Catalyst mixture for ring-opening metathesis polymerization

Details Catalyst mixture for ring-opening metathesis polymerization Catalyst mixture for ring-opening metathesis polymerization

1997-11-14

2001-01-09

Bell, Mark L. (Department: 1755)

Catalyst, solid sorbent, or support therefor: product or process

Catalyst or precursor therefor

Organic compound containing

C502S152000, C502S150000, C502S156000, C502S158000, C502S169000, C502S172000

Reexamination Certificate

active

06171995

ABSTRACT:

The present invention relates to a catalyst composition consisting of a ruthenium or osmium phosphine complex and an alkyne; to a mixture comprising a Diels-Alder adduct of cyclopentadiene and such a catalyst composition; to a process for the preparation of a metathesis polymer as well as to the use of the polymerisable composition as casting resin, impregnating resin or as encapsulating material for electrical or electronic components.
WO 93/13171 describes air- and water-stable one- and two-component catalysts based on carbonyl group-containing molybdenum and tungsten compounds as well as ruthenium and osmium compounds having at least one polyene ligand for the thermal and photoactivated ring-opening metathesis polymerisation (ROMP) of strained cycloolefins, in particular norbornenes and norbornene derivatives.
1-Alkynes are, inter alia, recommended as co-catalysts for the two-component catalysts.
Demonceau et al. [A. Demonceau, A. F. Noels, E. Saive and A. J., Hubert: J. Mol. Catal. 76, 123-132 (1992)] describe (C
6
H
5
)
3
]
3
PRuCl
2
, (C
6
H
5
)
3
]
3
PRuHCl and (p-cymene)RuCl
2
P(C
6
H
11
)
3
as thermal catalysts for the ring-opening metathesis polymerisation of norbornene. The relatively low activity of these catalysts is increased by addition of diazo esters. It is also mentioned that only (p-cymene)RuCl
2
P(C
6
H
11
)
3
is able to polymerise norbornene in relatively short time at 60° C. Another monomer mentioned is cyclooctene. No other cycloolefins suitable for the metathesis polymerisation are mentioned.
WO 96/20235 describes ruthenium and osmium complex compounds as excellent catalysts for the metathesis polymerisation of di- and oligocyclopentadienes.
Surprisingly, it has now been found that the addition of 1-alkynes increases the catalytic activity of the ruthenium and osmium phosphines very substantially and improves the properties of the polymers considerably. In this manner it is possible to prepare polymers having excellent physical and mechanical properties within shorter polymerisation times. Moreover, the catalyst system is latent and storage-stable and not susceptible to air and moisture, which also permits marketing formulated polymerisable compositions.
This invention relates to a composition, comprising
(a) a compound of formula I
