Process for the photo-polymerisation of cyclic olefins using a thermostable molybdenum or tungsten catalyst

A process for photocatalytic polymerisation of a cyclic olefin or of at least two different cyclic olefins in the presence of a metal compound as catalyst, which process comprises carrying out a photochemically induced ring-opening metathesis polymerisation in the presence of a catalytic amount of at least one thermostable molybdenum (VI) or tungsten (VI) compound which contains at least two methyl groups or two monosubstituted methyl groups lacking .beta.-hydrogen atoms in the substituent and which are bonded to the metal atom. The process may be carried out by first irradiating and terminating the polymerisation by heating. The process is suitable for fabricating moulded articles, coatings and relief images.

The present invention relates to a process for the polymerisation of cyclic 
olefins by photochemical ring-opening metathesis polymerisation using 
catalytic amounts of a transition metal catalyst, and to compositions 
comprising said olefins together with a catalytic amount of said catalyst. 
Thermally induced ring-opening metathesis polymerisation using catalytic 
amounts of metal catalysts has been known for some considerable time and 
is widely described in the literature (q.v. inter alia K. J. Ivin, Olefin 
Metathesis, Academic Press, London, 1983). Such polymers are prepared 
industrially and are commercially available. However, photochemically 
induced ring-opening metathesis polymerisation is only little known and so 
far commercial utilities have not resulted. 
U.S. Pat. No. 4 060 468 discloses an olefin metathesis polymerisation which 
is carried out by charging a two-component mixture of a metal salt 
selected from tungsten, molybdenum, rhenium and tantalium salts and a 
substituted phenol or benzyl alcohol as co-catalysts to a reactor with the 
olefin monomer, and then irradiating the entire reaction mixture with UV 
light The only olefins mentioned are cyclic and acylic hydrocarbons 
without functional groups or substituents. The separate storage of the 
catalyst components and the process step of mixing the catalyst components 
directly before the actual reaction make the known process technically 
complicated and troublesome. 
In Tetrahedron Letters No. 52, pp. 4589-4592 (1977), C. Tanielan et al. 
describe the catalyst system W(CO).sub.6 /CCl.sub.4, which, after 
irradiation with UV light, can be used for the metathesis polymerisation 
of cyclopentene and norbornene. Metal carbonyls are volatile and toxic, so 
that their use requires elaborate protective measures for physiological 
reasons. In addition, a free radical addition reaction is observed as 
competing reaction to form monomeric 
1-chloro-2-trichlormethylcycloolefins. 
It is known from H. H. Thoi et al., Journal of Molecular Catalysis, 15 
(1982), pp. 245-270, that a tungsten pentacarbonylcarbene complex of 
formula 
##STR1## 
is a thermal catalyst for the ring-opening metathesis polymerisation of 
dimethyl norbornene and, together with phenyl acetylene as co-catalyst, is 
also a photocatalyst system for the same polymerisation. This catalyst 
system has the serious shortcoming that, as ready-for-use formulation, it 
has only poor storage stability, the carbonyl compound is physiologically 
unacceptable, and the tolerance to functional groups in cycloolefins is 
too low. 
J. Feldmann et al describe in Progress in Inorganic Chemistry, Vol. 39, pp. 
3-73, Edited by Stephen J. Lippard (1991), molybdenum and tungsten 
alkylidene complexes which, singly, are only poor, but together with Lewis 
acids, are effective, thermal catalysts for the polymerisation of 
cycloolefins. 
In WO 93/13171 are described one component catalysts on the basis of 
carbonyl containing Mo- and W-compounds and Ru- or Os-compounds with a 
polyene ligand for the ring-opening photometathesis of strained 
cycloolefines. With this catalysts are obtained storage stable 
compositions under exclusion of light. 
N. A. Petasis et al. mention in J. Am. Chem. Soc. 115 (1993), pages 
7208-7214 the thermal ring-opening photometathesis of norbornene in using 
(cyclopentadienyl).sub.2 TiCH.sub.2 -Si(CH.sub.3).sub.3 !.sub.2 as 
thermal catalysts. A photoinitiating activity is not mentioned. 
The known catalysts which can be activated photochemically thus mainly 
require a co-catalyst, for which reason the quality of the resultant 
polymers can vary greatly owing to the chosen nature and sequence of the 
reactants. 
Polymers obtained from cyclic olefins by photochemical ring-opening 
metathesis polymerisation can only be prepared by the known processes with 
a great deal of trouble and in an economically unsatisfactory manner. 
Particular disadvantages are the poor stability, which only permits the 
components to be mixed directly before the preparation, the lack of 
tolerance to functionalised cyclic olefins, and the necessity of using two 
components as catalyst system. Hence for technical, economic and 
environmental reasons there is a need to provide an improved and generally 
useful process for the preparation of polymers from cyclic olefins by 
photochemical ring-opening metathesis polymerisation. 
It has been found that compositions of cycloolefins and a single component 
catalyst are photochemically polymerisable if the composition contains a 
molybdenum or tungsten compound in a high state of oxidation, in which at 
least two alkyl groups lacking .beta.-hydrogen atoms are bonded to the 
metal atom. Surprisingly, these thermally stable compounds have been found 
to be effective catalysts for the photochemically induced ring-opening 
metathesis polymerisation and, despite the photochemical reactivity, the 
storage stability of mixtures of cycloolefins and the molybdenum or 
tungsten compounds is retained. 
It has also surprisingly been found that the above catalysts act as thermal 
catalysts even after brief irradiation in the presence of cycloolefins, so 
that the photochemical and thermal polymerisation can be carried out 
together. 
In one of its aspects, the invention relates to a process for 
photocatalytic polymerisation of a cyclicolefin, or of at least two 
different cyclic olefins, in the presence of a metal compound as catalyst, 
which process comprises carrying out a photochemically induced 
ring-opening metathesis polymerisation in the presence of a catalytic 
amount of at least one thermostable molybdenum (VI) or tungsten (VI) 
compound that contains at least two methyl groups or two monosubstituted 
methyl groups lacking .beta.-hydrogen atoms in the substituent and which 
are bonded to the metal atom. Substituent means the substituted methyl 
group. 
The cyclic olefins can be monocyclic or polycyclic fused ring systems, 
typically containing two to four rings which are unsubstituted or 
substituted and containing hetero atoms such as O, S, N or Si in one or 
more than one ring, and/or fused aromatic or heteroaromatic rings such as 
o-phenylene, o-naphthylene, o-pyridinylene or o-pyrimidinylene. The cyclic 
rings may contain 3 to 16, preferably 3 to 12 and, most preferably, 3 to 
8, ring members. The cyclic olefins may contain further non-aromatic 
double bonds, preferably 2 to 4 such additional double bonds, depending on 
the size of the ring. The ring substituents are those that are inert, i.e. 
that do not impair the chemical stability and the thermostability of the 
molybdenum or tungsten compounds. Thermostability means within the scope 
of this invention that the photocatalytically active molybdenum or 
tungsten compounds, when heated, form no active species for the 
ring-opening metathesis polymerisation. For example, it has been found 
that, after heating these catalysts, with exclusion of air, to 110.degree. 
C. for 24 hours, no such active species are detectable. The catalyst 
cannot, for example, at room temperature to slightly elevated temperature, 
e.g. +40.degree. C., initiate any ring-opening metathesis polymerisation 
over a period of weeks to months, with exclusion of light, and during this 
time less than 0.2% by weight of monomer is reacted. The thermostabiity 
can be determined by storing an ethanolic solution containing 20% by 
weight of monomer and 0.33% by weight of tungsten or molybdenum catalyst 
at 50.degree. C. for 96 hours in the dark, and any polymer formed 
(detectable from the turbidity) is not more than 0.2% by weight and 
preferably not more than 0.1% by weight. 
