Ethylene interpolymer products having unique melt flow-intrinsic viscosity (MFIVI) and high unsaturation
This disclosure relates to ethylene interpolymer products comprising a Melt Flow-Intrinsic Viscosity Index value, MFIVI, of from ≥0.05 to ≤0.80; a first derivative of a melt flow distribution function, formula (I) at a loading of 4000 g, of from ≥−1.85 to ≤−1.51; a sum of unsaturation, SUM U , from ≥0.047 to ≤0.100 unsaturations per 100 carbon atoms; and a residual QC catalytic metal of from ≥0.03 to ≤5 ppm of hafnium. Ethylene interpolymer products comprise at least two ethylene interpolymers. Ethylene interpolymer products are characterized by a melt index (I 2 ) from 0.3 to 500 dg/minute, a density from 0.855 to 0.975 g/cc and from 0 to 25 mole percent of one or more a-olefins. Ethylene interpolymer products have polydispersity, M w /M n , from 1.7 to 25; and CDBI 50 values from 1% to 98%. These ethylene interpolymer products have utility in flexible as well as rigid applications.
1. An ethylene interpolymer product comprising at least two ethylene interpolymers, wherein the ethylene interpolymer product comprises:
a) a dimensionless Melt Flow-Intrinsic Viscosity Index, MFIVI, of from ≥0.05 to ≤0.80, as defined by Eq.1
MFIVI
=
(
1
.9507
×
(
f
b
i
m
o
d
a
l
i
t
y
×
f
c
o
monmer
I
f
)
0.21678
IV
+
3.0122
×
10
-
6
×
(
Comonomer
Wt
%
)
×
M
v
0.725
)
-
1
Eq
.
1
wherein, f bimodality , is defined by Eq.2,
f bimodality =10 (−0.94831×Log (pd)−0.94322×C f −0.71879) Eq2
wherein a polydispersity of said ethylene interpolymer product, Pd (in Eq.2), is determined by Size Exclusion Chromatography (SEC), Pd=M w /M n , where M w and M n are a weight average and a number average molecular weight, respectively;
wherein, a correction factor, C f , (in Eq.2) is determined according to the following two steps (i) and (ii),
(i) a melt flow distribution function of said ethylene interpolymer product defined by Eq.3,
Log(1/ I n )=β 0 +/β 1 ×Log(loading)+β 2 ×(Log(loading)) 2 Eq.3
is determined by plotting Log(I/I n ) versus Log(loading), where I n is a measured melt index, of said ethylene interpolymer product, at loadings of 21600, 10000, 6480 and 2160 grams, measured at 190° C. according to ASTM D1238,
(ii) a first derivative of said melt flow distribution function is defined by Eq.4,
d
Log
(
1
/
I
n
)
d
Log
(
loading
)
=
β
1
+
2
×
β
2
×
Log
(
loading
)
Eq
.
4
and said correction factor, C f (Eq.2), is the value of said first derivative (Eq.4) at a loading of 4000 g;
wherein a comonomer weight percent, Comonomer Wt % (Eq.1), is the weight percent of comonomer in said ethylene interpolymer product as measured by FTIR according to ASTM D6645, if Comonomer Wt % is >14.95%, a comonomer factor, f comonomer (Eq.1), is defined by Eq.5, if Comonomer Wt % is ≤14.95%, said comonomer factor is defined by Eq.6,
f comonomerEq =10 (0.01879×(Comonomer Wt %)−0.28053) Eq.5
f comonomer =1 Eq.6;
wherein a fitted melt index, I f (Eq.1), of said ethylene interpolymer product, is determined by the value of said melt flow distribution function (Eq.3) at a loading of 4000 g;
wherein, IV and M v (Eq.1) are an intrinsic viscosity and a viscosity average molar mass, respectively, of said ethylene interpolymer product as determined by 3D-SEC;
b) said first derivative,
d
Log
(
1
/
I
n
)
d
Log
(
loading
)
(
Eq
.
4
)
at a loading of 4000 g, having values from ≥−1.85 to ≤−1.51;
c) a sum of unsaturation, SUM U , of from ≥0.047 to ≤0.100 unsaturations per 100 carbon atoms, as defined by Eq.7,
SUM U =(2× I U +SC U +T U ) Eq.7,
wherein I U , SC U and T U are the amount of an internal, side chain and terminal unsaturation per 100 carbons, respectively, in said ethylene interpolymer product, as determined by ASTM D3124-98 and ASTM D6248-98; and
d) a residual catalytic metal of from ≥0.03 to ≤5 ppm of hafnium, wherein the residual catalytic metal is measured using neutron activation.
2. The ethylene interpolymer product of claim 1 , wherein the ethylene interpolymer product comprises a first ethylene interpolymer, a second ethylene interpolymer, and optionally a third ethylene interpolymer.
3. The ethylene interpolymer product of claim 2 , wherein the said first and said second interpolymers, or said first and said third ethylene interpolymers, are synthesized using a bridged metallocene catalyst formulation.
4. The ethylene interpolymer product of claim 3 , wherein said bridged metallocene catalyst formulation comprises a component A defined by Formula (I):
wherein:
M is Ti, Hf, or Zr;
G is C, Si, Ge, Sn, or Pb;
X is a halogen atom;
R 6 , at each occurrence, is independently selected from H, a C 1-20 hydrocarbyl radical, a C 1-20 alkoxy radical, or a C 6-10 aryl oxide radical, wherein these radicals may be linear, branched, or cyclic or further substituted with a halogen atom, a C 1-10 alkyl radical, a C 1-10 alkoxy radical, a C 6-10 aryl, or an aryloxy radical;
R 1 is H, a C 1-20 hydrocarbyl radical, a C 1-20 alkoxy radical, a C 6-10 aryl oxide radical, or an alkylsilyl radical containing at least one silicon atom and C 3-30 carbon atoms;
R 2 and R 3 are independently selected from H, a C 1-20 hydrocarbyl radical, a C 1-20 alkoxy radical, a C 6-10 aryl oxide radical, or an alkylsilyl radical containing at least one silicon atom and C 3-30 carbon atoms; and
R 4 and R 5 are independently selected from H, a C 1-20 hydrocarbyl radical, a C 1-20 alkoxy radical, a C 6-10 aryl oxide radical, or an alkylsilyl radical containing at least one silicon atom and C 3-30 carbon atoms.
5. The ethylene interpolymer product of claim 1 , wherein the ethylene interpolymer product has a melt index from 0.3 to 500 dg/minute and a density from 0.855 to 0.975 g/cc, wherein the melt index is measured according to ASTM D1238 (2.16 kg load and 190° C.) and the density is measured according to ASTM D792.
6. The ethylene interpolymer product of claim 1 , wherein the ethylene interpolymer product further comprises from 0 to 25 mole percent of one or more α-olefins.
7. The ethylene interpolymer product of claim 6 , wherein the one or more α-olefins comprise a C 3 to C 10 α-olefin.
8. The ethylene interpolymer product of claim 7 , wherein the one or more α-olefins are 1-hexene, or 1-octene, or a mixture 1-hexene and 1-octene.
9. The ethylene interpolymer product of claim 1 , wherein the ethylene interpolymer product has a polydispersity, M w /M n from 1.7 to 25, wherein the weight average molecular weight, M w , and the number average molecular weight, M n are measured using conventional size exclusion chromatography.
10. The ethylene interpolymer product of claim 1 , wherein the ethylene interpolymer product has a CDBI 50 from 1% to 98%, wherein CDBI 50 is measured using CTREF.
11. The ethylene interpolymer product of claim 1 , wherein the ethylene interpolymer product is manufactured by a solution polymerization process.