The alkyl groups in formulae I and II may be straight-chain or branched. This also applies to the, or every, alkyl moiety of alkoxy- or haloalkyl-containing groups and other groups containing alkyl. These alkyl groups preferably contain 1 to 12, particularly preferably 1 to 8 and, most preferably, 1 to 4, carbon atoms.
Alkyl typically includes methyl, ethyl, isopropyl, n-propyl, n-butyl, isobutyl, sec-butyl, tert-butyl as well as the different isomeric pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl and eicosyl groups.
Alkoxy is typically methoxy, ethoxy, propyloxy, isopropyloxy, n-butyloxy, isobutyloxy, sec-butyloxy and tert-butyloxy.
Haloalkyl typically comprises fluoromethyl, difluoromethyl, trifluoromethyl, chloromethyl, dichloromethyl, trichloromethyl, 2,2,2-trifluoroethyl, 2-fluoroethyl, 2-chloroethyl, 2,2,2-trichloroethyl as well as halogenated, in particular fluorinated or chlorinated, isopropyl, n-propyl, n-butyl, isobutyl, sec-butyl and tert-butyl groups as well as the different isomeric halogenated pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl and eicosyl groups.
Cycloalkyl is preferably C
5
-C
8
cycloalkyl, in particular C
5
- or C
6
cycloalkyl. Typical examples are cyclopropyl, dimethylcyclopropyl, cyclobutyl, cyclopentyl, methylcyclopentyl, cyclohexyl, cycloheptyl and cydooctyl.
Cycloalkoxy groups are, for example, cyclopentyloxy, methylcyclopentyloxy and cydohexyloxy.
Aryl preferably contains 6 to 10 carbon atoms and may typically be phenyl, pentalinyl, indenyl, naphtyl, azulinyl and anthryl.
Aryloxy groups are, for example, phenyloxy, naphthyloxy and anthryloxy.
Aralkyl preferably contains 7 to 12 carbon atoms and, particularly preferably, 7 to 10 carbon atoms. Aralkyl may typically be benzyl, phenethyl, 3-phenylpropyl, &agr;-methylbenzyl, 4-phenylbutyl and &agr;,&agr;-dimethylbenzyl.
Illustrative examples of aralkyloxy groups are benzyloxy, phenethyloxy, 3-phenylpropyloxy, &agr;-methylbenzyloxy, 4-phenylbutyloxy and &agr;,&agr;-dimethylbenzyloxy.
Preferred components (a) are compounds of formula I, wherein Me is ruthenium.
Other preferred components (a) are compounds of formula I, wherein R
1
, R
2
and R
3
are each independently of one another C
1
-C
6
alkyl, C
1
-C
6
alkoxy, C
4
-C
12
cycloalkyl, C
4
-C
12
cycloalkoxy, C
6
-C
16
aryl or C
6
-C
16
aryloxy.
Particularly preferred compounds of formula I are those, wherein R
1
, R
2
and R
3
are each independently of one another isopropyl, sec-butyl, phenyl, tolyl, cyclopentyl or cyclohexyl.
L in formula I is preferably benzene, thiophene, benzonitrile or acetonitrile which are unsubstituted or substituted by 1 to 3 C
1
-C
4
alkyl, nitrogen (N
2
), unsubstituted or partially or completely fluorinated C
1
-C
4
alcohol, CO, H
2
O or NH
3
.
Those compounds of formula I are also preferred, wherein Z
1
−
and Z
2
−
are each independently of the other H
−
, F
−
, Cl
−
, Br
−
, I
−
, or cyclopentadienyl which is unsubstituted or substituted by one or several hydroxide groups, amino groups, halogen atoms, C
1
-C
20
alkyl groups, C
1
-C
20
alkoxy groups, C
