Process for producing cycloolefin random copolymer

Abstract

A process for producing a cycloolefin random copolymer, which comprises (1) copolymerizing (a) ethylene or both ethylene and an alpha-olefin having at least 3 carbon atoms with (b) a cycloolefin such as octahydronaphthalenes and bicyclo[2,2,1]hept-2-ene in the presence of (c) a catalyst formed from a soluble vanadium compound and an organoaluminum compound at least one of which has halogen, in (d) a liquid phase composed of a hydrocarbon medium to form a solution of a cycloolefin random copolymer, and (2) contacting the resulting copolymer solution with (e) an adsorbent containing a metal cation.

We claim: 
     
       1. A process for producing a cycloolefin random copolymer, which comprises (1) copolymerizing (a) ethylene or both ethylene and an alpha-olefin having at least 3 carbon atoms with (b) at least one cycloolefin selected from the group consisting of unsaturated monomers of the following formula (I) ##STR47##  wherein n is 0 or a positive integer, and each of R 1  to R 10  represents halogen atom or a hydrocarbon group, and unsaturated monomers of the following formula (II) ##STR48## wherein m is 0 or a positive integer, and R 1  and R 10  are as defined above, and .[.1.]. .Iadd.l .Iaddend.is an integer of at least 3, in the presence of (c) a catalyst formed from a soluble vanadium compound and an organoaluminum compound at least one of which has halogen, in (d) a liquid phase composed of a hydrocarbon medium to form a solution of cycloolefin random copolymer containing a halogenated by-product of the cycloolefin, and   (2) .Iadd.subjecting the solution from step (d) to deashing treatment to remove catalyst residues remaining in the cycloolefin random copolymer, and   (3) .Iaddend.contacting the resulting copolymer solution .Iadd.from step (2) .Iaddend.with (e) .[.an.]. .Iadd.a zeolite .Iaddend.adsorbent containing a metal cation to remove the halogenated by-product from said solution. .[.   
     
     
       2.  The process of claim 1 in which after step (1) but before step (2), the random copolymer solution formed in step (1) is subjected to a deashing treatment..]. 
     
     
       3. The process of claim 1 in which the .Iadd.zeolite .Iaddend.adsorbent containing a metal cation is an adsorbent containing at least one cation selected from alkali metal cations and alkaline earth metal cations. 
     
     
       4. .[.The.]. .Iadd.A .Iaddend.process .[.of claim 1 in which the adsorbent.]. .Iadd.for producing a cycloolefin random copolymer, which comprises (1) copolymerizing (a) ethylene or both ethylene and an alpha-olefin having at least 3 carbon atoms with (b) at least one cycloolefin selected from the group consisting of unsaturated monomers of the following formula (I) ##STR49##  wherein n is 0 or a positive integer, and each of R 1  to R 10  represents halogen atom or a hydrocarbon group, and unsaturated monomers of the following formula (II) ##STR50##  wherein m is 0 or a positive integer, and R 1  to R 10  are as defined above, and l is an integer of at least 3, in the presence of (c) a catalyst formed from a soluble vanadium compound and an organoaluminum compound at least one of which has halogen, in (d) a liquid phase composed of a hydrocarbon medium to form a solution of cycloolefin random copolymer containing a halogenated by-product of the cycloolefin and   (2) contacting the resulting copolymer solution with (e) an adsorbent which .Iaddend.contains at least 5% by weight, in a condition free from water of crystallization, of an alkali metal cation .Iadd.to remove the halogenated by-product from said solution.Iaddend..   
     
     
       5. The process of claim 1 in which the .Iadd.zeolite .Iaddend.adsorbent contains many pores and has a maximum pore diameter of at least 0.5 nm. 
     
     
       6. The process of claim 1 in which the .Iadd.zeolite .Iaddend.adsorbent has a specific surface area of 100 to 1,000 m 2  /g. 
     
     
       7. The process of claim 1 which produces a random copolymer having a halogen content of not more than 200 ppm. 
     
     
       8. .[.The.]. .Iadd.A .Iaddend.process .[.of claim 1 in which the.]. .Iadd.for producing a cycloolefin random copolymer, which comprises (1) copolymerizing (a) ethylene or both ethylene and an alpha-olefin having at least 3 carbon atoms with (b) at least one cycloolefin selected from the group consisting of unsaturated monomers of the following formula (I) ##STR51##  wherein n is 0 or a positive integer, and each of R 1  to R 10  represents halogen atom or a hydrocarbon group, and unsaturated monomers of the following formula (II) ##STR52##  wherein m is 0 or a positive integer, and R 1  to R 10  are as defined above, and l is an integer of at least 3, in the presence of (c) a catalyst formed from a soluble vanadium compound and an organoaluminum compound at least one of which has halogen, in (d) a liquid phase composed of a hydrocarbon medium to form a solution of cycloolefin random copolymer containing a halogenated by-product of the cycloolefin and   (2) contacting the resulting copolymer solution with (e) an .Iaddend.adsorbent .Iadd.which .Iaddend.is a zeolite containing alkali metal cation .Iadd.to remove the halogenated by-product from said solution.Iaddend..