Modified polyethylene resins and process for making the same
The present invention is a process to modify a starting polyethylene resin composition. In the process, a starting polyethylene resin composition is extruded with at least one primary antioxidant and a free-radical generator to make a modified polyethylene resin composition.
1 . A process to make a modified polyethylene formulation, which process comprises the steps of:
a) providing a starting polyethylene resin composition (SPEC) containing one or more polyethylene (co) polymer(s), wherein the SPEC has a melt index (12) of from 0.5 dg/min to 5 dg/min and contains
i) from 0 to no more than 1.5 weight percent (based on the total weight of SPEC) of a high molecular weight Cumulative Detector Fraction-Light Scattering (CDF LS ) fraction with a molecular weight (MW) of greater than 5,000,000 grams per mole (g/mol) and
ii) from 0 to no more than 0.3 weight percent (based on the total weight of SPEC) of an ultra-high molecular weight CDF LS fraction with a molecular weight (MW) of greater than 10,000,000 g/mol;
b) extruding and mixing together in a melt
i) the SPEC,
ii) a total quantity of one or more primary antioxidants that is effective to provide a concentration of least 2001 parts of the one or more primary antioxidants per 1 million parts by weight of the modified polyethylene formulation (“ppmw”), and
iii) from 11 to 250 parts of free-radical generator per 1 million parts of the SPEC, by weight (“ppmw”), and
iv) optionally, a total quantity of one or more secondary antioxidants that is effective to provide a concentration of at least 395 ppmw of the one or more secondary antioxidants in the modified polyolefin formulation,
wherein the one or more primary antioxidants and the optional one or more secondary antioxidants are collectively referred to as the “primary and any secondary antioxidant(s)”;
wherein the melt is maintained at a temperature and for a time sufficient to substantially decompose the free-radical generator without substantially degrading the polyethylene resin or the one or more primary antioxidants, such that a modified polyethylene formulation is produced which has:
(i) a modified polyethylene resin component (MPEC) having
1. At least 2 weight percent (based on the total weight of MPEC) of a high molecular weight CDF LS fraction with a molecular weight (MW) of greater than 5,000,000 g/mol and
2. At least 0.3 weight percent (based on the total weight of MPEC) of an ultra-high molecular weight CDF LS fraction with a molecular weight (MW) of greater than 10,000,000 g/mol; and
(ii) a total of at least 2,001 parts of the one or more primary antioxidant per 1 million parts of the MPEC by weight (ppmw); and
(iii) less than 10 weight percent of polyethylene gels (based on the total weight of MPEC), and
(iv) optionally, a total of at least 395 ppmw of the one or more secondary antioxidants.
2 . The process of claim 1 characterized by any one of limitations (i) to (vii): (i) wherein at least some of the from 11 to 250 ppmw of the free-radical generator is added before the adding of the primary and any secondary antioxidant(s); (ii) wherein at least some of the from 11 to 250 ppmw of the free-radical generator is added simultaneously with the adding of the primary and any secondary antioxidant(s); (iii) wherein at least some of the from 11 to 250 ppmw of the free-radical generator is added after the adding of the primary and any secondary antioxidant(s); (iv) a combination of (i) and (ii) but not (iii); (v) a combination of (i) and (iii) but not (ii); (vi) a combination of (ii) and (iii), but not (i); and (vii) a combination of each of (i), (ii), and (iii).
3 . The process of claim 1 wherein all of the from 11 to 250 ppmw of the free-radical generator is added after or simultaneously with the adding of the primary and any secondary antioxidant(s).
4 . The process of claim 1 wherein all of the from 11 to 250 ppmw of the free-radical generator is added simultaneously with the adding of the primary and any secondary antioxidant(s).
5 . The process of claim 1 wherein the free-radical generator is an organic peroxide having a molecular weight of 200 to 1000 g/mol and the free-radical generator is added in a quantity of 20 to 250 parts free radical generator per one million parts of SPEC, by weight.
6 . The process in claim 1 characterized by any one of limitations (i) to (iii): (i) wherein and the one or more secondary antioxidants is/are used and the total quantity of the one or more secondary antioxidants that is added is effective to provide from 400 to 2000 ppmw of the one or more secondary antioxidants in the modified polyethylene formulation (based on the weight of MPEC); (ii) wherein the MPEC has a total of from 2001 to 4500 ppmw of the one or more primary antioxidants (based on the weight of MPEC); and (iii) both (i) and (ii).
7 . The process in claim 1 wherein melt strength of the modified polyethylene formulation is at least 2 cN higher than the melt strength of the starting polyethylene resin component.
8 . The process in claim 1 wherein melt-index (I 2 ) of the modified polyethylene formulation is from 0.05 dg/min to 2.0 dg/min.
9 . The process of claim 1 wherein the content of the high molecular weight CDF LS fraction with a molecular weight (MW) of greater than 5,000,000 g/mol in the modified polyethylene formulation is between 2.4 weight percent and 30 weight percent, based on the total weight of MPEC.
10 . The process of claim 1 wherein the content of the ultra-high molecular weight CDF LS fraction with a molecular weight (MW) of greater than 10,000,000 g/mol in the modified polyethylene formulation is between 0.4 weight percent and 15 weight percent, based on the total weight of MPEC.
11 . The process of claim 1 wherein the modified polyethylene formulation contains less than 3 weight percent gels based on the weight of MPEC.
12 . The process of claim 1 wherein the starting polyethylene resin component contains less than 0.20 vinyl groups per 1000 carbon atoms.
13 . The process of claim 1 wherein the process is carried out in an extruder-pelletizer.
14 . The process of claim 1 wherein the process is carried out in multiple extruders, by extruding the starting polyethylene resin component on a first extruder with part of the free-radical generator and/or the primary and any secondary antioxidant(s) and then extruding the resulting composition again on a second extruder with the remaining free-radical generator and/or the primary and any secondary antioxidant(s); wherein
either: (a) the first and second extruders are in communication with a conveying operation all located in a same manufacturing plant and the composition resulting from the first extruder is fed to the second extruder via the conveying operation; or (b) the first and second extruders are located in different manufacturing plants and the composition resulting from the first extruder is transported by vehicle therebetween.
15 . A modified polyethylene formulation made by the process of claim 1 .