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 method of using a norbornene-based crosslinked polymer, comprising:
 forming the norbornene-based crosslinked polymer, then   forming an insulation material comprising the norbornene-based crosslinked polymer; and then   using said insulation material in an application selected from the group consisting of automobile application, construction and industrial machinery application, recreational application, medical application, industrial application, electric insulation application, and house facility application;   wherein the norbornene-based crosslinked polymer has a glass transition temperature of 240° C. or higher, and   wherein the norbornene-based crosslinked polymer is obtained by
 step (1) heating a blend comprising tricyclopentadiene-based monomers in an amount of 50% or more of the entire monomers, and a metathesis polymerization catalyst to a temperature lower than a temperature of 230° C. 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 temperature of 230° C. to carry out a secondary curing. 
   
     
     
         2 . The method according to  claim 1 , wherein the blend comprises monomers having a polar group. 
     
     
         3 . The method according to  claim 1 , wherein said metathesis polymerization catalyst is general formula (5): 
       
         
           
           
               
               
           
         
         where 
         Z indicates an oxygen atom, sulfur atom, selenium atom, NR 12 , PR 12 , or AsR 12 , where R 12  indicates a hydrogen atom; halogen atom; or one selected from the group consisting of C 1  to C 20  organic groups which may contain at least one atom selected from the group consisting of halogen atom, oxygen atom, nitrogen atom, sulfur atom, phosphorus atom, and silicon atom; 
         R 1  and R 2  respectively independently indicate a hydrogen atom; halogen atom; or one selected from the group consisting of C 1  to C 20  organic groups which may contain at least one atom selected from the group consisting of halogen atom, oxygen atom, nitrogen atom, sulfur atom, phosphorus atom and silicon atom, where R 1  and R 2  may be substituted and, further, may bond together to form a ring; 
         X 1  indicates an anionic ligand; 
         L 1  indicates a hetero atom-containing carbene compound or a neutral electron donor compound other than the hetero atom-containing carbene compound; 
         where R 1 , R 2 , X 1 , and L 1  may respectively independently and/or in any combination bond together to form a multi-dentate chelate ligand; 
         R 7  and R 8  respectively independently indicate a hydrogen atom, or one selected from the group consisting of C 1  to C 20  alkyl groups, C 2  to C 20  alkenyl groups, and C 6  to C 20  heteroaryl groups, where R 7  and R 8  may be substituted and, further, may bond together to form a ring; and 
         R 9 , R 10 , and R 11  respectively independently indicate a hydrogen atom; halogen atom; or one selected from the group consisting of C 1  to C 20  organic groups which may contain at least one atom selected from the group consisting of halogen atom, oxygen atom, nitrogen atom, sulfur atom, phosphorus atom, and silicon atom, where R 9 , R 10  and R 11  may be substituted and may bond together to form a ring. 
       
     
     
         4 . The method according to  claim 1 , wherein said metathesis polymerization catalyst is general formula (6): 
       
         
           
           
               
               
           
         
         where 
         m is 0 or 1; 
         Q is an oxygen atom, nitrogen atom, sulfur atom, methylene group, ethylene group, or carbonyl group; 
         - - - - is a single bond or double bond; 
         R 1  indicates a hydrogen atom; halogen atom; or one selected from the group consisting of C 1  to C 20  organic groups which may contain at least one atom selected from the group consisting of halogen atom, oxygen atom, nitrogen atom, sulfur atom, phosphorus atom and silicon atom, where R 1  may be substituted; 
         X 1  and X 2  respectively independently indicate an anionic ligand; 
         L 1  indicates a hetero atom-containing carbene compound or a neutral electron donor compound other than the hetero atom-containing carbene compound; 
         where R 1 , X 1 , X 2 , and L 1  may respectively independently and/or in any combination bond together to form a multi-dentate chelate ligand; and 
         R 13  to R 21  are each a hydrogen atom; halogen atom; or one selected from the group consisting of C 1  to C 20  organic groups which may contain at least one atom selected from the group consisting of halogen atom, oxygen atom, nitrogen atom, sulfur atom, phosphorus atom, and silicon atom, where R 13  to R 21  may be substituted, and further, may bond together to form a ring. 
       
     
     
         5 . The method according to  claim 1 , wherein the norbornene-based crosslinked polymer has a one-minute withstand voltage at a measurement temperature of 23° C. of 60 kV/mm or more. 
     
     
         6 . The method according to  claim 1 , wherein the blend further comprises a filler. 
     
     
         7 . The method according to  claim 1 , wherein the blend further comprises a radical generator. 
     
     
         8 . A method for producing a power semiconductor, comprising conducting encapsulation with the insulation material according to  claim 1 . 
     
     
         9 . The method according to  claim 1 , wherein said insulation material is used in the application of producing power semiconductors.