If the cyclic olefins contain more than one double bond, for example 2 to 4 
double bonds, crosslinked polymers are formed. This feature is also 
observed when using (norbornenehydroxymethyl)norbornenecarboxylic acid 
esters of formula 
##STR2## 
In a preferred embodiment of the novel process, the cycloolefins are of 
formula I 
##STR3## 
wherein Q.sub.1 is a radical having at least one carbon atom which, 
together with the --CH.dbd.CQ.sub.2 -- group, forms an at least 3-membered 
alicyclic ring which may contain one or more hetero atoms selected from 
the group consisting of silicon, phosphorus, oxygen, nitrogen and sulfur; 
and which radical is unsubstituted or substituted by halogen, .dbd.O, 
--CN, --NO.sub.2, R.sub.1 R.sub.2 R.sub.3 Si--(O).sub.u --, --COOM, 
--SO.sub.3 M, --PO.sub.3 M, --COO(M.sub.1).sub.1/2, --SO.sub.3 
(M.sub.1).sub.1/2, --PO.sub.3 (M.sub.1).sub.1/2, C.sub.1 -C.sub.20 alkyl, 
C.sub.1 -C.sub.20 hydroxyalkyl C.sub.1 -C.sub.20 haloalkyl, C.sub.1 
-C.sub.6 cyanoalkyl, C.sub.3 -C.sub.8 cycloalkyl, C.sub.6 -C.sub.16 aryl, 
C.sub.7 -C.sub.16 aralkyl, C.sub.3 -C.sub.6 heterocycloalkyl, C.sub.3 
-C.sub.6 heteroaryl, C.sub.4 -C.sub.16 heteroaralkyl or R.sub.4 --X--; or 
in which two adjacent C atoms are substituted by --CO--O--CO-- or 
--CO--NR.sub.5 --CO--; or in which an aromatic or heteroaromatic ring, 
which is unsubstituted or substituted by halogen, --CN, --NO.sub.2, 
R.sub.6 R.sub.7 R.sub.8 Si--(O).sub.u --, --COOM, --SO.sub.3 M, PO.sub.3 
M, --COO(M.sub.1).sub.1/2, --SO.sub.3 (M.sub.1).sub.1/2, --PO.sub.3 
(M.sub.1).sub.1/2, C.sub.1 -C.sub.20 alkyl, C.sub.1 -C.sub.20 haloalkyl, 
C.sub.1 -C.sub.20 hydroxyalkyl, C.sub.1 -C.sub.6 cyanoalkyl, C.sub.3 
-C.sub.8 cycloalkyl, C.sub.6 -C.sub.16 aryl, C.sub.7 -C.sub.16 aralkyl, 
C.sub.3 -C.sub.6 heterocycloalkyl, C.sub.3 -C.sub.16 heteroaryl, C.sub.4 
-C.sub.16 heteroaralkyl or R.sub.13 --X.sub.1 --, is fused to adjacent 
carbon atoms of the alicyclic ring; 
X and X.sub.1 are each independently of the other --O--, --S--, --CO--, 
--SO--, --SO.sub.2 --, --O--C(O)--, --C(O)--O--, --C(O)--NR.sub.5 --, 
--NR.sub.10 --C(O)--, --SO.sub.2 --O-- or --O--SO.sub.2 --; 
R.sub.1, R.sub.2 and R.sub.3 are each independently of one another 
C.sub.1-C.sub.12 alkyl, C.sub.1 -C.sub.12 perfluoroalkyl, phenyl or 
benzyl; 
R.sub.4 and R.sub.13 are each independently of the other C.sub.1 -C.sub.20 
alkyl, C.sub.1-C.sub.20 haloalkyl, C.sub.1 -C.sub.20 hydroxyaLkyl, C.sub.3 
-C.sub.8 cycloalkyl, C.sub.6 -C.sub.16 aryl or C.sub.7 -C.sub.16 aralkyl; 
R.sub.5 and R.sub.10 are each independently of the other hydrogen, C.sub.1 
-C.sub.12 alkyl, phenyl or benzyl, the alkyl groups in turn being 
unsubstituted or substituted by C.sub.1 -C.sub.12 alkoxy or C.sub.3 
-C.sub.8 cycloalkyl; 
R.sub.6, R.sub.7 and R.sub.8 are each independently of one another C.sub.1 
-C.sub.12 alkyl, C.sub.1 -C.sub.12 perfluoroalkyl, phenyl or benzyl; 
M is an alkali metal and 
M.sub.1 is an alkaine earth metal; and 
u is 0 or 1; 
and the alicyclic ring formed with Q.sub.1, may contain further 
non-aromatic double bonds; 
Q.sub.2 is hydrogen, C.sub.1 -C.sub.20 alkyl, C.sub.1 -C.sub.20 haloalkyl, 
C.sub.1 -C.sub.12 alkoxy, halogen, --CN or R.sub.11 --X.sub.2 --; 
R.sub.11 is C.sub.1 -C.sub.20 alkyl, C.sub.1 -C.sub.20 haloalkyl, C.sub.1 
-C.sub.20 hydroxyalkyl, C.sub.3 -C.sub.8 cycloalkyl, C.sub.6 -C.sub.16 
aryl or C.sub.7 -C.sub.16 aralkyl; 
X.sub.2 is --C(O)--O-- or --C(O)--NR.sub.12 --; 
R.sub.12 is hydrogen, C.sub.1 -C.sub.12 alkyl, phenyl or benzyl; 
and the above mentioned cycloalkyl, heterocycloalkyl, aryl, heteroaryl, 
aralkyl and heteroaralkyl groups are unsubstituted or substituted by 
C.sub.1 -C.sub.12 alkyl, C.sub.1 -C.sub.12 alkoxy, --NO.sub.2, --CN or 
halogen, and the hetero atoms of the above mentioned heterocycloalkyl, 
heteroaryl and heteroaralkyl groups are selected from the group consisting 
of --O--, --S--, --NR.sub.9 -- and --N.dbd.; and 
R.sub.9 is hydrogen, C.sub.1 -C.sub.12 alkyl, phenyl or benzyl. 
Other olefins which are capable of metathesis can be used concurrently in 
the process of this invention, for example in amounts of up to 40 mol %, 
preferably 0.01 to 30 mol %, and particularly preferably 0.1 to 20 mol %, 
based on the total amount of cycloolefins and olefins present. 
Olefins which are capable of metathesis, and which the novel polymerisable 
mixtures of formula I may additionally comprise, can be used for 
crosslitiing or for regulating the molecular weight. Examples of suitable 
olefins are cyclooctadiene or cyclooctatriene or compounds having the 
following structures: 
##STR4## 
Furthermore, compounds such as 2-butene-1,4-diol, as described in Feast, 
W. J., Harison, B. J. Mol. Catal. 65, 63 (1991), or 1-hexene 
(rearrangements) are also suitable. 
If the compounds of the formula I contain a centre of asymmetry, then the 
compounds may be obtained in the form of optical isomers. Some of the 
compounds of formula I may occur in tautomeric forms (for example 
keto-enol tautomerism). If an aliphatic C.dbd.C double bond is present, 
geometric isomerism (E-form and Z-form) can also occur. In addition, 
exo-endo configurations are also possible. Formula I thus embraces all 
possible stereoisomers which exist in the form of enantiomers, tautomers, 
diastereomers, E/Z isomers or mixtures thereof. 
In the definition of the substituents, the alkyl, alkenyl and alkynyl 
groups may be straight-chain or branched, as may also the alkyl moiety or 
each alkyl moiety of alkoxy, alkylthio, alkoxycarbonyl and other 
alkyl-containing groups. These alkyl groups preferably contain 1 to 12, 
more particularly 1 to 8, and, most preferably, 1 to 4, carbon atoms. 
These alkenyl and alkynyl groups preferably contain 2 to 12, more 
particularly 2 to 8, and, most preferably, 2 to 4, carbon atoms. 
Alkyl typically comprises methyl, ethyl, isopropyl, n-propyl, n-butyl, 
isobutyl, sec-butyl, tert-butyl and the various isomeric pentyl, hexyl, 
heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, 
pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl and eicosyl 
radicals. 
