Polymerization of olefins

Details Polymerization of olefins Polymerization of olefins

2000-02-01

2003-08-12

Zitomer, Fred (Department: 1713)

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

Synthetic resins

Polymers from only ethylenic monomers or processes of...

C526S243000, C526S248000, C526S310000, C526S312000

Reexamination Certificate

active

06605679

ABSTRACT:

FIELD OF THE INVENTION
Olefin (co)polymerization where the olefins contain certain functional groups such as silyl may be carried out using certain transition metal compounds as catalysts. Olefins containing other functional groupssuch as ester or alkenyl may be similarly polymerized and/or the polymerization improved if the olefin contains a “blocking group” such as a quaternary carbon atom.
TECHNICAL BACKGROUND
Polyolefins are useful in many areas as, for example, molding resins for toys and automotive parts, resins for film in packaging, elastomers and other uses. Many times it is desirable to copolymerize an olefin containing one or more functional groups, which may serve to later help crosslink the polymer, change the surface or other physical properties of the polymer, etc. Many olefins may be polymerized by using various transition metal compounds as polymerization catalysts, such as Ziegler-Natta or metallocene-type catalysts. However many times these polymerizations either won't proceed or proceed poorly in the presence of olefins containing functional groups.
Olefins may also be polymerized using catalysts containing late transition metals such as palladium or nickel, and sometimes functionalized olefins may be copolymerized. However, the range of useful functionalized olefins is limited, and often the efficiency of the polymerization is reduced in the presence of these olefins. Therefore more versatile and/or more efficient polymerizations of functionalized olefins are desired.
World Patent Applications 96/23010 and 97/02298 describe the polymerization of olefins, some of them containing functional groups, using certain transition metal containing compounds. The use of olefins containing blocking groups is not described in these applications.
SUMMARY OF THE INVENTION
This invention concerns a process for the polymerization of olefins, comprising, contacting a first olefin selected from the group consisting of cyclopentene, norbornene, and a compound of the formula R
1
CH═CHR
1
, a second olefin containing one or more of the functional groups selected from the group consisting of —SiR
2
3
, —CO
2
R
3
, a nonconjugated ketone, —SO
2
R
7
, alkenyl, —C(O)—O—C(O)R
4
, —C
6
F
5
, —OR
8
, —CO
2
H, —OH, —CHO, —OP(O) (OR
5
)
2
, —BR
6
2
, —SR
9
, —SH, ether, epoxy, and —CONR
68
R
69
, and a nickel or palladium coordination compound of
Ar
1
Z
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 Z is —NR
52
R
53
or —CR
54
=NR
5
;
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;
each R
42
and R
43
is independently hydrogen or acyl containing 1 to 20 carbon atoms;
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
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
are independently hydrocarbyl or substituted hydrocarbyl;
R
28
and R
29
are each in independently hydrogen, hydrocarbyl or substituted hydrocarbyl; and
n is 2 or 3; which is an olefin polymerization catalyst, and wherein:
each R
1
is independently hydrogen or alkyl;
each R
2
is independently hydrocarbyl, substituted hydrocarbyl, halogen, acyloxy, amino, siloxy, or —OR
12
;
R
3
is hydrogen, hydrocarbyl or substituted hydrocarbyl;
R
4
is hydrocarbyl or substituted hydrocarbyl;
each R
5
is independently hydrocarbyl or substituted hydrocarbyl;
R
6
is hydrocarbyl or substituted hydrocarbyl;
R
7
is hydrocarbyl or substituted hydrocarbyl;
R
8
is hydrocarbyl or substituted hydrocarbyl;
R
9
is hydrocarbyl or substituted hydrocarbyl; and
R
68
and R
69
are each independently hydrogen, hydrocarbyl or substituted hydrocarbyl;
 and provided that:
when said functional group is alkenyl, —OR
8
, —OH, —CHO, —OP(O)(OR
5
)
2
, —SR
9
, —SH, ether, epoxy, or —CONR
68
R
69
there is a blocking group between a carbon-carbon double bond of said olefin containing one or more of the functional groups and said functional groups; and
when said functional group is a nonconjugated ketone, alkenyl, —C(O)—O—C(O)R
4
, —CO
2
H, —OH, —CHO, —OP(O)(OR
5
)
2
, —SR
9
, or —SH, epoxy, said coordination compound is preferably a palladium compound.
Also disclosed herein is a compound of the formula
H
2
C═CH—T—NR
71
—C(O)CFR
72
(OCF
2
CFR
72
)
a
OCF
2
(CFR
72
)
b
SO
2
F,  (XXVI),
wherein:
T is alkylene or substituted alkylene;
R
71
is hydrocarbyl or substituted hydrocarbyl;
each R
72
is independently fluorine, chlorine or perfluoroalkyl containing 1 to 10 carbon atoms;
a is 0, 1 or 2; and
b is 0 or an integer of 1 to 6.
Also disclosed herein is a copolymer comprising repeat units of the formula
wherein:
T is alkylene or substituted alkylene;
R
71
is hydrocarbyl or substituted hydrocarbyl;
each R
72
is independently fluorine, chlorine or perfluoroalkyl containing 1 to 10 carbon atoms;
a is 0, 1 or 2;
b is 0 or an integer of 1 to 6;
R
73
is alkyl or hydrogen; and
R
74
is hydroxyl, fluorine, chlorine, or OM, wherein M is a metal cation.
DETAILS OF THE INVENTION
In the polymerization processes and catalyst compositions described herein certain groups may be present. By hydrocarbyl is meant a univalent radical containing only carbon and hydrogen. By saturated hydrocarbyl is meant a univalent radical which contains only carbon and hydrogen, and contains no carbon-carbon double bonds, triple bonds and aromatic groups. By substituted hydrocarbyl herein is meant a hydrocarbyl group which contains one or more (types of) substitutents that does not interfere with the operation of the polymerization catalyst system. Suitable substituents include halo, ester, keto (oxo), amino, imino, carboxyl, phosphite, phosphonite, phosphine, phosphinite, thioether, amide, nitrile, and ether. Preferred substituents are halo, ester, amino, imino, carbox

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