Procatalyst Particles And Polymerization Process For Impact Copolymers

Abstract

Particles of a procatalyst composition having a particle size D50 from 19 microns to 30 microns. A polymerization process comprising halogenating, in the presence of a substituted phenylene aromatic diester, particles of a MagTi procatalyst precursor to form particles of a procatalyst composition having a particle size D50 from 19 microns to 30 microns; first contacting a propylene and optionally one or more first comonomers with a catalyst composition comprising the particles of the procatalyst composition in a first polymerization reactor to form an active propylene-based polymer; and second contacting the active propylene-based polymer with at least one second comonomer in a second polymerization reactor to form a propylene impact copolymer.

1 . (canceled) 
     
     
         2 . A polymerization process comprising:
 halogenating, in the presence of a substituted 1,2-, 1,3- or 1,4-phenylene aromatic diester, particles of a MagTi procatalyst precursor having a particle size D50 from 26 microns to 30 microns to form particles of a procatalyst composition having a particle size D50 from 26 microns to 30 microns;   wherein halogenating is carried out with a halogenating agent selected from a titanium halide having the formula Ti(OR e ) f X h :
 wherein R e  is an aliphatic or aromatic hydrocarbon radical having 1 to 14 carbon atoms or COW, wherein R′ is an aliphatic or aromatic hydrocarbon radical having 1 to 14 carbon atoms; each OR e  group is the same or different; X is independently chlorine, bromine or iodine, f is an integer from 0 to 3; h is an integer from 1 to 4; and f+h is 4; 
 first contacting, under first polymerization conditions, propylene monomer and optionally one or more first comonomers with a catalyst composition comprising the particles of the procatalyst composition in a first polymerization reactor to form an active propylene-based polymer; and 
 second contacting, under second polymerization conditions, the active propylene-based polymer with at least one second comonomer in a second polymerization reactor to form a propylene impact copolymer comprising a heterophasic copolymer comprising a discontinuous or elastomeric phase comprising propylene-based polymer and one or more comonomers. 
   
     
     
         3 . The process of  claim 2  wherein the at least one second comonomer is an olefin monomer. 
     
     
         4 . The process of  claim 2  comprising halogenating the particles of the MagTi procatalyst precursor in the presence of 3-methyl-5-t-butyl-1,2-phenylene dibenzoate. 
     
     
         5 . The process of  claim 2  comprising forming propylene impact copolymer having an Fc from 10 wt % to 55 wt % or from 25 wt % to 55 wt % or from 30 wt % to 55 wt %, wherein Fc is the weight percent of the discontinuous phase present in the heterophasic copolymer based on the total weight of the propylene impact copolymer. 
     
     
         6 . The process of  claim 2  comprising forming propylene impact copolymer having an Ec value from 10 wt % to 90 wt % or 30 wt % to 80 wt % or 50 wt % to 70 wt %, wherein Ec is the weight percent of ethylene present in the discontinuous or elastomeric phase of the propylene impact copolymer based on the total weight of the discontinuous phase. 
     
     
         7 . The process of  claim 2  comprising forming propylene impact copolymer having:
 (i) an Fc value from:
 (a) 5 wt %, or 10 wt %, or 20 wt %, or 25 wt %, or 30 wt %; to 
 (b) 35 wt %, or 40 wt %, or 45 wt %, or 50 wt %, or 55 wt %; and 
 
 (ii) an Ec value from:
 (c) 10 wt %, or 20 wt %, or 30 wt %, or 40 wt %, or 50 wt %; to 
 (d) 60 wt %, or 70 wt %, or 80 wt %, or 90 wt %. 
 
 
     
     
         8 . The process of  claim 2  comprising forming particles of propylene impact copolymer having a settled bulk density greater than 17 lbs/ft 3 . 
     
     
         9 . The process of  claim 2  wherein the halogenating agent is titanium tetrabromide, or titanium tetrachloride or titanium trichloride. 
     
     
         10 . The process of  claim 2  wherein the substituted 1,2-phenylene aromatic diester has the structure (I), 
       
         
           
           
               
               
           
         
         wherein R 1 -R 14  are the same or different, each of R 1 -R 14  may be independently selected from a hydrogen, substituted hydrocarbyl group having 1 to 20 carbon atoms, an unsubstituted hydrocarbyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, a heteroatom, and combinations thereof, provided that at least one of R 1 -R 14  is not hydrogen. 
       
     
     
         11 . Particles of a procatalyst composition formed from a MagTi procatalyst precursor and a substituted phenylene aromatic diester, wherein the particles of the procatalyst composition have a particle size D50 from 26 to 30 microns. 
     
     
         12 . A polymerization process comprising:
 halogenating, in the presence of a substituted 1,2-, 1,3- or 1,4-phenylene aromatic diester, particles of a MagTi procatalyst precursor having a particle size D50 from 26 microns to 30 microns to form particles of a procatalyst composition having a particle size D50 from 26 microns to 30 microns;   first contacting, under first polymerization conditions, propylene monomer and optionally one or more first comonomers with a catalyst composition comprising the particles of the procatalyst composition in a first polymerization reactor, comprising forming an active propylene-based polymer; and   second contacting, under second polymerization conditions, the active propylene-based polymer with at least one second comonomer in a second polymerization reactor to form a propylene impact copolymer.   
     
     
         13 . The process of  claim 12  wherein the at least one second comonomer is an olefin monomer. 
     
     
         14 . The process of  claim 12  comprising halogenating the particles of the MagTi procatalyst precursor in the presence of 3-methyl-5-t-butyl-1,2-phenylene dibenzoate. 
     
     
         15 . The process of  claim 12  comprising forming propylene impact copolymer having an Fc from 10 wt % to 55 wt % or from 25 wt % to 55 wt % or from 30 wt % to 55 wt %, wherein Fc is the weight percent of the discontinuous phase present in the heterophasic copolymer based on the total weight of the propylene impact copolymer. 
     
     
         16 . The process of  claim 12  comprising forming propylene impact copolymer having an Ec from 10 wt % to 90 wt % or 30 wt % to 80 wt % or 50 wt % to 70 wt %, wherein Ec is the weight percent of ethylene present in the discontinuous or elastomeric phase of the propylene impact copolymer based on the total weight of the discontinuous phase. 
     
     
         17 . The process of  claim 12  comprising forming propylene impact copolymer having:
 (i) an Fc value from:
 (a) 5 wt %, or 10 wt %, or 20 wt %, or 25 wt %, or 30 wt %; to 
 (b) 35 wt %, or 40 wt %, or 45 wt %, or 50 wt %, or 55 wt %; and 
 
 (ii) an Ec value from:
 (c) 10 wt %, or 20 wt %, or 30 wt %, or 40 wt %, or 50 wt %; to 
 (d) 60 wt %, or 70 wt %, or 80 wt %, or 90 wt %. 
 
 
     
     
         18 . The process of  claim 12  comprising forming particles of propylene impact copolymer having a settled bulk density greater than 17 lbs/ft 3 . 
     
     
         19 . The process of  claim 12  wherein the substituted 1,2-phenylene aromatic diester has the structure (I), 
       
         
           
           
               
               
           
         
         wherein R 1 -R 14  are the same or different, each of R 1 -R 14  may be independently selected from a hydrogen, substituted hydrocarbyl group having 1 to 20 carbon atoms, an unsubstituted hydrocarbyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, a heteroatom, and combinations thereof, provided that at least one of R 1 -R 14  is not hydrogen.