Hydroxyalkyl typically comprises hydroxymethyl, hydroxyethyl, 
1-hydroxyisopropyl, 1-hydroxy-n-propyl, 2-hydroxy-n-butyl, 
1-hydroxy-iso-butyl, 1-hydroxy-sec-butyl, 1hydroxy-tert-butyl and the 
hydroxy forms of the various isomeric pentyl, hexyl, heptyl, octyl, nonyl, 
decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, 
heptadecyl, octadecyl, nonadecyl and eicosyl radicals. 
Haloalkyl typically comprises fluoromethyl, difluoromethyl, 
trifluoromethyl, chloromethyl, dichloromethyl, trichloromethyl, 
2,2,2-trifluoroethyl, 2-fluoroethyl, 2-chloroethyl, 2,2,2-trichloroethyl 
and halogenated, in particular fluorinated or chlorinated, alkanes, for 
example the isopropyl, n-propyl, n-butyl, iso-butyl, sec-butyl, tert-butyl 
and the various isomeric pentyl, hexyl, heptyl, octyl, nonyl, decyl, 
undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, 
octadecyl, nonadecyl and eicosyl radicals. 
Alkenyl typically comprises propenyl, isopropenyl, 2-butenyl, 3-butenyl, 
isobutenyl, n-penta-2,4dienyl, 3-methyl-but-2-enyl, n-oct-2-enyl, 
n-dodec-2-enyl, iso-dodecenyl, n-octadec-2-enyl and n-octadec-4-enyl. 
Cycloalkyl is preferably C.sub.5 -C.sub.8 cycloalkyl, most preferably 
C.sub.5 - or C.sub.6 cycloalkyl. Typical examples are cyclopropyl, 
dimethylcyclopropyl, cyclobutyl, cyclopentyl, methylcyclopentyl, 
cyclohexyl, cycloheptyl and cyclooctyl. 
Cyanoalkyl typically comprises cyanomethyl (methylnitrile), cyanoethyl 
(ethylnitrile), 1-cyanoisopropyl, 1-cyano-n-propyl, 2-cyano-n-butyl, 
1-cyano-iso-butyl, 1-cyano-sec-butyl, 1-cyano-tert-butyl and the different 
isomeric cyanopentyl and cyanohexyl radicals. 
Aralkyl preferably contains 7 to 12 carbon atoms and, most preferably, 7 to 
10 C atoms. Aralkyl may typically be benzyl, phenethyl, 3-phenylpropyl, 
.alpha.-methylbenzyl, phenbutyl and .alpha.,.alpha.-dimethylbenzyl. 
Aryl preferably contains 6 to 10 carbon atoms and may typically be phenyl, 
pentalene, indene, naphthalene, azulene and anthracene. 
Heteroaryl preferably contains 4 or 5 carbon atoms and one or two hetero 
atoms selected from the group consisting of O, S and N. heteroaryl may 
typically be pyrrole, furan, thiophene, oxazole, thioazole, pyridine, 
pyrazine, pyrimidine, pyridazine, indole, purine and quinoline. 
Heterocycloalkyl preferably contains 4 or 5 carbon atoms and one or two 
hetero atoms selected from the group consisting of O, S and N. It may 
typically be oxirane, azirine, 1,2oxathiolane, pyrazoline, pyrrolidine, 
piperidine, piperazine, morpholine, tetrahydrofuran and 
tetrahydrothiophene. 
Alkoxy is typically methoxy, ethoxy, propoxy, isopropoxy, n-butoxy, 
isobutoxy, sec-butoxy and tert-butoxy. 
Alkali metal in the context of this invention will be understood as meaning 
lithium, sodium, potassium, rubidium and caesium, preferably lithium, 
sodium and potassium. 
Alkaline earth metal in the context of the present invention will be 
understood as meaning beryllium, magnesium, calcium, strontium and barium, 
preferably magnesium and calcium. 
In the above definitions, halogen will be understood as meaning fluoro, 
chioro, bromo and iodo. Fluoro, chloro and bromo are the preferred 
meanings. 
Particularly suitable compounds of the formula I for the process of the 
invention are those in which Q.sub.2 is hydrogen. 
Further compounds of formula I which are preferred for the polymerisation 
are those in which the alicyclc ring that Q.sub.1 forms together with the 
--CH.dbd.CQ.sub.2 -- group contains 3 to 16, more particularly 3 to 12 
and, most preferably, 3 to 8, ring atoms, which ring system may be 
monocyclic, bicyclic, tricyclic or tetracyclic. 
The inventive process can be carried out with particular advantage with 
those compounds of the formula I, wherein 
Q.sub.1 is a radical having at least one carbon atom which, together with 
the --CH.dbd.CQ.sub.2 -- group, forms a 3- to 20-membered alicyclic ring 
which may contain one or more hetero atoms selected from the group 
consisting of silicon, oxygen, nitrogen and sulfur; which radical is 
unsubstituted or substituted by halogen, .dbd.O, --CN, --NO.sub.2, R.sub.1 
R.sub.2 R.sub.3 Si--(O).sub.u --, --COOM, --SO.sub.3 M, --PO.sub.3 M, 
--COO(M.sub.1).sub.1/2, --SO.sub.3 (M.sub.1).sub.1/2, --PO.sub.3 
(M.sub.1).sub.1/2, C.sub.1 -C.sub.12 alkyl, C.sub.1 -C.sub.12 haloalkyl, 
C.sub.1 -C.sub.12 hydroxyalkyl, C.sub.1 -C.sub.4 cyanoalkyl, C.sub.3 
-C.sub.6 cycloalkyl, C.sub.6 -C.sub.12 aryl, C.sub.7 -C.sub.12 aralkyl, 
C.sub.3 -C.sub.6 heterocycloalkyl, C.sub.3 -C.sub.12 heteroaryl, C.sub.4 
-C.sub.12 heteroaralkyl or R.sub.4 --X--; or two adjacent carbon atoms in 
said radical Q.sub.1 are substituted by --CO--O--CO-- or --CO--NR.sub.5 
--CO--; or an aromatic or heteroaromatic ring which is unsubstituted or 
substituted by halogen, --CN, --NO.sub.2, R.sub.6 R.sub.7 R.sub.8 Si--, 
--COOM, --SO.sub.3 M, --PO.sub.3 M, --COO(M.sub.1).sub.1/2, --SO.sub.3 
(M.sub.1).sub.1/2, --PO.sub.3 (M.sub.1).sub.1/2, C.sub.1-C.sub.12 alkyl, 
C.sub.1 -C.sub.12 haloalkyl, C.sub.1 -C.sub.12 hydroxyalkyl, C.sub.1 
-C.sub.4 cyanoalkyl, C.sub.3 -C.sub.6 cycloalkyl, C.sub.6 -C.sub.12 aryl, 
C.sub.7 -C.sub.12 aralkyl, C.sub.3 -C.sub.6 heterocycloalkyl, C.sub.3 
-C.sub.12 heteroaryl, C.sub.4 -C.sub.12 hetroaralkyl or R.sub.13 --X.sub.1 
-- can be fused to adjacent carbon atoms; 
X and X.sub.1 are each independently of the other --O--, --S--, --CO--, 
--SO--, --SO.sub.2 --, --O--C(O)--, --C(O)--O--, --C(O)--NR.sub.5 --, 
--NR.sub.10 --C(O)--, --SO.sub.2 --O-- or --O--SO.sub.2 --; and R.sub.1, 
R.sub.2 and R.sub.3 are each independently of one another C.sub.1 -C.sub.6 
alkyl, C.sub.1 -C.sub.6 perfluoroalkyl, phenyl or benzyl; 
M is an alkali metal and M.sub.1 is an alkaline earth metal; 
R.sub.4 and R.sub.13 are each independently of the other C.sub.1 -C.sub.12 
alkyl, C.sub.1 -C.sub.12 haloalkyl, C.sub.1 -C.sub.12 hydroxyalkyl, 
C.sub.3 -C.sub.8 cycloalkyl, C.sub.6 -C.sub.12 aryl or C.sub.7 -C.sub.12 
aralkyl; 
R.sub.5 and R.sub.10 are each independently of the other hydrogen, C.sub.1 
-C.sub.6 alkyl, phenyl or benzyl, the alkyl groups in turn being 
unsubstituted or substituted by C.sub.1 -C.sub.6 alkoxy or C.sub.3 
-C.sub.6 cycloalkyl; 
R.sub.6, R.sub.7 and R.sub.8 are each independently of one another C.sub.1 
-C.sub.6 alkyl, C.sub.1 -C.sub.6 perfluoroalkyl, phenyl or benzyl; 
u is 0 or 1; 
and the alicyclic ring formed with Q.sub.1 may contain further non-aromatic 
double bonds; 
Q.sub.2 is hydrogen, C.sub.1 -C.sub.12 alkyl, C.sub.1 -C.sub.12 haloalkyl, 
C.sub.1 -C.sub.6 alkoxy, halogen, --CN or R.sub.11 --X.sub.2 --; 
R.sub.11 is C.sub.1 -C.sub.12 alkyl, C.sub.1 -C.sub.12 halogalkyl, C.sub.1 
-C.sub.12 hydroxyalkyl, C.sub.3 -C.sub.6 cycloalkyl, C.sub.6 -C.sub.12 
aryl or C.sub.7 -C.sub.12 aralkyl; 
X.sub.2 is --C(O)--O-- or --C(O)--NR.sub.12 --; and 
R.sub.12 is hydrogen, C.sub.1 -C.sub.6 alkyl, phenyl or benzyl; 
and the cycloalkyl, heterocycloalkyl, aryl, heteroaryl, aralkyl and 
heteroaralkyl groups are unsubstituted or substituted by C.sub.1 -C.sub.6 
alkyl, C.sub.1 -C.sub.6 alkoxy, --NO.sub.2, --CN or halogen, and the 
hetero atoms of the heterocycloalkyl, heteroaryl and heteroaralkyl groups 
are selected from the group consisting of --O--, --S--, --NR.sub.9 -- and 
--N.dbd.; and 
R.sub.9 is hydrogen, C.sub.1 -C.sub.6 alkyl, phenyl or benzyl. 
