Process for manufacturing cycloolefin addition polymer
A process for manufacturing a cycloolefin addition polymer includes polymerizing monomers containing a cycloolefin compound using a catalyst containing a nickel compound or a palladium compound by addition polymerization in the presence of a molecular weight controlling agent in two steps, that is a step of a initiating the polymerization reaction using the monomers in an amount of not more than 80 wt % of the total monomers and a step of supplying the remaining monomers to the reaction system during the polymerization reaction. A cycloolefin addition polymer with a uniform quality, having a narrow molecular weight distribution and a controlled molecular weight, and excellently balanced processability and mechanical strength can be obtained at a high polymerization conversion rate using the process. The process can be operated at a highly controlled polymerization temperature, and is thus suitable for industrially manufacturing a cycloolefin addition polymer.
1. A process for manufacturing a cycloolefin addition polymer, comprising:
initiating polymerization with at most 80 wt % of a total amount of a monomer composition comprising at least one cycloolefin compound represented by formula (1):
wherein
A 1 to A 4 each, independently, represent a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a hydrocarbon group containing an oxygen atom or a nitrogen atom and having 1 to 20 carbon atoms, a trialkylsilyl group having 3 to 12 carbon atoms, or a hydrolyzable silyl group having 0 to 12 carbon atoms, and
m is 0 or 1,
in the presence of a catalyst comprising at least one of a nickel compound or a palladium compound and at least one molecular weight controlling agent, and then
adding the remaining amount of the monomer composition during the polymerization.
2. The process of claim 1 , wherein the polymerization reaction is a continuous polymerization reaction and the conversion rate is 97% or more.
3. The process of claim 1 , wherein the molecular weight controlling agent is a 1-alkene compound.
4. The process of claim 1 , wherein the monomer composition comprises at least one compound selected from the group consisting of bicyclo[2.2.1]hept-2-ene and 5-alkylbicyclo[2.2.1]hept-2-enes having an alkyl group with 1 to 12 carbon atoms in an amount of 90 mol % or more.
5. The process of claim 1 , wherein the monomer composition comprises at least one compound selected from the group consisting of 5-butylbicyclo[2.2.1]hept-2-ene, 5-hexylbicyclo[2.2.1]hept-2-ene, 5-octylbicyclo[2.2.1]hept-2-ene, and 5-decylbicyclo[2.2.1]hept-2-ene.
6. The process of claim 1 , wherein the catalyst contains (a), (b), and (d) or the catalyst contains (c) and (d):
(a) an organic acid salt of palladium or a beta-diketonate compound of palladium,
(b) a phosphine compound represented by formula (b),
P(R 1 ) 2 (R 2 ) (b)
wherein R 1 represents a group selected from a cyclopentyl group, a cyclohexyl group, and an isopropyl group, and R 2 represents a hydrocarbon group having 3 to 10 carbon atoms,
(c) a phosphine complex of divalent palladium shown by the following formula (c),
Pd[P(R 1 ) 2 (R 2 ) n ]X 2 (c)
wherein R 1 represents a group selected from a cyclopentyl group, a cyclohexyl group, and an isopropyl group, and R 2 represents a hydrocarbon group having 3 to 10 carbon atoms, X is an organic anion or a beta-diketonate anion, and n is 1 or 2, and
(d) an ionic boron compound.
7. The process of claim 6 , wherein (b) is tricyclopentyl phosphine or tricyclohexyl phosphine.
8. The process of claim 6 , wherein the phosphine complex of divalent palladium (c) is a complex of palladium and tricyclopentylphosphine or a complex of palladium and tricyclohexylphosphine.
9. The process of claim 6 , wherein the ionic boron compound (d) is a compound consisting of a carbenium cation and a tetrakis(pentafluorophenyl) borate anion or a tetrakis(perfluoroalkylphenyl) borate anion.
10. The process of claim 1 , wherein the polymerization is initiated with 20 to 80 wt % of the total amount of the monomer composition.
11. The process of claim 1 , wherein the polymerization is initiated with 30 to 75 wt % of the total amount of the monomer composition.
12. The process of claim 1 , wherein the polymerization is initiated with 20 to 70 wt % of the total amount of the monomer composition.
13. The process of claim 1 , wherein the cycloolefin addition polymer has a polystyrene-reduced number average number average molecular weight (Mn) of 20,000 to 200,000.
14. The process of claim 1 , wherein the cycloolefin addition polymer has a ratio Mw/Mn of 4.3 or less.
15. The process of claim 1 , wherein the cycloolefin addition polymer has a ratio Mw/Mn of 4.0 or less.
16. The process of claim 1 , wherein the cycloolefin addition polymer has a ratio Mw/Mn of 3.5 or less.
17. The process of claim 1 , wherein the cycloolefin addition polymer has a luminous transmission measured using a film with a thickness of 100 micrometers of 85% or more.
18. The process of claim 1 , wherein the cycloolefin addition polymer has a haze value normally of 2.0% or less.
19. The process of claim 1 , wherein the amount of the molecular weight controlling agent is 0.001 to 0.5 mol per one mol of the monomers used.
20. The process of claim 1 , wherein the monomer composition comprises at least two different monomers, wherein at least one monomer comprises at least 20 wt % of the monomer composition, and wherein a portion of each monomer that comprises at least 20 wt % of the monomer composition is used in the initiation of the polymerization and the remaining portion is added during the polymerization.
21. The process of claim 1 , wherein the monomer composition comprises at least two different monomers, wherein at least one monomer comprises at least 10 wt % of the monomer composition, and wherein a portion of each monomer that comprises at least 10 wt % of the monomer composition is used in the initiation of the polymerization and the remaining portion is added during the polymerization.
22. The process of claim 1 , wherein the monomer composition comprises at least two different monomers, wherein at least one monomer comprises at least 5 wt % of the monomer composition, and wherein a portion of each monomer that comprises at least 5 wt % of the monomer composition is used in the initiation of the polymerization and the remaining portion is added during the polymerization.
23. The process of claim 1 , wherein the monomer composition comprises at least two different monomers, wherein at least two monomers each comprise at least 20 wt % of the monomer composition, and wherein a portion of each monomer that comprises at least 20 wt % of the monomer composition is used in the initiation of the polymerization and the remaining portion is added during the polymerization.
24. A method of producing optical materials, electrical and electronic parts, medical application substrates, comprising manufacturing a cycloolefin addition polymer according to claim 1 and incorporating the cycloolefin addition polymer into an optical material, electrical part, electronic parts or medical application substrates.