminum compounds are effective cocatalysts, they often suffer from one or more drawbacks, such as relatively low catalyst productivity and/or rates, poor catalyst stability, and/or the need for relatively high amounts of the alkylaluminum compound in order to obtain good polymerization rates and/or catalyst productivity. Therefore catalysts systems which are overall improved are desirable.
The use of various alkylaluminum compounds as cocatalysts for the polymerization of olefins using various early transition metal catalysts such as Ziegler-Natta-type catalysts and metallocene-type catalysts is well known. Among the alkylaluminum compounds which have been used for such cocatalysts have been alkylhaloaluminoxanes such as diethyldichloroaluminoxane.
L. A. Volkov, et al., Vysokomol. Soedin., Ser. B, vol. 15, p. 455-457 (1973) report the use of bis(ethylchloroaluminum)oxide as a cocatalyst (with other cocatalysts) for the polymerization of 1,3-butadiene using a CoCl
2
(pyridine)
2
complex. The use of bidentate ligands is not mentioned.
Netherlands Patent Application 66/04717 reports the polymerization of butadiene using cobalt tris(acetylacetonate) and bis(ethylchloroaluminum)oxide as a cocatalyst. The use of neutral ligands is not mentioned.
U.S. Pat. Nos. 5,714,556 and 5,866,663 describe the use of various polymerization processes using various late transition metal complexes as catalysts, together with various alkyaluminum compounds as catalysts. The use of alkylhaloaluminoxanes is not specifically described, and the polymerization processes described herein with haloalkylaluminum compounds are also not specifically described.
SUMMARY OF THE INVENTION
This invention concerns a process for the polymerization of an olefin or olefins comprising the step of contacting, under polymerizing conditions:
(a) a transition metal polymerization catalyst wherein a metal of Groups 3 through 10 (new notation) is complexed to a neutral bidentate ligand,
(b) an alkylaluminum cocatalyst, and
(c) at least one olefin capable of being polymerized thereby,
wherein the alkylaluminum cocatalyst comprises a compound of the formula R
1
a
X
b
AlO
d
, wherein:
a and b are each independently about 0.50 to about 1.50, and d is 0.5 to 1.0, both provided that a+b+d is 2.0-2.5;
each R
1
is independently hydrocarbyl or substituted hydrocarbyl; and
X is carboxylate, fluoride, chloride, bromide or iodide.
This invention also concerns a process for the polymerization of olefins, and particularly ethylene, comprising the step of contacting, under polymerizing conditions:
(a) a transition metal polymerization catalyst wherein a metal of Groups 3 through 10 (new notation) is completed to a neutral bidentate ligand;
(b) an alkylaluminum cocatalyst; and
(c) ethylene,
wherein the alkylaluminum cocatalyst comprises a compound of the formula R
60
q
AlZ
t
, wherein:
q and t are each independently about 0.50 to about 2.50, provided that q+t is about 3.0;
each R
60
is independently hydrocarbyl or substituted hydrocarbyl; and
Z is fluoride, chloride, bromide or iodide;
and further provided that the molar ratio of aluminum in R
60
q
AlZ
t
to the transition metal in said transition metal polymerization catalyst is 75 to 500.
In the aforementioned processes, the polymerization catalyst is preferably a V, Cr, a rare earth metal, Fe, Co, Ni or Pd complex of a ligand selected from the group consisting of:
 Ar
1
Q
p
  (VIII);
R
31
R
32
N—CR
33
R
34
(CR
35
R
36
)
m
—NR
31
R
32
  (IX);
 R
47
R
48
R
49
P  (XXII);
and
R
31
S—CR
33
R
34
(CR
35
R
36
)
m
—SR
31
  (XXIV);
wherein:
Ar
1
is an aromatic moiety with n free valencies, or diphenylmethyl;
each Q is —NR
52
R
53
or —CR
54
═NR
55
;
p is 1 or 2;
E is 2-thienyl or 2-furyl;
each R
52
is independently hydrogen, benzyl, substituted benzyl, phenyl or substituted phenyl;
each R
54
is independently hydrogen or hydrocarbyl; and
each R
55
is independently a monovalent aromatic moiety;
m is 1, 2 or 3;
R
53
is hydrogen or alkyl;
each R
33
, R
34
, R
35
, and R
36
is independently hydrogen, hydrocarbyl or substituted hydrocarbyl;
each R
31
is independently hydrocarbyl or substituted hydrocarbyl containing 2 or more carbon atoms;
each R
32
is independently hydrogen, hydrocarbyl or substituted hydrocarbyl;
Ar
2
is an aryl moiety;
R
38
, R
39
, and R
40
are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl or an inert functional group;
R
37
and R
41
are each independently hydrocarbyl, substituted hydrocarbyl or an inert functional group whose E
s
is about −0.4 or less;
Ar
3
is an aryl moiety;
R
45
and R
46
are each independently hydrogen or hydrocarbyl;
Ar
4
is an aryl moiety;
Ar
5
and Ar
6
are each independently hydrocarbyl;
Ar
7
and Ar
8
are each independently an aryl moiety;
Ar
9
and Ar
10
are each independently an aryl moiety or —CO
2
R
56
, wherein R
56
is alkyl containing 1 to 20 carbon atoms;
Ar
11
is an aryl moiety;
R
50
is hydrogen or hydrocarbyl;
R
51
is hydrocarbyl or —C(O)—NR
50
—Ar
11
;
R
44
is aryl;
R
47
and R
48
are each independently phenyl groups substituted by one or more alkoxy groups, each alkoxy group containing 1 to 20 carbon atoms;
R
49
is alkyl containing 1 to 20 carbon atoms, or an aryl moiety;
R
22
and R
23
are each independently phenyl groups substituted by one or more alkoxy groups, each alkoxy group containing 1 to 20 carbon atoms; and
R
24
is alkyl containing 1 to 20 carbon atoms, or an aryl moiety;
each R
26
is hydrogen, hydrocarbyl, or substituted hydrocarbyl, provided that both of R
26
taken together may form a ring;
R
10
and R
11
are each independently hydrogen or acyl containing 1 to 20 carbon atoms;
R
13
and R
16
are each independently hydrocarbyl or substituted hydrocarbyl, provided that the carbon atom bound to the imino nitrogen atom has at least two carbon atoms bound to it;
R
14
and R
15
are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl, or R
14
and R
15
taken together are hydrocarbylene substituted hydrocarbylene to form a carbocyclic ring;
R
18
is hydrocarbyl or substituted hydrocarbyl, and R
20
is hydrogen, hydrocarbyl or substituted hydrocarbyl or R
18
and R
20
taken together form a ring;
R
19
is hydrocarbyl or substituted hydrocarbyl, and R
21
is hydrogen, substituted hydrocarbyl or hydrocarbyl, or R
19
and R
21
taken together form a ring;
each R
17
is independently hydrogen, substituted hydrocarbyl or hydrocarbyl, or two of R
17
taken together form a ring;
R
27
and R
30

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