Polymers of substituted cyclopentenes

Details Polymers of substituted cyclopentenes Polymers of substituted cyclopentenes

2001-04-02

2003-12-30

Choi, Ling-Siu (Department: 1713)

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

Synthetic resins

Polymers from only ethylenic monomers or processes of...

C526S308000, C526S169100, C526S217000, C526S236000, C526S133000, C526S141000, C502S200000, C502S229000

Reexamination Certificate

active

06670433

ABSTRACT:

FIELD OF THE INVENTION
Cyclopentenes which are substituted with various hydrocarbyl groups can be homopolymerized or copolymerized with cyclopentene itself to form polymers useful as molding resins. Nickel and palladium &agr;-diimine complexes can be used as catalysts for these polymerizations, but also disclosed herein are &agr;-diimine complexes which are novel catalysts for the polymerization of cyclopentenes.
TECHNICAL BACKGROUND
Nickel and palladium &agr;-diimine complexes are known catalysts for the polymerization of various olefins, including cyclopentene itself, see for instance World Patent Application 96/23010. However, methods for polymerization of various substituted cyclopentenes have not been reported with such catalysts.
Homopolymers of 3-methylcyclopentene have been reported, see for instance J. Boor, et al., Die Makromolekulare Chemie, vol. 90, p. 26-37 (1966).
World Patent Applications 96/23010 and 98/27124, and U.S. Pat. No. 5,880,241 describe homopolycyclopentenes which are melt processible.
SUMMARY OF THE INVENTION
This invention concerns a polymer, comprising, repeat units derived from one or more of 3-methylcyclopentene, 4-methylcyclopentene, 3-ethylcyclopentene or 3-cyclopentylcyclopentene, and optionally cyclopentene, provided that when said polymer is a homopolymer of 3-methylcyclopentene, at least about 40 mole percent of repeat units present are of the formula
This invention also concerns a process for the polymerization of one or more olefins selected from the group consisting of 3-methylcyclopentene, 4-methylcyclopentene, 3-ethylcyclopetnene and 3-cyclopentylcyclopentene, and optionally cyclopentene, by contacting, at a temperature of −100° C. to about +200° C., said olefin with a olefin polymerization catalyst system containing a nickel or palladium complex of a compound of the formula
and optionally other cocatalysts, wherein
R
2
and R
5
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; and
R
3
and R
4
are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl, or R
3
and R
4
taken together are hydrocarbylene or substituted hydrocarbylene to form a carbocyclic ring.
Disclosed herein is a compound of the formula
wherein:
each X is independently an anion;
n is 2 or 3;
R
3
and R
4
taken together are
R
5
, R
6
, R
7
, R
8
, R
9
, R
10
, R
11
, R
12
, R
13
, and R
14
are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl or a functional group;
and provided that:
when R
5
is the same as R
10
, and R
9
is the same as R
14
, said compound is in an anti form;
no more than one of R
5
, R
9
, R
10
, and R
14
is hydrogen;
any two of R
5
, R
6
, R
7
, R
8
, R
9
, R
10
, R
11
, R
12
, R
13
, and R
14
vicinal to one another may form a ring; and
R
5
is different than R
9
.
This invention also concerns a process for the polymerization of one or more of cyclopentene and a substituted cyclopentene, comprising, contacting, at a temperature of −100° C. to about +200° C., said olefin with a olefin polymerization catalyst system containing a compound of the formula
and optionally cocatalysts, wherein:
each X is independently a monoanion;
n is 2 or 3;
R
3
and R
4
taken together are
R
5
, R
6
, R
7
, R
8
, R
9
, R
10
, R
11
, R
12
, R
13
, and R
14
are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl or a functional group;
and provided that:
when R
5
is the same as R
10
, and R
9
is the same as R
14
, said compound is in an anti form;
no more than one of R
5
, R
9
, R
10
, and R
14
is hydrogen;
any two of R
5
, R
6
, R
7
, R
8
, R
9
, R
10
, R
11
, R
12
, R
13
, and R
14
vicinal to one another may form a ring; and
R
5
is different than R
9
.
This invention also concerns a homopolycyclopentene that has an end of melting point of 325° C. to about 380° C.