Among this group, those compounds of formula I are preferred wherein 
Q.sub.1 is a radical having at least one carbon atom which, together with 
the --CH.dbd.CQ.sub.2 --group, forms a 3- to 10-membered alicyclic ring 
which may contain a hetero atom selected from the group consisting of 
silicon, oxygen, nitrogen and sulfur, and which radical is unsubstituted 
or substituted by halogen, --CN, --NO.sub.2, R.sub.1 R.sub.2 R.sub.3 Si--, 
--COOM, --SO.sub.3 M, --PO.sub.3 M, --COO(M.sub.1).sub.1/2, --SO.sub.3 
(M.sub.1).sub.1/2, --PO.sub.3 (M.sub.1).sub.1/2, C.sub.1 -C.sub.6 alkyl, 
C.sub.1 -C.sub.6 haloalkyl, C.sub.1 -C.sub.6 hydroxyallyl, C.sub.1 
-C.sub.4 cyanoalkyl, C.sub.3 -C.sub.6 cycloalkyl, phenyl, benzyl or 
R.sub.4 --X--; or an aromatic or heteroaromatic ring which is 
unsubstituted or substituted by halogen, --CN, --NO.sub.2, R.sub.6 R.sub.7 
R.sub.8 Si--, --COOM, --SO.sub.3 M, --PO.sub.3 M, --COO(M.sub.1).sub.1/2, 
--SO.sub.3 (M.sub.1).sub.1/2, --PO3(M.sub.1).sub.1/2, C.sub.1 -C.sub.6 
alkyl, C.sub.1 -C.sub.6 haloalkyl, C.sub.1 -C.sub.6 hydroxyalkyl, C.sub.1 
-C.sub.4 cyanoalkyl, C.sub.3 -C.sub.6 cycloalkyl, phenyl, benzyl or 
R.sub.13 --X.sub.1 -- can be fused to adjacent carbon atoms; 
R.sub.1, R.sub.2 and R.sub.3 are each independently of one another C.sub.1 
-C.sub.4 alkyl, C.sub.1 -C.sub.4 perfluoroalkyl, phenyl or benzyl; 
M is an alkali metal and M.sub.1 is an alkaline earth metal; 
R.sub.4 and R.sub.13 are each independently of the other C.sub.1 -C.sub.6 
alkyl, C.sub.1 -C.sub.6 haloalkyl, C.sub.1 -C.sub.6 hydroxyalkyl or 
C.sub.3 -C.sub.6 cycloalkyl; --O--, --S--, --CO--, --SO--or --SO2--; 
X and X.sub.1 are each independently of the other --O--, --S--, --CO--, 
--SO-- or --SO.sub.2 --; R.sub.6, R.sub.7 and R.sub.8 are each 
independently of one another C.sub.1 -C.sub.4 alkyl, C.sub.1 -C.sub.4 
perfluoroalkyl, phenyl or benzyl; and 
Q.sub.2 is hydrogen. 
The process of this invention is particularly suitable for the 
polymerisation of norbornenes and norbornene derivatives. Among these 
norbornene derivatives, those compounds are especially preferred which 
conform to formula II 
##STR5## 
wherein X.sub.3 is --CHR.sub.16 --, oxygen or sulfur, R.sub.14 and 
R.sub.15 are each independently of the other hydrogen, --CN, 
trifluoromethyl, (CH.sub.3).sub.3 Si--O--, (CH.sub.3).sub.3 Si-- or 
--COOR.sub.17 ; and 
R.sub.16 and R.sub.17 are each independently of the other hydrogen, C.sub.1 
-C.sub.12 alkyl, phenyl or benzyl; or to formula III 
##STR6## 
wherein X.sub.4 is --CHR.sub.19 --, oxygen or suilir; 
R.sub.19 is hydrogen, C.sub.1 -C.sub.12 alkyl, phenyl or benzyl; and 
R.sub.18 is hydrogen, C.sub.1 -C.sub.6 alkyl or halogen; or to formula IV 
##STR7## 
wherein X.sub.5 is --CHR.sub.22 --, oxygen or sulfur; 
R.sub.22 is hydrogen, C.sub.1 -C.sub.12 alkyl, phenyl or benzyl; 
R.sub.20 and R.sub.21 are each independently of the other hydrogen, CN, 
trifluoromethyl, (CH.sub.3).sub.3 Si--O--, (CH.sub.3).sub.3 Si-- or 
--COOR.sub.23 ; and 
R.sub.23 is hydrogen, C.sub.1 -C.sub.12 alkyl, phenyl or benzyl; 
or to formula V 
##STR8## 
wherein X.sub.6 is --CHR.sub.24 --, oxygen or sulfur; 
R.sub.24 is hydrogen, C.sub.1 -C.sub.12 alkyl, phenyl or benzyl; 
Y is oxygen or 
##STR9## 
and R.sub.25 is hydrogen, methyl, ethyl or phenyl. 
The following compounds of formula I are particularly suitable for the 
polymerisation process of this invention: 
##STR10## 
The molybdenum and tungsten compounds to be used in the practice of this 
invention may be those which contain one metal atom or two metal atoms 
linked through a single. double or triple bond. The compounds contain at 
least two, more particularly two to six and, most preferably, two to four 
methyl groups or monosubstituted methyl groups lacking .beta.-hydrogen 
atoms as metal-ligand bonds. The other valencies of molybdenum and 
tungsten are preferably saturated with thermostable neutral ligands (the 
definition of thermostability has been stated at the outset). This ligand 
without .beta.-hydrogen atoms preferably has the formula VII 
EQU --CH.sub.2 --R (VII), 
wherein R is H, --CF.sub.3, --CR.sub.26 R.sub.27 R.sub.28, --SiR.sub.29 
R.sub.30 R.sub.31, unsubstituted or C.sub.1 -C.sub.6 alkyl- or C.sub.1 
-C.sub.6 alkoxy-substituted C.sub.6 -C.sub.16 aryl or C.sub.4 -C.sub.15 
heteroaryl containing 1 to 3 hetero atoms selected from the group 
consisting of O, S and N; and 
R.sub.26, R.sub.27 and R.sub.28 are each independently of one another 
C.sub.1 -C.sub.10 alkyl which is unsubstituted or substituted by C.sub.1 
-C.sub.10 alkoxy, or R.sub.26 and R.sub.27 have this meaning and R.sub.28 
is C.sub.6 -C.sub.10 aryl or C.sub.4 -C.sub.9 heteroaryl which is 
unsubstituted or substituted by C.sub.1 -C.sub.6 alkyl or C.sub.1 -C.sub.6 
alkoxy; and 
R.sub.29, R.sub.30 and R.sub.31 are each independently of one another 
C.sub.1 -C.sub.6 alkyl, C.sub.5 - or C.sub.6 cycloalkyl, or unsubstituted 
phenyl or benzyl or phenyl or benzyl each substituted by C.sub.1 -C.sub.6 
alkyl or C.sub.1 -C.sub.6 alkoxy. 