4
-C
12
cycloalkyl groups, C
4
-C
12
cycloalkoxy groups, C
6
-C
16
aryl group, C
6
-C
16
aryloxy groups or C
7
-C
16
aralkyl groups.
The complex compounds of formula I are known and are described, inter alia, in WO 96/16100 and WO 96/20235.
Typical examples of ruthenium and osmium compounds of of formula I are [tos denotes tosylate, Cp is cyclopentadienyl, and C
6
H
11
is cyclohexyl]: (C
6
H
11
)
2
HPRu(p-cymene)Cl
2
, (C
6
H
11
)
3
PRu(p-cymene)Cl
2
, (C
6
H
11
)
3
PRu(p-cymene)(tos)
2
, (C
6
H
11
)
3
PRu(p-cymene)Br
2
, (C
6
H
11
)
3
PRu(p-cymene)CIF, (C
6
H
11
)
3
PRu(C
6
H
6)(tos)
2
, (C
6
H
11
)
3
PRu(CH
3
-C
6
H
5
)(tos)
2
, (C
6H
11
)
3
PRu(C
10
H
8
)(tos)
2
, (i-C
3
H
7
)
3
PRu(p-cymene)Cl
2
, (CH
3
)
3
PRu(p-cymene)Cl
2
, (C
6
H
11
)
3
PRu(CH
3
—CN)(C
2
H
5
—OH)(tos)
2
, (C
6
H
11
)
3
PRu(p-cymene)(CH
3
—CN)
2
(PF
6
)
2
, (C
6
H
11
)
3
PRu(p-cymene)(CH
3
—CN)
2
(tos)
2
, (n-C
4
H
9
)
3
PRu(p-cymene)(CH
3
—CN)
2
(tos)
2
, (C
6
H
11
)
3
PRu(CH
3
CN)Cl
2
, (C
6
H
11
)
3
PRu(CH
3
—CN)
2
Cl
2
, (n-C
4
C
4
H
9
)
3
PRu(p-cymene)Cl
2
, (C
6
H
11
)
3
PRu(p-cymene)(C
2
H
5
OH)
2
(BF
4
)
2
, (C
6
H
11
)
3
PRu(p-cymene)(C
2
H
5
OH)
2
(PF
6
)
2
, (i-C
3
H
7
)
3
POs(p-cymene)Cl
2
, (CH
3
)
3
POs(p-cymene)Cl
2
, (C
6
H
5
)
3
POs(p-cymene)Cl
2
, [(C
8
H
11
)
3
P]
3
Ru(CH
3
—CN), (C
5
H
9
)
3
PRu(p-cymene)Cl
2
, (C
6
H
11
)
3
PRu(p-cymene)HCl, (C
6
H
11
)
3
PRu[1,2,4,5-(CH
3
)
4
C
6
H
2
]Cl
2
, (C
6
H
11
)
3
PRu[1,3,5-(i-C
3
H
7
)
3
C
6
H
3
]Cl
2
, (C
6
H
11
)
3
PRu[(C
4
H
9
)-C
6
H
5
]Cl
2
, (C
6
H
11
)
3
POs(p-cymene)Cl
2
, (C
6
H
5
)
3
PRu(p-cymene)HCl, [(C
6
H
11
)
3
P]
2
Ru(CH
3
—CN)(tos)
2
, RuCl
2
(p-cymeme)[(C
6
H
11
)
2
PCH
2
CH
2
P(C
6
H
11
)
2
], (C
6
H
11
)
3
PRu(p-cymene)(C
2
H
5
OH)(BF
4
)
2
, (C
6
H
11
)
3
PRu(C
6
H
6
)(C
2
H
5
OH)
2
(tos)
2
, (C
6
H
11
)
3
PRu(i-C
3
H
7
-C
6
H
5
)(tos)
2
,(C
6
H
11
)
3
PRu(C
6
H
6
)(p-cymene)Br
2
, (C
6
H
11
)
3
PRu(biphenyl)(tos)
2
, (C
6
H
11
)
3
PRu(anthracene)(tos)
2
, (2-CH
3
C
6
H
4
)
3
POs(p-cymene)Cl
2
and C
6
H
11
)
3
PRu(chrysene)(tos)
2
.
Particularly preferred compounds of formula I are [(C
6
H
11
)
3
P]
2
RuCl
2
, [(C
6
H
5
)
3
P]
3
RuCl
2
, [(C
6
H
5
)
3
P]
3
(CO)RuH
2
, [(C
6
H
5
)
3
P]
3
RuClCp, [(C
6
H
11
)
3
P]
2
(CH
3
OH)Ru(tos)
2
, [(o-tolyl)
3
P]
3
RuCl
2
, [(CH
3
)
2
CH]
3
P(p-cymene)RuCl
2
and, in particular, (C
6
H
11
)
3
P(p-cymene)RuCl
2
.
The compounds of

Affiliated with

Also associated with

Rating

Catalyst mixture for ring-opening metathesis polymerization does not yet have a rating. At this time, there are no reviews or comments for this patent.

If you have personal experience with Catalyst mixture for ring-opening metathesis polymerization, we encourage you to share that experience with our LandOfFree.com community. Your opinion is very important and Catalyst mixture for ring-opening metathesis polymerization will most certainly appreciate the feedback.

Rate now

Comments { 0 }

Profile ID: LFUS-PAI-O-2458478