DETAILS OF THE INVENTION
Herein certain terms are used to define certain chemical groups or compounds. These terms are defined below.
A “hydrocarbyl group” is a univalent group containing only carbon and hydrogen. If not otherwise stated, it is preferred that hydrocarbyl groups herein contain 1 to about 30 carbon atoms.
By “substituted hydrocarbyl” herein is meant a hydrocarbyl group which contains one or more substituent groups which are inert under the process conditions to which the compound containing these groups is subjected. The substituent groups also do not substantially interfere with the process. If not otherwise stated, it is preferred that substituted hydrocarbyl groups herein contain 1 to about 30 carbon atoms. Included in the meaning of “substituted” are heteroaromatic rings.
By an alkyl aluminum compound is meant a compound in which at least one alkyl group is bound to an aluminum atom. Other groups such as alkoxide, oxygen, and halogen may also be bound to aluminum atoms in the compound.
By “hydrocarbylene” herein is meant a divalent group containing only carbon and hydrogen. Typical hydrocarbylene groups are —(CH
2
)
4
—, —CH
2
CH(CH
2
CH
3
)CH
2
CH
2
— and
If not otherwise stated, it is preferred that hydrocarbylene groups herein contain 1 to about 30 carbon atoms.
By “substituted hydrocarbylene” herein is meant a hydrocarbylene group which contains one or more substituent groups which are inert under the process conditions to which the compound containing these groups is subjected. All of the hydrogen atoms may be substituted, as in trifluoromethyl. The substituent groups also do not substantially interfere with the process. If not otherwise stated, it is preferred that substituted hydrocarbylene groups herein contain 1 to about 30 carbon atoms. Included within the meaning of “substituted” are heteroaromatic rings.
By an (inert) functional groups is meant a functional group that does not substantially interfere with the utility of the compound in which that group is located and does not make that compound unstable to the point where it is not useful for its intended purpose. Useful functional groups include halo and ether.
By “anti” herein is meant that when R
5
is identical to R
10
, and R
9
is identical to R
14
, the identical groups (i.e., the pairs R
5
and R
10
, and R
9
and R
14
are on opposite sides of the approximate plane formed by the two carbons and the two nitrogen atoms of the &agr;-diimine grouping and the nickel atom.
In the polymerization process described herein for the substituted cyclopentenes (SCP) using &agr;-diimine complexes of nickel or palladium, the same catalysts compounds and systems and conditions as reported in World Patent Application 96/23010, which is hereby included by reference, are used. Preferred nickel and palladium complexes reported therein, especially those preferred for the polymerization of cyclopentene itself, are preferred for the polymerization of the SCP reported herein. Likewise, preferred conditions, such as temperature and solvent (if used) are also preferred herein. A preferred cocatalysts, as in WO 96/23010 is an alkyl aluminum compound.
The various SCP reported herein polymerize to form one or more “unusual” repeat units in the resulting polymer. Rarely if at all does any of the SCP polymerize into the polymer merely by adding across the double bond present in the cyclopentyl ring. Also, there may be a difference between repeat structures obtained using nickel and palladium complexes. The structures of various polymers are described below.
3- and 4-Methylcyclopentene with Pd Catalyst (see Examples 4, 5 and 8). These two monomers give almost identical polymers with Pd catalysts. The majority of the repeat units are 1,3′-trans of the formula
typically about 80 mole percent of the repeat units. 1,2′-Trans units,
are also present in minor amounts, typically about 10-25 mole percent of the repeat units. There may also be small amounts of repeat units containing pendant methyl groups, especially from 4-methylcyclopentene.
3-Methylcyclopentene with Ni Catalyst (Example 6). This polymerization gives polymers with substantial amoun

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