Polymerizable composition and polymerization method

Details Polymerizable composition and polymerization method Polymerizable composition and polymerization method

1998-04-13

2001-08-21

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...

C526S280000, C526S281000, C526S283000

Reexamination Certificate

active

06277935

ABSTRACT:

The present invention relates to a solventless polymerizable composition comprising a strained cycloolefin and a ruthenium(IV) or osmium(IV) carbene, to a method of polymerising the composition, and to the use of the composition in the production of mouldings.
The thermal metathesis polymerization of strained cycloolefins has recently been gaining increasing importance. The polymerization requires the use of catalysts. Known catalysts are mainly transition metal compounds. While, as a rule, systems consisting of a catalyst and co-catalyst have been used in the first instance (see, for example, U.S. Pat. No.4,060,468 and WO 93/13171), one-component catalysts are also known [Thoi, H. H., Ivin, K. J., Rooney, J. J., J. Mol. Catal. 15:245-270 (1982)]. WO 93/20111 discloses ruthenium(IV) and osmium(IV) compounds having a ═CH—CH═CR
1
R
2
group bonded to the metal atoms as catalysts for thermal metathesis polymerization. Those “metal carbenes” are sparingly soluble compounds, so that polymerization is possible only in polar and, where appropriate, protic solutions. The same catalysts are described by Kanaoka and Grubbs [Kanaoka, S., Grubbs, R. H., Macromolecules 28:4707-4713 (1995)] under the same conditions of solution polymerization for the preparation of copolymers with silicon-containing norbomene derivatives. In that procedure the polymers have to be isolated and purified and also converted into a processible form, for example granules. For the production of shaped articles it is then necessary to employ in addition thermoplastic shaping procedures. The large number of processing steps generally results in a reduction in the mechanical and other performance properties, for example in discoloration. The use of solvents and the additional process steps are so disadvantageous from ecological and economic standpoints that industrial application is out of the question. In addition, the direct processing of solvent-containing systems to form bubble-free and homogeneous mouldings is either not possible at all or is possible only with difficulty, but such processing is necessary, however, because on the one hand the solvents used adversely affect the mechanical properties (for example there may be a plasticiser effect) and those properties will channe until all the solvent has been lost, and on the other hand a constant release of solvents ecologically harmful.
Fraser et al. [Fraser, C., Hillmyer, M., Gutierrez, E., Grubbs, R. H., Polym. Prepr. 36:237-238 (1995)] disclose for the first time [(C
6
H
11
)
3
P]
3
(C
6
H
5
—CH═)RuCl
2
(a ruthenium carbene) as thermal catalyst for the polymerization of mixtures of cyclooctadiene and 4,7-dihydro-1,3-oxepine. That ruthenium carbene is a very active catalyst which is capable of initiating polymerization even at room temperature. Here too, polar and halogenated solvents, specifically a concentrated solution of the catalyst in methylene chloride, are used in the polymerization, so that the above-described disadvantages are not overcome.
The preparation of [(C
6
H
11
)
3
P]
3
(C
6
H
5
—CH═)RuCl
2
and other ruthenium carbene compounds is disclosed by Schwab et al. [Schwab, P., France, M. B., Ziller, J. W., Grubbs, R. H., Angew. Chem. 107:2179-2181 (1995)]. They are described as highly active catalysts for ring-opening metathesis polymerization. For polymerizations carried out with norbomene and substituted cyclobutenes, either methylene chloride or benzene is used as solvent.
It should also be mentioned that Tanielian et al. [Tanielian, C., Kiennemann, A., Osparpucu, T., Can. J. Chem. 57:2022-2027 (1979)] describe that the ruthenium compound RuCl
2
[P(C
6
H
5
)
3
]
3
is deactivated by dicyclopentadiene and no polymers are formed by metathesis polymerization.
