Polymerization of dicyclopentadiene

Details Polymerization of dicyclopentadiene Polymerization of dicyclopentadiene

1997-06-19

2001-05-22

Wilson, Donald R. (Department: 1713)

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

Synthetic resins

Polymers from only ethylenic monomers or processes of...

C526S172000, C526S283000, C526S336000, C526S340300, C526S308000, C526S309000, C585S022000, C585S023000

Reexamination Certificate

active

06235856

ABSTRACT:

The present invention relates to a composition of dicyclopentadiene (DCPD), by itself or mixed with at least one stretched cycloolefin, and a single-component catalyst from the group consisting of ruthenium- and osmiumphosphine; a process for the thermal metathesis polymerization of dicyclopentadiene; coated materials; and linear or crosslinked copolymers of dicyclopentadiene and at least one strained cycloolefin.
Thermally induced ring-opening metathesis polymerization using catalytic amounts of metal compounds has already been known for a relatively long time and is described in many instances in the literature [cf., for example, Ivin, K. J., Olefin Metathesis 1-12, Academic Press, London (1983)]. Such polymers are prepared industrially and are commercially obtainable, for example as Vestenamer®.
Feldman et al. [Feldman, J., Schrock, R. R., in: Lippard, S. J. (editor), Progress in Inorganic Chemistry 39:1-74 (1991)] describe molybdenum- and tungsten-alkylidene complexes which by themselves are only weak but together with Lewis acids are active thermal catalysts for the polymerization of cycloolefins.
WO 93/13171 describes air- and water-stable single-component and two-component catalysts based on carbonyl group-containing molybdenum and tungsten compounds and ruthenium and osmium compounds having at least one polyene ligand for thermal metathesis polymerization, and a photoactivated metathesis polymerization of strained cycloolefins, in particular norbornene and norbornene derivatives. Other polycyclic—in particular non-fused polycyclic—cycloolefins are not mentioned. The single-component catalysts of the ruthenium compounds used, namely [Ru(cumene)Cl
2
]
2
and [(C
6
H
6
)Ru(CH
3
CN)
2
Cl]
+
PF
6
—, can indeed be activated by UV irradiation; however, the storage stability of the compositions with norbornene are completely inadequate. These catalysts are capable of replacing the known two-component catalysts only inadequately.
Demonceau et al. [Demonceau, A., Noels, A. F., Saive, E., Hubert, A. J., 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-cumene)RuCl
2
P(C
6
H
11
)
3
as thermal catalysts for ring-opening metathesis polymerization of norbornene, a fused polycycloolefin. These catalysts have not been able to find acceptance in industrial preparations because their activity is too low. It is therefore proposed to increase the activity by addition of diazo esters. It is also mentioned that only (p-cumene)RuCl
2
P(C
6
H
11
)
3
is capable of polymerizing norbornene at 60° C. within a relatively short time. Cyclooctene is also mentioned as a further monomer. Other cycloolefins for metathesis polymerization are not mentioned.
WO 93/20111 describes osmium- and ruthenium-carbene compounds with phosphine ligands, for example [(H
5
C
6
)
3
P]
2
Cl
2
═CH—CH═C(C
6
H
5
)
2
, as purely thermal catalysts for ring-opening metathesis polymerization of strained cycloolefins, in which cyclodienes, such as dicyclopentadiene, act as catalyst inhibitors and cannot be polymerized. These catalysts are difficult to prepare and are moderately stable towards moisture, so that particular protective measures must be taken for storage and processing of compositions comprising these catalysts.
Tanielan et al. [Tanielan, C., Kieffer, R., Harfouch, A., Tetrahedron Letters 52:4589-4592 (1977)] report that the ruthenium compound RuCl
2
[P(C
6
H
5
)
3
]
3
is deactivated by dicyclopentadiene and no polymers are formed by thermal metathesis polymerization.
