Modified Polyethylene Compositions with Enhanced Melt Strength

Abstract

The present invention relates to a branched modifier and a composition comprising more than 25 wt % (based on the weight of the composition) of one or more linear ethylene polymers having a g′ vis of 0.97 or more and an Mw of 20,000 g/mol or more and at least 0.1 wt % of a branched modifier where the modifier has a) a g′ vis of 0.70 or less; b) an Mw of 100,000 g/mol or more; c) an Mw/Mn of 4.0 or more; d) a shear thinning ratio of 110 or more, e) a melt strength of 10 cN or more; f) a complex viscosity at 0.1 rad/sec at 190° C. of at least 130,000 Pa·s; and g) a phase angle of Z° or less where Z=138.3 G* (−0.142) , where G* is the complex modulus reported in Pascals measured at 190° C. and the phase angle units are reported in degrees, wherein the G* is from 1,000 to 1,000,000 Pa.

1 .- 9 . (canceled) 
     
     
         10 . A blend comprising:
 1) branched polyethylene modifier comprising at least 50 mol % ethylene, one or more C 4  to C 40  comonomers, and a polyene having at least two polymerizable bonds, wherein said branched polyethylene modifier has: a) a g′ vis  of 0.70 or less;   b) an Mw of 100,000 g/mol or more; c) an Mw/Mn of 4.0 or more; d) a shear thinning ratio of 110 or more, e) a melt strength of 10 cN or more; f) a complex viscosity at 0.1 rad/sec at 190° C. of at least 130,000 Pa·s; and g) a phase angle of Z° or less where Z=138.3 G* (−0.142) , where G* is the complex modulus reported in Pascals measured at 190° C. and the phase angle units are reported in degrees, wherein the G* is from 1,000 to 1,000,000 Pa;   2) polyethylene having a density of 0.88 g/cc or more, a g′ vis  of 0.97 or more.   
     
     
         11 . The blend of  claim 10 , wherein the complex viscosity at 0.1 rad/sec of the branched polyethylene modifier is at least 320% greater than the complex viscosity at 0.1 rad/sec of the polyethylene prior to combination with the branched polyethylene modifier. 
     
     
         12 . The blend of  claim 10 , wherein the branched polyethylene modifier is present at 0.5 wt % to 10 wt %, based upon the weight of the blend. 
     
     
         13 . The blend of  claim 10 , wherein the polyethylene comprises a copolymer of ethylene and one or more C 3  to C 20  alphaolefins and has an Mw of 20,000 to 1,000,000 g/mol. 
     
     
         14 . The blend of  claim 10 , wherein the polyethylene has a density of 0.91 to 0.96 g/cm 3 . 
     
     
         15 . (canceled) 
     
     
         16 . The blend of  claim 10 , wherein the branched polyethylene modifier has a strain-hardening ratio of 1.5 or greater. 
     
     
         17 . (canceled) 
     
     
         18 . The blend of  claim 10 , wherein where the polyethylene has a g′ vis  of 0.975 or more. 
     
     
         19 .- 22 . (canceled) 
     
     
         23 . A film comprising the blend of  claim 10 . 
     
     
         24 . (canceled) 
     
     
         25 . The blend of  claim 10 , wherein the branched polyethylene modifier has an Mw of 200,000 g/mol or more. 
     
     
         26 . The blend of  claim 10 , wherein the blend has a melt strength at least 60% higher than the melt strength of the polyethylene having a density of 0.88 g/cc or more and an Mw of 20,000 g/mol or more used in the blend. 
     
     
         27 . The blend of  claim 10 , wherein the blend has a melt strength at least 100% higher than the melt strength of the polyethylene prior to combination with the branched polyethylene modifier. 
     
     
         28 .- 30 . (canceled) 
     
     
         31 . The blend of  claim 10 , wherein the composition of linear PE and branched modifier blend has a melt strength ratio of T or more, where T=1.6762[(η* blend  minus η* matrix ) divided by (η* matrix )]−5, where η* blend  is the complex viscosity of the blend measured at 0.158 rad/sec and 190° C., and η* matrix  is the complex viscosity of the linear polyethylene measured at 0.158 rad/sec and 190° C.; and the ratio of melt strength to viscosity is defined to be melt strength ratio is defined to be [(MS blend  minus MS matrix ) divided by (MS matrix )], where MS blend  is the melt strength of the composition, MS matrix  is the melt strength of the linear polyethylene. 
     
     
         32 .- 37 . (canceled) 
     
     
         38 . The blend of  claim 10 , wherein the blend has a strain hardening ratio of at least 50% higher than the strain hardening ratio of the polyethylene of step 2). 
     
     
         39 . The blend of  claim 10 , wherein the polyene is selected from the group consisting of: 1,4-pentadiene, 1,5-hexadiene, 1,6-heptadiene, 1,7-octadiene, 1,8-nonadiene, 1,9-decadiene, 1,10-undecadiene, 1,11-dodecadiene, 1,12-tridecadiene, 1,13-tetradecadiene, tetrahydroindene, norbornadiene also known as bicyclo-(2.2.1)-hepta-2,5-diene, dicyclopentadiene, 5-vinyl-2-norbornene, 1,4-cyclohexadiene, 1,5-cyclooctadiene, and 1,7-cyclododecadiene. 
     
     
         40 . The blend of  claim 10 , wherein the polyethylene has an Mw of 20,000 g/mol or more, wherein the melt strength ratio is Q or more, where Q=0.0805[(η* modifier −η* matrix )/(η* matrix )]+0.5, wherein η* modifier  is the complex viscosity of the modifier measured at 0.158 rad/sec and 190° C., and η* matrix  is the complex viscosity of the polyethylene measured at 0.158 rad/sec and 190° C.; and the melt strength ratio is defined to be [(MS blend −MS matrix )/(MS matrix )], where MS blend  is the melt strength of the blend, MS matrix  is the melt strength of the polyethylene. 
     
     
         41 . The blend of  claim 10 , wherein the branched polyethylene modifier has a complex viscosity ratio of Y or more, where Y=−0.27*(Log η* matrix )+1.4, and the complex viscosity ratio is defined to be (Log η* modifier  minus Log η* matrix ) divided by (Log η* matrix ), wherein η* modifier  is the complex viscosity of the modifier measured at 0.1 rad/sec and 190° C., and η* matrix  is the complex viscosity of the polyethylene of step 2) below measured at 0.1 rad/sec and 190° C.