R.sub.26 to R.sub.31 in the significance of alkyl may be linear or branched 
and contain preferably 1 to 8 and, most preferably, 1 to 4, carbon atoms. 
R.sub.28 to R.sub.31 defined as aryl are preferably phenyl or naphthyl. 
R in defined in formula VII as aryl is preferably phenyl or naphthyl. R 
defined in formula VII as heteroaryl is preferably pyridinyl, furanyl, 
thiophenyl or pyrrolyl. 
Preferred substituents for R.sub.26 to R.sub.31 within the scope of the 
definitions are methyl, ethyl, methoxy and ethoxy. Exemplary substituents 
R.sub.26 to R.sub.31 have been cited previously in connection with the 
compounds formula I. 
In a preferred embodiment of the invention, the group R in formula VII is 
H, --C(CH.sub.3).sub.3, --C(CH.sub.3).sub.2 C.sub.6 H.sub.5, unsubstituted 
phenyl or phenyl which is substituted by methyl, ethyl, methoxy or ethoxy, 
--CF.sub.3, or --Si(CH.sub.3).sub.3. 
The other 1 to 4 valencies of the Mo(VI) and W(VI) atoms can be saturated 
with identical or different ligands selected from the group consisting of 
.dbd.O, .dbd.N--R.sub.33, secondary amines containing 2 to 18 carbon 
atoms, R.sub.32 O-- or R.sub.32 S--, halogen, cyclopentadienyl or bridged 
biscylopentadienyl, tridentate monoanionic ligands, or neutral ligands 
such as arenes, olefins, ethers, nitriles, CO and tertiary phosphines and 
amines, wherein the R.sub.32 substituents independently of each other are 
unsubstituted or C.sub.1 -C.sub.6 alkoxy- or halogen-substituted linear or 
branched C.sub.1 -C.sub.18 alkyl, C.sub.5 -- or C.sub.6 cycloalkyl which 
is unsubstituted or substituted by C.sub.1 -C.sub.6 alkyl, C.sub.1 
-C.sub.6 alkoxy or halogen, or phenyl which is unsubstituted or 
substituted by C.sub.1 -C.sub.6 alkyl, C.sub.1 -C.sub.6 alkoxy, C.sub.1 
-C.sub.6 alkoxymethyl, C.sub.1 -C.sub.6 alkoxyethyl or halogen, or benzyl 
which is unsubstituted or substituted by C.sub.1 -C.sub.6 alkyl, C.sub.1 
-C.sub.6 alkoxy, C.sub.1 -C.sub.6 alkoxymethyl, C.sub.1 -C.sub.6 
alkoxyethyl or halogen, or phenylethyl; and R.sub.33 is unsubstituted or 
C.sub.1 -C.sub.6 alkoxy-substituted linear or branched C.sub.1 -C.sub.18 
alkyl, C.sub.5 - or C.sub.6 cycloalkyl which is unsubstituted or 
substituted by C.sub.1 -C.sub.6 alkyl, C.sub.1 -C.sub.6 alkoxy or halogen, 
phenyl which is unsubstituted or substituted by C.sub.1 -C.sub.6 alkyl, 
C.sub.1 -C.sub.6 alkoxy, C.sub.1 -C.sub.6 alkoxymethyl, C.sub.1 -C.sub.6 
alkoxyethyl, di(C.sub.1 -C.sub.6 -alkyl)amino, di(C.sub.1 -C.sub.6 
alkyl)amino-C.sub.1 -C.sub.3 alkyl or halogen, or benzyl which is 
unsubstituted or substituted by C.sub.1 -C.sub.6 alkyl, C.sub.1 -C.sub.6 
alkoxy, C.sub.1 -C.sub.6 alkoxymethyl, C.sub.1 -C.sub.6 alkoxyethyl or 
halogen, or phenylethyl. 
Secondary amines are preferably those of formula R.sub.34 R.sub.35 N--, 
wherein R34 and R.sub.35 are each independently of the other linear or 
branched C.sub.1 -C.sub.18 alkyl, C.sub.5 - or C.sub.6 cycloalkyl, 
unsubstituted or C.sub.1 -C.sub.6 alkoxy- or halogen-substituted benzyl or 
phenylethyl, (C.sub.1 -C.sub.6 alkyl).sub.3 Si or, taken together, are 
tetramethylene, pentamethylene or 3-oxapentan-1,5-diyl. Alkyl preferably 
contains 1 to 12 and, most preferably, 1 to 6, carbon atoms. Typical 
examples are dimethylamino, diethylamino, di-n-propylamino, 
diisopropylamino, di-n-butylamino, methylethylamino, dibenzylamino, 
benzylmethyereino, diphenylamino, phenylmethylamino and 
di(tdriethylsilyl)amino. 
Halogen as ligand or substituent is preferably F and, most preferably, Cl. 
Cyclopentadienyl may be unsubstituted or substituted by one to five C.sub.1 
-C.sub.4 alkyl groups, preferably methyl, or --Si(C.sub.1 -C.sub.4 alkyl), 
preferably --Si(CH.sub.3)3. Bridged cyclopentadienyls are preferably those 
of formula R.sub.36 --A--R.sub.36, wherein R.sub.36 is cyclopentadienyl 
which is unsubstituted or substituted by one to five C.sub.1 -C.sub.4 
alkyl groups, preferably methyl, or --Si(C.sub.1 -C.sub.4 alkyl), 
preferably --Si(CH.sub.3).sub.3, and A is --CH.sub.2 --, --CH.sub.2 
--CH.sub.2 --, --Si(CH.sub.3).sub.2 --, --Si(CH.sub.3).sub.2 
--Si(CH.sub.3).sub.2 -- or --Si(CH.sub.3).sub.2 --O--Si(CH.sub.3).sub.2 
--. 
Suitable arenes are typically aromatic hydrocarbons or fused hydrocarbons 
containing 6 to 18 carbon atoms, or 5- or 6membered heterocycles or fused 
heterocycles containing one hetero atom selected from the group consisting 
of O, S and N and containing 4 to 17 carbon atoms. Typical examples are 
benzene, naphthalene, naphthacene, pyrene, pyridine, quinoline and 
thiophene. 
Olefins as neutral ligands may typically be open-chain or cyclic mono- or 
diolefins containing 2 to 8 carbon atoms. Typical examples are ethene, 
propene, butene butadiene, hexene, hexadiene, cyclohexadiene and 
cyclooctadiene. 
Ethers suitable as neutral ligands may be dialkyl ethers containing 2 to 8 
carbon atoms or cyclic ethers containing 5 or 6 ring members. Typical 
examples are diethyl ether, methyl ethyl ether, diethyl ether, di-n-propyl 
ether, diisopropyl ether, di-n-butyl ether, ethylene glycol dimethyl 
ether, tetrahydrofuran and dioxane. 
Nitriles suitable as neutral ligands may be aliphatic or aromatic nitriles 
containing 1 to 12, preferably 1 to 8, carbon atoms. Typical examples are 
acetonitrile, propionitrile, butyl nitrile, benzonitrile and benzyl 
nitrile. 
