Ruthenium complexes, process for preparation thereof, and processes for producing open-ring polymer of cycloolefins and hydrogenation products thereof by using the complex as catalyst
The present invention relates to ruthenium complex compound wherein a heteroatom-containing carbene compound having a six-membered ring structure is bonded to ruthenium and a process for the preparation thereof; a process for producing ring-opened cyclic olefin polymer by subjecting a cyclic olefin to ring-opening metathesis polymerization in the presence of such a ruthenium complex compound; and a process for producing hydrogenated product of ring-opened cyclic olefin polymers by hydrogenating the carbon-carbon double bonds of the above ring-opened polymers. The invention gives hydrogenated product of ring-opened cyclic olefin polymers having physical properties different from those of hydrogenated product of ring-opened polymers of the prior art. Particularly, the use of dicyclopentadiene can give a hydrogenated product of ring-opened cyclic olefin polymer excellent in heat resistance, and this product can be advantageously used as parts or formed products for medical appliances or electrical components.
1. A ruthenium complex compound comprising a hetero atom-containing carbene compound having a six-membered ring structure bonded to ruthenium, the carbene compound including at least one hetero atom and at least one methylene free radical in the six-membered ring structure.
2. The compound according to claim 1 , shown by the formula:
wherein R 1 –R 8 independently represent a hydrogen atom, a halogen atom, or a hydrocarbon group, and at least two of R 1 –R 8 may be bonded together to form a ring, X 1 and X 2 independently represent an anionic ligand, L represents a neutral ligand, and R 9 and R 10 independently represent a hydrogen atom or an organic group.
3. The compound according to claim 2 , wherein R 1 and R 2 are independently an alkyl group having 1–20 carbon atoms or an aryl group having 6–20 carbon atoms, and either R 9 or R 10 is a hydrogen atom and the other is an alkoxyl group having 1–20 carbon atoms or an aryl group having 6–20 carbon atoms.
4. A process for producing the compound as claimed in claim 1 , comprising reacting a ruthenium complex compound having a neutral ligand with a hetero atom-containing carbene compound having a six-membered ring structure.
5. A metathesis reaction catalyst for an olefin compound, comprising the ruthenium complex compound as claimed in claim 1 .
6. The metathesis reaction catalyst according to claim 5 for ring-opening metathesis polymerization.
7. A hydrogenation catalyst for an olefin compound, comprising the ruthenium complex compound as claimed in claim 1 .
8. A process for producing a ring-opened cyclic olefin polymer, comprising polymerizing a cyclic olefin by ring-opening metathesis polymerization in the presence of the ruthenium complex compound as claimed in claim 1 .
9. The process for producing a ring-opened cyclic olefin polymer according to claim 8 , wherein dicyclopentadiene is used as the cyclic olefin.
10. A process for producing a hydrogenated product of ring-opened cyclic olefin polymer, comprising a step of polymerizing a cyclic olefin by ring-opening metathesis polymerization in the presence of the ruthenium complex compound as claimed in claim 1 , and a step of hydrogenating carbon-carbon double bonds in the obtained polymer.
11. The process for producing a hydrogenated product of ring-opened cyclic olefin polymer according to claim 10 , wherein dicyclopentadiene is used as the cyclic olefin.