It has now been found, surprisingly, that dicyclopentadiene is accessible to thermal metathesis polymerization with a single-component catalyst if carbene-free ruthenium(II)- or osmium(II)-phosphine catalysts are used. It has furthermore been found that even linear polycyclopentadiene can be prepared if the polymerization is carried out in suitable solvents, and crosslinked polymers are obtained if the polymerization is carried out in bulk. It has also been found that the polymerization takes place even in the presence of plastics additives, for example fillers, and shaped articles, foils (films) or coatings with excellent physical and mechanical properties are obtained. It has also been observed that the compositions of DCPD and carbene-free ruthenium(II)- or osmium(II)-phosphine catalysts are stable to air and moisture, and therefore both have a high storage stability, if appropriate with exclusion of light, and also necessitate no particular protective measures for the polymerization, which offers considerable advantages during processing. It has also additionally been found that, using these catalysts, DCPD can be copolymerized together with strained cycloolefins as comonomers. As a result, properties can be modified in a controlled manner and adapted to suit the desired intended use.
The invention relates to a composition of (a) dicyclopentadiene by itself or as a mixture with a strained cycloolefin and (b) a catalytic amount of at least one carbene-free, divalent-cationic ruthenium or osmium compound, as a single-component catalyst, which contains at least one phosphine group and a total of 2 to 5 ligands bonded to the metal atom and which contains acid anions for charge balancing.
In the context of the invention, total means the sum of the phosphine groups and the ligands. The ruthenium and osmium compounds preferably contain a total of 2 or 3 ligands.
The phosphine group is preferably tertiary phosphines and phosphites, in particular phosphines having 3 to 40, preferably 3 to 30, and particularly preferably 3 to 24 C atoms.
Dicyclopentadiene of the formula
is a dimer of cyclopentadiene, which is known and commercially obtainable. However, it is known that dicyclopentadiene forms further Diels-Alder adducts with cyclopentadiene and thus forms oligomers, which can also be used. Pure dicyclopentadiene, oligomers of dicyclopentadiene or mixtures thereof can thus be used according to the invention in the composition. The oligomers can correspond to the formula
in which p is a number from 1 to 100, preferably 1 to 50, particularly preferably 1 to 20, and especially preferably 1 to 10.
A very large number of strained cycloolefins which the composition according to the invention can comprise as comonomers are known.
The cyclic olefins can be monocyclic or polycyclic fused and/or bridged ring systems, for example with two to four rings, which are unsubstituted or substituted and can contain heteroatoms, for example O, S, N or Si, in one or more rings and/or fused aromatic or heteroaromatic rings, for example o-phenylene, o-naphthylene, o-pyridinylene or o-pyrimidinylene. The individual cyclic rings can contain 3 to 16, preferably 3 to 12, and particularly preferably 3 to 8 ring members. The cyclic olefins can contain further nonaromatic double bonds, preferably 2 to 4 such additional double bonds, depending on the ring size. The ring substituents are those which are inert, i.e. which do not impair the chemical stability of ruthenium and osmium compounds. The cycloolefins are strained rings or ring systems.
If the cyclic olefins contain more than one double bond, for example 2 to 4 double bonds, crosslinked polymers can also be formed, depending on the reaction conditions, the monomer chosen and the amount of catalyst.
Fused-on alicyclic rings preferably contain 3 to 8, particularly preferably 4 to 7, and especially preferably 5 or 6 ring C atoms.
In a preferred embodiment of the process according to the invention, the cycloolefins correspond to the formula I
wherein
Q
1
is a radical having at least one carbon atom which, together with the —CH═CQ
2
-group, forms an alicyclic ring which has at least 3 members and which optionally contains one or more heteroatoms chosen from the group consisting of silicon, phosphorus, oxygen, nitrogen and sulfur; and which is unsubstituted or substituted by halogen, ═O, —CN, —NO
2
, R
1
R
2
R
3
Si—(O)
u
—, —COOM, —SO
3
M, —PO
3
M, —COO(M)
1
)
1/2
, —SO

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