High pressure low density polyethylene resins with improved optical properties produced through use of highly active chain transfer agents

Abstract

Disclosed is an ethylene-based polymer with a density from about 0.90 to about 0.94 in grams per cubic centimeter, with a molecular weight distribution (M w /M n ) from about 2 to about 30, a melt index (I 2 ) from about 0.1 to about 50 grams per 10 minutes, and further comprising sulfur from about 5 to about 4000 parts per million. The amount of sulfur is also determined based upon the total weight of the ethylene-based polymer. Also disclosed is process for making an ethylene-based polymer which includes the steps of splitting a process fluid for delivery into a tubular reactor; feeding an upstream process feed stream into a first reaction zone and at least one downstream process feed stream into at least one other reaction zone, where the process fluid has an average velocity of at least 10 meters per second; and initiating a free-radical polymerization reaction.

1 . An ethylene-based polymer with a density from about 0.90 to about 0.94 in grams per cubic centimeter, with a molecular weight distribution (M w /M n ) from about 2 to about 30, a melt index (I 2 ) from about 0.1 to about 50 grams per 10 minutes, and further comprising from about 5 to about 4000 parts per million by weight of sulfur as determined using a Total Sulfur Concentration method and based upon the total weight of the ethylene-based polymer. 
   
   
       2 . An ethylene-based polymer with long chain branching as characterized by a gpcBR value greater than 0.05 as determined by a gpcBR Branching Index and a GPC-LS Characterization value greater than 2.1 as determined by a GPC-LS Characterization method. 
   
   
       3 . The ethylene-based polymer of  claim 2 , where the GPC-LS Characterization value is from about 2.1 to about 10. 
   
   
       4 . An ethylene-based polymer with a zero-shear viscosity, η 0 , in Pascal-seconds at 190° C. as determined using a Zero Shear Viscosity method, an absolute weight average molecular weight value, M w, Abs , in g/mol, and a conventional weight average molecular weight value, M w, GPC , in g/mol, where the numerical values of η 0 , M w, Abs , and M w, GPC  correspond to the relationship:
   (3.6607*Log  M   w, Abs )−16.47<Log η 0 *( M   w, GPC   /M   w, Abs )<(3.6607*Log  M   w, Abs )−14.62,   
     and where the ethylene-based polymer further comprises sulfur. 
   
   
       5 . The ethylene-based polymer of  claim 4 , where the numerical values of η 0 , M w, Abs , and M w, GPC  correspond to the relationship:
   (3.6607*Log  M   w, Abs )−16.47<Log η 0 *( M   w, GPC   /M   w, Abs )<(3.6607*Log  M   w, Abs )−14.62   
     for log M w, Abs  values less than 5.23, and where the numerical values correspond to the relationship:
   2.675<Log η 0 *( M   w, GPC   /M   w, Abs )<(3.6607*Log  M   w, Abs )−14.62 
 
     for log M w, Abs  values equal to or greater than 5.23. 
   
   
       6 . The ethylene-based polymer of  claim 4 , where the ethylene-based polymer has long chain branching as characterized by a gpcBR value greater than 0.05 as determined by a gpcBR Branching Index by 3D-GPC method. 
   
   
       7 . An ethylene-based polymer, wherein a film comprising the ethylene-based polymer has a surface haze, S, an internal haze, I, both in units of % haze and both determined using a Surface and Internal Haze method, and a melt index (I 2 ) in grams per 10 minutes, where the numerical values of S, I, and I 2  correspond to the following relationship:
     S/I ≦(−0.057 *I   2 )+1.98.   
   
   
       8 . The ethylene-based polymer of  claim 7 , where the numerical values of S, I, and I 2  correspond to the following relationship:
     S/I ≦(−0.057 *I   2 )+1.85.   
   
   
       9 . The ethylene-based polymer of  claim 7 , wherein the ethylene based polymer has long chain branching as characterized by a gpcBR value greater than 0.05 to as high as 10 as determined by a gpcBR Branching Index by 3D-GPC method. 
   
   
       10 . A process, comprising
 a. Splitting a process fluid, a portion of which comprises ethylene, for delivery into a tubular reactor, into an upstream process feed stream and at least one downstream process feed stream;   b. Feeding the upstream process feed stream into a first reaction zone and the at least one downstream process feed stream into an at least one other reaction zone to recombine the process fluid, where inside the tubular reactor in at least one of several reaction zones the process fluid has an average velocity of at least 10 meters per second; and   c. Initiating a free-radical polymerization reaction inside the tubular reactor so as to produce an ethylene-based polymer adduct and heat,   
     where the tubular reactor comprises several reaction zones including a first reaction zone and at least one other reaction zone, and where the upstream process feed stream further comprises at least one chain transfer agent with a chain transfer constant, Cs, greater than 1. 
   
   
       11 . A process, comprising
 a. Feeding a process fluid via an upstream process feed stream into a first reaction zone of a tubular reactor, where the process fluid has an average velocity in the tubular reactor in at least one of several reaction zones of at least 10 meters per second; and   b. Initiating a free-radical polymerization reaction inside the tubular reactor so as to produce an ethylene-based polymer adduct and heat,   
     where the tubular reactor comprises several reaction zones including a first reaction zone and at least one other reaction zone, and where a portion of the process fluid comprises ethylene and another portion comprises at least one chain transfer agent with a chain transfer constant, Cs, greater than 1. 
   
   
       12 . The process of  claim 10  or  11 , where the process fluid further comprises at least one chain transfer agent with a Cs less than 1. 
   
   
       13 . The process of  claim 10  or  11 , where the upstream process feed stream has a CTA molar flow ratio from about 0.01 to about 100. 
   
   
       14 . The process of  claim 10  or  11 , where the at least one chain transfer agent with a Cs greater than 1 has a concentration in the upstream process feed stream from about 1 molar ppm to about 600 molar ppm. 
   
   
       15 . The process of  claim 10  or  11 , where the difference in the ethylene conversion percent at steady state conditions is at least 0.3 percent higher than the ethylene conversion percent in an analogous process with comparable steady-state conditions lacking the at least one chain transfer agent with a Cs greater than 1.