Norbornene cross-linked polymer and method for producing same

Abstract

The present invention relates to a norbornene-based crosslinked polymer containing at least one member selected from the group consisting of dicyclopentadiene-based monomer units, tetracyclododecene-based monomer units, and tricyclopentadiene-based monomer units in an amount of 50% by mass or more, wherein the norbornene-based crosslinked polymer has a glass transition temperature of 240° C. or higher. Further, the present invention relates to a method for producing a norbornene-based crosslinked polymer as defined above, including step (1): heating a blend containing at least one member of the above monomer components, and a metathesis polymerization catalyst to a temperature lower than a deactivation temperature of the metathesis polymerization catalyst to carry out a primary curing; and step (2): heating a cured product obtained in the step (1) to a temperature equal to or higher than the deactivation temperature of the above metathesis polymerization catalyst to carry out a secondary curing.

1 . A norbornene-based crosslinked polymer comprising at least one member selected from the group consisting of dicyclopentadiene-based monomer units, tetracyclododecene-based monomer units, and tricyclopentadiene-based monomer units in an amount of 50% by mass or more, wherein the norbornene-based crosslinked polymer has a glass transition temperature of 240° C. or higher. 
     
     
         2 . The norbornene-based crosslinked polymer according to  claim 1 , wherein the tricyclopentadiene-based monomer units are contained in an amount of 50% by mass or more. 
     
     
         3 . The norbornene-based crosslinked polymer according to  claim 2 , wherein a one-minute withstand voltage at a measurement temperature of 23° C. is 60 kV/mm or more. 
     
     
         4 . A method for producing a norbornene-based crosslinked polymer as defined in  claim 1 , comprising
 step (1) heating a blend comprising at least one member selected from the group consisting of dicyclopentadiene-based monomers, tetracyclododecene-based monomers, and tricyclopentadiene-based monomers, and a metathesis polymerization catalyst to a temperature lower than a deactivation temperature of said metathesis polymerization catalyst to carry out a primary curing; and   step (2) heating a cured product obtained in the step (1) to a temperature equal to or higher than the deactivation temperature of said metathesis polymerization catalyst to carry out a secondary curing.   
     
     
         5 . The method according to  claim 4 , wherein the tricyclopentadiene-based monomers are contained in an amount of 50% by mass or more of the entire monomers contained in said blend. 
     
     
         6 . The method according to  claim 4 , wherein said blend in said step (1) is heated to a temperature of 25° C. or higher and lower than 220° C. to carry out a primary curing. 
     
     
         7 . The method according to  claim 4 , wherein said cured product in said step (2) is heated to a temperature of 250° C. or higher and lower than 350° C. to carry out a secondary curing. 
     
     
         8 . A method for producing a norbornene-based crosslinked polymer as defined in  claim 2 , comprising
 step (1) heating a blend comprising at least one member selected from the group consisting of dicyclopentadiene-based monomers, tetracyclododecene-based monomers, and tricyclopentadiene-based monomers, and a metathesis polymerization catalyst to a temperature lower than a deactivation temperature of said metathesis polymerization catalyst to carry out a primary curing; and   step (2) heating a cured product obtained in the step (1) to a temperature equal to or higher than the deactivation temperature of said metathesis polymerization catalyst to carry out a secondary curing.   
     
     
         9 . A method for producing a norbornene-based crosslinked polymer as defined in  claim 3 , comprising
 step (1) heating a blend comprising at least one member selected from the group consisting of dicyclopentadiene-based monomers, tetracyclododecene-based monomers, and tricyclopentadiene-based monomers, and a metathesis polymerization catalyst to a temperature lower than a deactivation temperature of said metathesis polymerization catalyst to carry out a primary curing; and   step (2) heating a cured product obtained in the step (1) to a temperature equal to or higher than the deactivation temperature of said metathesis polymerization catalyst to carry out a secondary curing.   
     
     
         10 . A method for producing a norbornene-based crosslinked polymer as defined in  claim 3 , comprising
 step (1) heating a blend comprising at least one member selected from the group consisting of dicyclopentadiene-based monomers, tetracyclododecene-based monomers, and tricyclopentadiene-based monomers, and a metathesis polymerization catalyst to a temperature lower than a deactivation temperature of said metathesis polymerization catalyst to carry out a primary curing; and   step (2) heating a cured product obtained in the step (1) to a temperature equal to or higher than the deactivation temperature of said metathesis polymerization catalyst to carry out a secondary curing.   
     
     
         11 . The norbornene-based crosslinked polymer according to  claim 10 , wherein a one-minute withstand voltage at a measurement temperature of 23° C. is 60 kV/mm or more. 
     
     
         12 . The method according to  claim 5 , wherein said blend in said step (1) is heated to a temperature of 25° C. or higher and lower than 220° C. to carry out a primary curing. 
     
     
         13 . The method according to  claim 5 , wherein said cured product in said step (2) is heated to a temperature of 250° C. or higher and lower than 350° C. to carry out a secondary curing. 
     
     
         14 . The method according to  claim 6 , wherein said cured product in said step (2) is heated to a temperature of 250° C. or higher and lower than 350° C. to carry out a secondary curing.