Tertiary amines and phosphines suitable as neutral ligands may be those 
containing 3 to 24, preferably 3 to 18, carbon atoms. Typical examples are 
trimethylamine and trimethylphosphine, triethylamine and 
triethylphosphine, tri-n-propylamine and tri-n-propylphosphine, 
tri-n-butylarnine and tri-n-butylphosphine, triphenylamine and 
tri-phenylphosphine, tricyclohexylamine and tricyclohexylphosphine, 
phenyldimethylamine and phenyldimethylphosphine, benzyldimethylamine and 
benzyldimethylphosphine, 3,5-dimethylphenyldimethylamine and 
3,5-dimethylphenyldimethylphosphine. 
The tridentate monoanionic ligands may typically be 
hydro(trispyrazol-1-yl)borates or alkyl(trispyrazol-1-yl)borates, which 
are unsubstituted or substituted by 1 to 3 C.sub.1 -C.sub.4 alkyl groups 
q.v. S. Trofimenko, Chem. Rev., 93, pp. 943-980 (1993)!, or C.sub.5 
(R'.sub.5)Co(R.sub.37 R.sub.38 P.dbd.O!.sup..crclbar., wherein R' is H or 
methyl and R.sub.37 and R.sub.38 are each independently of the other 
C.sub.1 -C.sub.4 alkyl, C.sub.1 -C.sub.4 alkoxy or phenyl q.v. W. Klaui, 
Angew. Chem. 102, pp. 661-670 (1990)!. 
Halogen as substituent of R.sub.32 and R.sub.33 is preferably fluoro and, 
most preferably, chloro. The substituents alkyl, alkoxy or alkoxy in 
alkoxymethyl or alkoxyethyl preferably contain 1 to 4 and, most 
preferably, 1 or 2 carbon atoms. Typical examples are methyl, ethyl, n- 
and isopropyl, n-, iso- and tert-butyl, methoxy, ethoxy, n- and isopropoxy 
and n-, iso- and tert-butoxy. 
R.sub.32 and R.sub.33 contain as alkyl preferably 1 to 12, more 
particularly 1 to 8 and, most preferably, 1 to 4, carbon atoms. Branched 
alkyl is preferred. Typical examples of of R.sub.32 are methoxy, ethoxy, 
n- and isopropoxy, n-, iso- and tert-butoxy, hexafluoroisopropoxy and 
hexa- and perfluorobutoxy. 
Typical examples of substituted phenyl and benzyl for R.sub.32 and R.sub.33 
are p-methylphenyl or benzyl p-fluorophenyl or p-chlorophenyl or 
p-chlorobenzyl, p-ethylphenyl or ethylbenzyl, p-n- or isopropylphenyl or 
p-n- or isopropylbenzyl, p-isobutylphenyl or p-isobutylbenzyl, 
3-methylphenyl or 3-methylbenzyl, 3-isopropylphenyl or 3-isopropylbenzyl 
3,5-dimethylphenyl or 3,5-dimethylbenzyl, 3,5-isopropylphenyl or 
3,5-isopropylbenzyl, 3,5-n- or -tert-butylphenyl and 3,5-n- or 
-tert-butylbenzyl. R.sub.33 is most preferably unsubstituted or C.sub.1 
-C.sub.4 alkyl- or C.sub.1 -C.sub.4 alkoxy-substituted phenyl. 
In a preferred embodiment of the invention, the molybdenum and tungsten 
compounds are in particular compounds of formula VIII and also of formulae 
VIIIa, VIIIb and VIIIc, 
##STR11## 
wherein Me is Mo(VI) or W(VI), 
at least two, preferably 2 to 4, of the substituents R.sub.39 to R44 are a 
radical --CH.sub.2 --R of formula VII, R is H, --CF.sub.3, --CR.sub.26 
R.sub.27 R.sub.28, --SiR.sub.29 R.sub.30 R.sub.31, unsubstituted or 
C.sub.1 -C6alkyl- or C.sub.1 -C.sub.6 alkoxy-substituted C.sub.6 -C.sub.6 
aryl or C.sub.4 -C.sub.15 heteroaryl containing 1 to 3 hetero atoms 
selected from the group consisting of O, S and N; 
R.sub.26, R.sub.27 and R.sub.28 are each independently of the other C.sub.1 
-C.sub.10 alkyl which is unsubstituted or substituted by C.sub.1 -C.sub.10 
alkoxy, or R.sub.26 and R.sub.27 have this meaning and R.sub.28 is C.sub.6 
-C.sub.10 aryl or C.sub.4 -C.sub.9 heteroaryl which is unsubstituted or 
substituted by C.sub.1 -C.sub.6 alkyl or C.sub.1 -C.sub.6 alkoxy; and 
R.sub.29, R.sub.30 and R.sub.31 are each independently of one another 
C.sub.1 -C.sub.6 alkyl, C.sub.5 - or C.sub.6 cycloalkyl, or unsubstituted 
or C.sub.1 -C.sub.6 alkyl- or C.sub.1 -C.sub.6 alkoxy-substituted phenyl 
or benzyl; 
two each of the remaining substituents R.sub.39 to R.sub.44 are .dbd.O or 
.dbd.N--R.sub.33, and R.sub.33 is unsubstituted or C.sub.1 -C.sub.6 
alkoxy-substituted linear or branched C.sub.1 -C.sub.18 alkyl, 
unsubstituted or C.sub.1 -C.sub.6 aLkyl-, C.sub.1 -C.sub.6 alkoxy- or 
halogen-substituted C.sub.5 - or C.sub.6 cycloalkyl, unsubstituted phenyl 
or phenyl which is substituted by C.sub.1 -C.sub.6 alkyl, C.sub.1 -C.sub.6 
alkoxy, C.sub.1 -C.sub.6 alkoxymethyl, C.sub.1 -C.sub.6 alkoxyethyl or 
halogen, or benzyl or phenylethyl each of which is unsubstituted or 
substituted by C.sub.1 -C.sub.6 alkyl, C.sub.1 -C.sub.6 alkoxy, C.sub.1 
-C.sub.6 alkoxymethyl, C.sub.1 -C.sub.6 alkoxyethyl or halogen; and/or 
the remaining substituents R.sub.39 to R.sub.44 are secondary amino 
containing 2 to 18 carbon atoms, R.sub.32 O-- or R.sub.32 S--, halogen, 
cyclopentadienyl or bridged biscylopentadienyl or a neutral ligand, 
wherein the R.sub.32 substituents are each independently of the other 
unsubstituted or C.sub.1 -C.sub.6 alkoxy- or halogen-substituted linear or 
branched C.sub.1 -C.sub.18 alkyl, unsubstituted or C.sub.1 -C.sub.6 
alkyl-, C.sub.1 -C.sub.6 alkoxy or halogen-substituted C.sub.5 - or 
C.sub.6 cycloalkyl, unsubstituted phenyl or phenyl which is substituted by 
C.sub.1 -C.sub.6 alkyl, C.sub.1 -C.sub.6 alkoxy, C.sub.1 -C.sub.6 
alkoxymethyl, C.sub.1 -C.sub.6 alkoxyethyl, di(C.sub.1 -C.sub.6 
-alkyl)amino, di(C.sub.1 -C.sub.6 -alkyl)amino-C.sub.1 -C.sub.3 alkyl or 
halogen, or benzyl or phenylethyl each of which is substituted by C.sub.1 
-C.sub.6 alkyl, C.sub.1 -C.sub.6 alkoxy, C.sub.1 -C.sub.6 alkoxymethyl, 
C.sub.1 -C.sub.6 alkoxyethyl or halogen 
With respect to R and R.sub.26 to R.sub.33, the preferred meanings 
previously given apply. 
In a particularly preferred embodiment of the process of this invention, 
molybdenum and tungsten compounds of formula VIII are used, wherein 
a) R.sub.39 to R.sub.44 are a radical of formula VII --CH.sub.2 --R, or 
b) R.sub.39 and R.sub.40 are a radical of formula VII --CH.sub.2 --R, 
R.sub.41 and R.sub.42 together are a radical .dbd.N--R.sub.33, and 
R.sub.43 and R.sub.44 together are R.sub.32 --O-- or halogen, or 
c) R.sub.43 and R.sub.44 together and R.sub.41 and R.sub.42 together are 
the radical .dbd.N--R.sub.33, and R.sub.39 and R.sub.40 are a radical of 
formula VII --CH.sub.2 --R, 
and R, R.sub.32 and R.sub.33 have the meanings given above. With respect to 
R, R.sub.32 and R.sub.33, the preferred meanings given above apply. 