It has now surprisingly been found that those ruthenium carbenes have excellent solubility in monomeric strained cycloolefins even when the monomers do not contain polar groups or substituents and are composed only of carbon and hydrogen. This allows bulk polymerization and the direct production of mouldings. Despite the high activity of the catalysts, dilution and reduction of the reactivity with a polar solvent is unnecessary, and it is possible to prepare directly-processible compositions from the catalyst-containing monomer. The disadvantages resulting from a solvent content, such as the risk of bubble formation and a change in the mechanical properties, no longer exist.
The invention relates firstly to a solventless polymerizable composition comprising
(a) at least one strained cycloolefin that is liquid or is meltable without decomposition, and
(b) a catalytic amount of at least one compound of formula I or Ia or a mixture of compounds of formulae I and Ia
wherein
Me is ruthenium or osmium;
T
1
and T
2
are each independently of the other a tertiary phosphine or T
1
and T
2
together form a ditertiary diphosphine;
T
3
is hydrogen, C
1
-C
12
alkyl; C
3
-C
8
cycloalkyl, C
3
-C
7
heterocycloalkyl having one or two hetero atoms selected from the group —O—, —S— and —N—, C
6
-C
14
aryl, or C
4
-C
15
heteroaryl having from one to three hetero atoms selected from the group —O—, —S— and —N—, which are unsubstituted or substituted by C
1
-C
4
alkyl, C
1
-C
4
haloalkyl, C
1
-C
4
alkoxy, C
6
-C
10
aryl, C
6
-C
10
aryloxy, —NO
2
or by halogen;
T
4
is C
6
-C
16
arene or C
4
-C
15
heteroarene each of which is unsubstituted or substituted by from one to three C
1
-C
4
alkyl, C
1
-C
4
haloalkyl, C
1
-C
4
alkoxy, —OH, F, Cl or Br substituents, and
X
01
and X
02
are each independently of the other halogen.
Within the scope of this invention, a solventless composition contains from 0 to 4 %, preferably from 0 to 2 %, solvent, based on the cycloolefin.
The cyclic olefins may be monocyclic or polycyclic condensed and/or bridged and/or linked ring systems, for example having from two to four rings, which are unsubstituted or substituted and may contain hetero atoms, for example an O, S, N or Si atom, in one or more rings and/or may contain condensed aromatic or heteroaromatic rings, for example o-phenylene, o-naphthylene, o-pyridinylene or o-pyrimidinylene. The individual cyclic rings may contain from 3 to 16, preferably from 3 to 12 and especially from 3 to 8, ring members.
The cyclic olefins may contain further non-aromatic double bonds, preferably, depending upon the ring size, from 2 to 4 such additional double bonds. The ring substituents are inert, that is to say they do not adversely affect the chemical stability and the thermal stability of the ruthenium and osmium catalysts. The cycloolefins are strained rings or ring systems. Individual rings and ring systems having from 5 to 8 carbon atoms in the ring are especially preferred.
When the cyclic olefins contain more than one double bond, for example from 2 to 4 double bonds, or when mixtures of strained cycloolefins having one double bond and strained cycloolefins having at least two double bonds, for example from 2 to 4 double bonds, are used, then, depending upon the reaction conditions, the monomer chosen and the amount of catalyst, it is also possible for cross-linked polymerisates to be formed.
In a preferred embodiment of the composition according to the invention, the cycloolefins correspond to formula II
wherein
Q
1
is a radical having at least one carbon atom which, together with the —CH═CQ
2
— group, forms an at least 3-membered alicyclic ring which may contain one or more hetero atoms selected from the group Si, P, O, N and S; 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
)
½
, —SO
3
(M
1
)
½
, —PO
3
(M
1
)
½
, C
1
-C
20
alkyl, C
1
-C
20
hydroxyalkyl, C
1
-C
20
haloalkyl, C
1
-C
6
cyanoalkyl, C
3
-C
8
cycloalkyl, C
6
-C
16
aryl, C
7
-C
16
aralkyl, C
3
-C
6
heterocycloalkyl, C
3
-C
16
heteroaryl, C
4
-C
16
heteroaralkyl or by R
4
—X—; or wherein two adjacent carbon atoms, when present, are substituted by —CO—O—CO— or b

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