Pipe made from metathesis polymerized olefins

Abstract

Thermosetting resin pipes and pipe fittings are provided which are prepared by polymerizing a cyclic olefin monomer in the presence of a ruthenium or osmium metathesis polymerization catalyst. These articles may be prepared by various methods, such as centrifugal casting. Reinforced articles may also be prepared by filament winding.

We claim:  
     
         1 . A polyolefin article comprising: 
 a polyolefin prepared by polymerizing a cyclic olefin monomer in the presence of a metathesis polymerization catalyst which comprises a ruthenium complex catalyst or an osmium complex catalyst, wherein the article is a pipe or a pipe fitting.    
     
     
         2 . A method of making a polyolefin article, the method comprising the steps of: 
 a) adding a Ru of Os metathesis catalyst to a cyclic olefin monomer to form a reaction mixture;    b) forming the reaction mixture into a shape for the article, wherein the article is a pipe or a pipe fitting; and    c) allowing the formed reaction mixture to polymerize under polymerization conditions.    
     
     
         3 . The method of  claim 2  wherein the cyclic olefin monomer comprises a norbornene-type monomer.  
     
     
         4 . The method of  claim 2  wherein the cyclic olefin monomer comprises dicyclopentadiene.  
     
     
         5 . The method of  claim 2  wherein the reaction mixture is formed into the shape by feeding the reaction mixture into a spinning mold prior to allowing the reaction mixture to polymerize.  
     
     
         6 . The method of  claim 2  further comprising the step of incorporating a reinforcing material with the reaction mixture prior to allowing the reaction mixture to polymerize.  
     
     
         7 . The method of  claim 6  wherein the reinforcing material comprises fiberglass.  
     
     
         8 . The method of  claim 2  wherein the polymerization is carried out in ambient air.  
     
     
         9 . The method of  claim 2  wherein the polymerization is carried out at about ambient pressure.  
     
     
         10 . A centrifugally cast plastic article formed by a process comprising the steps of: 
 a) admixing a Ru or Os metathesis polymerization catalyst with a cyclic olefin monomer to form a reaction mixture;    b) feeding the reaction mixture into a spinning mold; and    c) allowing the reaction mixture to polymerize.    
     
     
         11 . The article of  claim 10  wherein the cyclic olefin monomer comprises a norbornene-type monomer.  
     
     
         12 . The article of  claim 10  wherein the cyclic olefin monomer comprises dicyclopentadiene.  
     
     
         13 . The article of  claim 10  wherein the article is a pipe or a pipe fitting.  
     
     
         14 . The article of  claim 10  wherein the article includes a reinforcing material embedded therein.  
     
     
         15 . The article of  claim 14  wherein the reinforcing material comprises fiberglass.  
     
     
         16 . A method of manufacturing polyolefin pipe or fittings by filament winding, the method comprising the steps of: 
 a) admixing a Ru or Os metathesis catalyst with a cyclic olefin monomer to form a reaction mixture;    b) coating at least a portion of a reinforcing material with the reaction mixture;    c) winding the coated reinforcing material around a mandrel; and    d) allowing the olefin monomer to polymerize while the coated reinforcing material is wound around the mandrel to form a polyolefin pipe or a pipe fitting.    
     
     
         17 . The method of  claim 16  wherein the method is carried out in ambient air.  
     
     
         18 . A filament wound polyolefin pipe or fitting comprising a polymerized olefin monomer and a reinforcing material, the pipe being formed by: 
 a) adding a Ru or Os metathesis catalyst to a cyclic olefin monomer to form a reaction mixture;    b) coating at least a portion of the reinforcing material with the reaction mixture;    c) winding the coated reinforcing material around a mandrel; and    d) allowing the olefin monomar to polymerize while the coated reinforcing material is wound around the mandrel to form a polyolefin pipe or fitting.    
     
     
         19 . The filament wound polyolefin pipe or fitting of  claim 18  wherein the olefin monomer comprises dicyclopentadiene.  
     
     
         20 . The filament wound polyolefin pipe or fitting of  claim 18  wherein the catalyst is of formula:  
       
         
           
           
               
               
           
         
       
       where: 
 M is Os or Ru;  
 R and R 1  are independently selected from hydrogen, or a substituent group selected from the group consisting of C 2 -C 20  alkenyl, C 2 -C 20  alkynyl, C 1 -C 20  alkyl, aryl, C 1 -C 20  carboxylate, C 1 -C 20  alkoxy, C 2 -C 20  alkenyloxy, C 2 -C 20  alkynyloxy, aryloxy, C 2 -C 20  alkoxycarbonyl, C 1 -C 20  alkylthio, C 1 -C 20  alkylsulfonyl and C 1 -C 20  alkylsufinyl, each substituent group optionally substituted with one or more groups selected from C 1 -C 5  alkyl, halide, C 1 -C 5  alkoxy, or a phenyl group optionally substituted with halide, C 1 -C 5  alkyl, or C 1 -C 5  alkoxy;  
 X and X 1  are independently selected from hydrogen or an anionic ligand; and  
 L and L 1  are any neutral electron donor.  
 
     
     
         21 . A method of manufacturing a polyolefin pipe by pultrusion, the method comprising the steps of: 
 a) admixing a Ru or Os metathesis catalyst with a cyclic olefin monomer to form a reaction mixture;    b) pulling a reinforcing material into a die where the reinforcing material is formed into a pipe profile;    c) before or after step b), at least partially coating the reinforcing material with the reaction mixture; and    d) curing the reaction mixture to form the polyolefin pipe.    
     
     
         22 . A pultruded polyolefin pipe comprising a polymerized olefin monomer and a reinforcing material, the pipe being formed by: 
 a) admixing a Ru or Os metathesis catalyst with a cyclic olefin monomer to form a reaction mixture;    b) pulling a reinforcing material into a die where the reinforcement is formed into a pipe profile;    c) before or after step b), at least partially coating the reinforcing material with the reaction mixture; and    d) curing the reaction mixture to form the pipe.