Among the compounds of formula VIIIc, those compounds are especially 
preferred in which R.sub.39, R.sub.40 and R.sub.4, are a radical of 
formula VII, which radical is most preferably --CH.sub.2 --Si(C.sub.1 
-C.sub.4 akyl).sub.3. 
In the process of this invention it is most especially preferred to use 
molybdenum and tungsten compounds of formulae IX, IXa or Ixb, 
##STR12## 
wherein Me is Mo(VI) or W(VI), 
R is H, --C(CH.sub.3).sub.3, --C(CH.sub.3).sub.2 --C.sub.6 H.sub.5, 
--C.sub.6 H.sub.5 or --Si(C.sub.1 -C.sub.4 alkyl).sub.3, 
R.sub.33 is phenyl or phenyl which is substituted by 1 to 3 C.sub.1 
-C.sub.4 alkyl or C.sub.1 -C.sub.4 alkoxy groups, 
R.sub.41 is unsubstituted or fluoro-substituted linear or, preferably, 
branched C.sub.1 -C.sub.4 alkoxy, and 
R.sub.42 has the same meaning as R.sub.41 or is F, Cl or Br. R.sub.41 is 
most preferably branched alkoxy or branched alkoxy which may be partially 
or completely fluorinated, typically isopropoxy, iso- and tert-butoxy, 
hexafluoropropoxy and nonafluoropropoxy. R.sub.42 is preferably Cl. 
Typical examples of molybdenum and tungsten compounds are: 
Mo.sub.2 CH.sub.2 Si(CH.sub.3).sub.3 !.sub.6, W(.dbd.N--C.sub.6 
H.sub.5)(OCH(CH.sub.3) 2)(Cl)(CH.sub.2 Si(CH.sub.3)3)!.sub.2, 
W(.dbd.N--C.sub.6 H.sub.5)(OCH(CF.sub.3)2)(CH.sub.2 
Si(CH.sub.3).sub.3)!.sub.2, 
Mo(.dbd.N--3,5-diisopropylC.sub.6 H.sub.5).sub.2 (CH.sub.2 C(CH.sub.3) 
.sub.2 --C6H.sub.5)!.sub.2, 
Mo(.dbd.N--3,5-diisopropylC.sub.6 H.sub.5).sub.2 (CH.sub.2 --C.sub.6 
H.sub.5)!.sub.2, Mo(.dbd.N--3,5-dimethylC.sub.6 H.sub.5).sub.2 (CH.sub.2 
--C.sub.6 H.sub.5)!.sub.2, 
Mo(.dbd.N--3,5-dimethylC.sub.6 H.sub.5).sub.2 (CH.sub.3).sub.2 
(tetrahydrofuran), 
(CH.sub.3).sub.3 SiCH.sub.2!.sub.3 Mo.tbd.MoCH.sub.2 Si(CH.sub.3).sub.3 
!.sub.3, W(.dbd.NC.sub.6 H.sub.5)CH.sub.2 Si(CH.sub.3).sub.3 !Cl. 
The molybdenum and tungsten compounds used in the process of this invention 
are known or can be prepared by known and analogous methods starting from 
metal halides and Grignard reactions q.v. inter alia F. Hug et al. J. 
Chem. Soc., Chem. Commun., page 1079 (1971) or R. R. Schrock et al., J. 
Am. Chem. Soc., Vol. 112, page 3875 (1990)!. 
The inventive process can be carried out in the presence of an inert 
solvent. A particular advantage of the inventive process is that, if 
liquid monomers are used, the process can be carried out without a 
solvent. Inert means that the choice of solvent will depend on the 
reactivity of the molybdenum and tungsten compounds, for example that 
protic polar solvents are not used if substitution reactions, such as 
replacement of halogen by alkoxy, are to be expected. 
Suitable inert solvents are typically protic polar and aprotic solvents, 
which can be used by themselves or in mixtures of at least two solvents. 
Examples of such solvents are: ethers (dibutyl ether, tetrahydrofuran, 
dioxane, ethylene glycol monomethyl or dimethyl ether, ethylene glycol 
monoethyl or diethyl ether, diethylene glycol diethyl ether and 
triethylene glycol dimethyl ether), halogenated hydrocarbons (methylene 
chloride, chloroform, 1,2-dichloroethane, 1,1,1-trichloroethane and 
1,1,2,2-tetrachloroethane), carboxylates and lactones (ethyl acetate, 
methyl propionate, ethyl benzoate, 2-methoxyethyl acetate, 
.gamma.-butyrolactone, .delta.-valerolactone, pivalolactone), carboxamides 
and lactams (N,N-dimethylformamide, N,N-diethylformamide, 
N,N-dimethylacetamide, tetramethylurea, hexamethyl phosphoric triam, 
.gamma.-butyrolactam, .epsilon.-caprolactaon, N-methylpyirolidone, 
N-acetylpyrrolidone, N-methylcaprolactam), sutfoxides (dimethyl 
sulfoxide), sulfones (dimethyl sulfone, diethyl sulfone, triethylene 
sulfone, tetraethylene sulfone), tertiary amines (N-methylpiperidine, 
N-methylmorpholine), aliphatic and aromatic hydrocarbons, for example 
petroleum ether, pentane, hexane, cyclohexane, methylcyclohexane, benzene 
or substituted benzenes (chiorobenzene, o-dichlorobenzene, 
1,2,4-trichiorobenzene, nitrobenzene, toluene, xylene) and nitrfles 
(acetonitrile, propionitrile, benzonitrile, phenylacetonitrile). Preferred 
solvents are aprotic polar and non-polar solvents. 
Preferred solvents are aliphatic and aromatic hydrocarbons and mixtures of 
such solvents. 
It is to be particularly highlighted that that the compositions used in the 
practice of this invention comprising a n unsubstituted or s ubstituted 
cycloolefin and catalyst are often insensitive to oxygen, thereby 
permitting storage and also the reaction to be carried out without an 
inert gas. It is, however, advisable to exclude atmospheric moisture, i.e. 
to use dry reaction and storage conditions. 
The monomers of formula I and catalysts used for the inventive process can 
be stored separately as well as together as mixture, as the catalyst has a 
particularly high stability. The mixture can be stored prior to the 
photochemical polymerisation as ready-for-use formulation, which is 
advantageous for the large-scale industrial application of the inventive 
process. Owing to its high photosensitivity, the formulation is stored in 
particular under UV light, preferably with exclusion of atmospheric 
moisture. 
In another of its aspects, the invention relates to a photopolymerisable 
composition comprising a cyclic olefin, or at least two different cyclic 
olefins, and a catalytically effective amount of at least one thermostable 
molybdenum (VI) or tungsten (VI) compound which contains at least two 
methyl groups or two monosubstituted methyl groups lacking .beta.-hydrogen 
atoms in the substituent and which are bonded to the metal atom. 
The inventive composition may contain formulation assistants, suitably 
those compounds listed above as solvents. Known formulation assistants are 
plasticisers, dyes, pigments, fillers, reinforcing fillers, lubricants and 
mould release agents. 
It is not necessary in the inventive process to maintain the irradiation of 
the reaction mixture over the entire duration of the reaction. Once the 
polymerisation has been photochemically initiated, the further reaction 
course proceeds by itself even in the dark. The irradiation time will 
depend on the type of light source employed. It is preferred to use UV 
lasers or UV lamps in the inventive process. Irradiation of the catalyst 
can be effected before, during and also after the addition of the 
monomers. 
Suitable irradiation times are from one minute to 8 hours, in particular 
from 5 minutes to 4 hours. The sequence of the addition of monomers and 
catalyst is not critical. The monomer can either be initially introduced 
into the reactor or added after introduction of the catalyst. Likewise, 
the catalyst can be irradiated beforehand and then added to the monomer. 
