Catalyst for polymerization of norbornene monomers, method for producing norbornene polymer, method for producing norbornene copolymer, norbornene polymer and transition metal complex
A catalyst for a polymerization of norbornene monomers includes a transition metal complex represented by a formula (1). A method for producing a norbornene copolymer includes copolymerizing first norbornene monomers corresponding to a first monomer unit represented by a formula (2) and second norbornene monomers corresponding to a second monomer unit represented by a formula (3) in a presence of the catalyst. The transition metal complex is preferably (π-allyl) {2-[N-(2,6-diisopropylphenyl) iminomethyl]phenolate}palladium, (π-allyl) {2-[N-(2,6-diisopropylphenyl)iminomethyl]-4-fluorophenolate}palladium, (π-allyl)[2-(N-phenyliminomethyl) phenolate]palladium or (π-allyl){2-[N-(2,6-diisopropylphenyl) iminomethyl]-6-methylphenolate}palladium.
1. A catalyst for a polymerization of norbornene monomers, the catalyst comprising:
a transition metal complex represented by a formula (1);
a cocatalyst to generate a cationic transition metal compound by reacting with the transition metal complex, the cocatalyst being an ionic compound; and
a phosphine ligand,
wherein
M represents one transition metal belonging to Group 8, Group 9 or Group 10 of the Periodic Table of the Elements issued in 1991,
each of R 1 , R 2 , R 3 and R 4 independently represents a hydrogen atom, a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms, a halogen atom, an alkoxy group, an aryloxy group, a silyl group having 1 to 20 carbon atoms, a siloxy group containing a hydrocarbon group having 1 to 20 carbon atoms, a nitro group, a cyano group, an amide group containing a hydrocarbon group having 1 to 10 carbon atoms or a dialkylamino group containing an alkyl group having 1 to 10 carbon atoms, or
each of R 1 , R 2 , R 3 and R 4 independently represents a hydrogen atom, a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms, a halogen atom, an alkoxy group, an aryloxy group, a silyl group having 1 to 20 carbon atoms, a siloxy group containing a hydrocarbon group having 1 to 20 carbon atoms, a nitro group, a cyano group, an amide group containing a hydrocarbon group having 1 to 10 carbon atoms or dialkylamino group containing an alkyl group having 1 to 10 carbon atoms, and at least two of R 1 , R 2 , R 3 and R 4 bond to each other to form a ring structure,
R 5 represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms,
R 6 represents a hydrocarbon group having 1 to 20 carbon atoms, and
each of R 7 , R 8 , R 9 , R 10 and R 11 independently represents a hydrogen atom, a halogen atom or a hydrocarbon group having 1 to 20 carbon atoms, or
each of R 7 , R 8 , R 9 , R 10 and R 11 independently represents a hydrogen atom, a halogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and at least two of R 7 , R 8 , R 9 , R 10 and R 11 bond to each other to form a ring structure.
2. The catalyst as claimed in claim 1 , wherein M represents palladium (Pd) or nickel (Ni), R 5 represents a hydrogen atom, R 6 represents a substituted or unsubstituted phenyl group, and each of R 7 , R 8 , R 9 , R 10 and R 11 represents a hydrogen atom.
3. The catalyst as claimed in claim 2 , wherein M represents palladium, R 1 represents a hydrogen atom or a methyl group, each of R 2 and R 4 represents a hydrogen atom, R 3 represents a hydrogen atom or a fluorine atom, and R 6 represents a phenyl group or a 2,6-diisopropylphenyl group.
4. The catalyst as claimed in claim 1 , wherein the cocatalyst is trityltetrakis(pentafluorophenyl)borate or N,N-dimethylaniliniumtetrakis(pentafluorophenyl)borate.
5. The catalyst as claimed in claim 1 , wherein the phosphine ligand is tricyclohexylphosphine, tri-t-butylphosphine or triisopropylphosphine.
6. A method for producing a norbornene polymer comprising:
homopolymerizing norbornene monomers in a presence of the catalyst as claimed in claim 1 .
7. A method for producing a norbornene copolymer comprising:
copolymerizing norbornene monomers in a presence of the catalyst as claimed in claim 1 .
8. A method for producing a norbornene copolymer comprising:
copolymerizing norbornene monomers and vinyl monomers in a presence of the catalyst as claimed in claim 1 .
9. A method for producing a norbornene copolymer comprising:
copolymerizing first norbornene monomers corresponding to a first monomer unit represented by a formula (2) and second norbornene monomers corresponding to a second monomer unit represented by a formula (3) in a presence of the catalyst as claimed in claim 1 to form the norbornene copolymer including the first monomer unit and the second monomer unit,
wherein R 12 represents an alkyl group having 1 to 10 carbon atoms, and each of R 13 , R 14 and R 15 independently represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms.
10. The method as claimed in claim 9 , wherein the norbornene copolymer essentially consists of the monomer unit represented by the formula (2) and the monomer unit represented by the formula (3).