Furthermore, the solution comprising catalyst and monomer can also be 
irradiated. 
The inventive process is preferably carried out at room temperature to 
slightly elevated temperature. An increase in temperature serves to 
increase the reaction rate. Only in exceptional cases do the catalysts 
themselves initiate a thermal polymerisation. Therefore mainly a 
photopolymerisation takes place at the temperatures chosen for the 
catalysis. It should be mentioned, however, that the catalysts can be 
converted into thermoactive catalysts by sufficient irradiation. 
It is preferred to carry out the inventive process in the temperature range 
from -20.degree. to +110.degree. C. 
A particular and surprising advantage of the inventive process is that the 
molybdenum and tungsten compounds employed act as thermal catalysts after 
irrdiation. This feature results in the possibility of continuing and 
terminating the polymerisation after a brief irradiation time by applying 
heat, thereby affording economic and technical advantages in different 
fields in the fabrication of moulded objects or coatings. The combined 
process is particularly suitable for the preparation of thermoplastics. 
The invention further relates to a process for the photocatalytic 
polymerisation of a cyclic olefin, or at least two different cyclic 
olefins, in the presence of a metal compound as catalyst, which process 
comprises 
a) initially irradiating the cycloolefins in the presence of a catalytic 
amount of at least one thermostable molybdenum (VI) or tungsten (VI) 
compound which contains at least two methyl groups or two monosubstituted 
methyl groups lacking .beta.-hydrogen atoms in the substituent and which 
are bonded to the metal atom; or irradiating a catalytic amount of at 
least one thermostable molybdenum (VI) or tungsten (VI) compound which 
contains at least two methyl groups or two monosubstituted methyl groups 
lacking .beta.-hydrogen atoms in the substituent and which are bonded to 
the metal atom, without a solvent or in an inert solven, and then mixing 
the catalyst with at least one cycloolefin; and 
b) terminating the polymerisation by heating and without irradiation. 
The preferences deflned above apply to process stage a). The irradiation 
time essentially depends on the desired reaction procedure. A brief 
irradiation is chosen if, for example, the polymerisation is to be only 
initiated by irradiation and terminated by heating. Brief may be an 
irradiation time of up to 60 seconds, preferably 5 to 60 seconds and, most 
preferably, 10 to 40 seconds. A longer irradiation time may be chosen if, 
for example, the polymerisation is to be carried out mainly by irradiation 
and the final polymerisation is to be terminated only by subsequent 
heating. 
Heating in process stage b) may be a reaction temperature in the range from 
50.degree. to 200.degree. C., preferably from 50.degree. to 150.degree. C. 
and, most preferably, from 70.degree. to 120.degree. C. 
Catalytic amounts within the scope of this invention preferably mean an 
amount of 0.001 to 20 mol %, more particularly 0.01 to 15 mol % and, most 
preferably, 0.1 to 10 mol %, based on the amount of monomer, 
A further object of the invention is a process for the preparation of 
thermal catalysts for the ring-opening metathesis polymerisation of cyclic 
olefins, which comprises irradiating a thermostable molybdenum (VI) or 
tungsten (VI) compound that contains at least two methyl groups or two 
monosubstituLed methyl groups lacking .beta.-hydrogen atoms in the 
substituent and which are bonded to the metal atom, without a solvent or 
in a solvent. 
Cyclohexene usually cannot be homopolymerised by olefin metathesis. Those 
skilled in the art are familiar with this exception, which is described, 
inter alia, in K. J. Ivin, T. Saegusa, Ring-Opening Polymerisadon Yolume 
1, page 139, Elsevier Applied Science Publishers, London and N.Y. 
By the inventive process radiation-cured oligomers and polymers can be 
prepared having identical or different structural units of formula IX 
##STR13## 
wherein Q.sub.1 and Q2 are as defined for formula I. 
The preferences defined above apply to these polymers. They can be 
homopolymers or copolymers having a random distribution of the structural 
units, or block polymers. They can have an average molecular weight (Mw) 
of, for example, 500 to 2,000,000 dalton, preferably 1000 to 1,000,000 
dalton (determined by GPC in comparison with a polystyrene standard of 
narrow distribution). 
Thermoplastical materials for the fabrication of moulded articles of all 
types, coatings and relief images can be prepared by the process according 
to the invention. 
The polymers of this invention can have very different properties, 
depending on the monomer used. Some are distinguished by a very high 
oxygen permeability, low dielectric constant, good heat stability and low 
water absorption. Others have outstanding optical properties, for example 
high transparency and low refractive indices. The low shrinkage is 
furthermore to be highlighted. They can therefore be used in widely 
different industrial fields. 
The compositions of the invention are distinguished by superior bonding 
strength to the surfaces of substrates. The coated materials are also 
distinguished by very good surface smoothness and gloss. Among the good 
mechanical properties, the low shrinkage and high impact strength are to 
be singled out for special mention, as well as the heat resistance. Easy 
mould removal and good resistance to solvents also merit mention. 
These polymers are suitable for the production of medical equipment, 
implants or contact lenses; for the production of electronic components; 
as binders for paints; as photocurable compositions for model construction 
or as adhesives for bonding to substrates having low surface energy (for 
example Teflon, polyethylene and polypropylene), and as a 
photopolymerisable composition in stereolithography. The compositions of 
the invention can also be used for the production of paints by 
photopolymerisation, for which utility clear (transparent) and even 
pigmented compositions to be used. Either white or coloured pigments can 
be used. The production of moulded objects of all types by thermoplastic 
shaping processes may also be mentioned. 
The photocurable compositions of the invention are particularly suitable 
for the production of protective layers and relief images. The invention 
furthermore relates to a variant of the process of the invention for the 
production of coated materials or relief images on substrates, comprising 
applying a composition of cyclic olefin, catalyst and, in some cases, 
solvent, as a layer to a substrate, for example by dipping, brushing, 
casting, rolling, knife-coating or spin-coating processes, removing the 
solvent, if used, and irradiating the layer to effect polymerisation, or 
irradiating the layer through a photo-mask and then removing 
non-irradiated portions with a solvent. Surfaces of substrates can be 
modified or protected or, for example, printed circuits, printing plates 
or printing rollers can be produced by this process. In the production of 
printed circuits, the compositions odf the invention can also be used as 
solder resists. Other possible utilities are the production of screen 
printing masks and use as radiation-curing printing inks for offset, 
screen and flexographic printing. 
The present invention further relates to a substrate which is coated with 
an oligomer or polymer prepared according to the invention and which 
comprises a crosslinking agent. These materials are suitable for the 
production of protective coatings or relief images by irradiation (usually 
through a photomask) and subsequent development with a solvenl Suitable 
crosslining agents which may be present in the materials in an amount of 
0.01 to 20% by weight, are preferably organic bisazides, more particularly 
the commercially available 2,6bis(4azidobenzylidene)4methylcyclohexanone. 
The invention further relates to a coated substrate having applied thereto 
a layer of at least one cyclic olefm which contains a catalytic amount of 
at least one thermostable molybdenum (VI) or tungsten (VI) compound that 
contains at least two methyl groups or two monosubstituted methyl groups 
lacking .beta.-hydrogen atoms in the substituent and which are bonded to 
the metal atom. 
The invention likweise relates to a coated substrate having thereon a 
radiation-cured layer of at least one cyclic olefin. 
Suitable substrates are typically those of glass, minerals, ceramics, 
plastics, wood, metals, metal oxides and metal nitrides. The layer 
thicknesses will essentially depend on the desired use, and may be 0.1 to 
1000 .mu.m, preferably 0.5 to 500 .mu.m, most preferably 1 to 100 .mu.m. 
The coated materials have superior bonding strength and good thermal and 
mechanical properties. 
The coated materials can be prepared by known methods such as brushing, 
knife-coating, and casting methods such as curtain coating or 
spin-coating. 
Particularly good coating results are obtained by using for the 
photometathesis polymerisation cycloolefins that additionally contain 
three and preferably one further double bond and which, within the scope 
of the invention, constitute fused ring systems, or if they have the 
formula 
##STR14##