IP Library › Granted Patent US 12,624,137
Granted Patent B2
US 12,624,137 · App. 18/005,892 · Granted May 12, 2026

Ethylene interpolymer products having a melt flow-intrinsic viscosity index (

Inventors: Zengrong Zhang (Calgary, CA); Fazle Sibtain (Calgary, CA); Stephen Brown (Calgary, CA); Monika Kleczek (Calgary, CA)
Assignee: NOVA Chemicals (International) S.A.
C08F210/16C08F4/65908
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Quick Facts
Patent No.
US 12,624,137
App. No.
18/005,892
Granted
May 12, 2026
Kind
B2
Abstract

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) of form ≥−1.85 to ≤−1.51; an unsaturation ratio, UR, of from >0.06 to ≤0.60; and a residual 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 and rigid applications. d ⁢ Log ⁡ ( 1 / I n ) d ⁢ Log ⁡ ( loading ) ( I )

Claims (136)

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

bimodality

×

f

comon

⁢

om

_

⁢

er

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)−0.94322xC f −0.71879)    Eq.2

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

wherein β 0 , β 1 , and β 2 are regression coefficients of the melt flow distribution function, and wherein the regression coefficients are determined by fitting a polynomial to experimental data of Log(1/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 comonomer =10 (0.018790×(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 dimensionless unsaturation ratio, UR, of from >0.06 to ≤0.6, wherein UR is defined by the following relationship;

UR=(SC U −T U )/ T U

wherein, SC U is the amount of a side chain unsaturation per 100 carbons and T U is amount of a terminal unsaturation per 100 carbons, 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 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.

4 . 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.

5 . The ethylene interpolymer product of claim 4 , wherein the one or more α-olefins comprise a C 3 to C 10 α-olefin.

6 . The ethylene interpolymer product of claim 5 , wherein the one or more α-olefins are 1-hexene, or 1-octene, or a mixture 1-hexene and 1-octene.

7 . The ethylene interpolymer product of claim 1 , wherein the ethylene interpolymer product has a polydispersity, M w /M n from 1.7 to 25.

8 . 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.

9 . The ethylene interpolymer product of claim 1 , wherein the ethylene interpolymer product is manufactured by a solution polymerization process.

10 . The ethylene interpolymer product of claim 2 , wherein the said first and said second interpolymers, or said first and said third ethylene interpolymers, or said first, said second and said third ethylene interpolymers are synthesized using a bridged metallocene catalyst formulation.

11 . The ethylene interpolymer product of claim 10 , 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, at each occurrence, is independently selected from a halogen atom, 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.

Assignments (1)
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Jan 18, 2023
From: ZHANG, ZENGRONG; SIBTAIN, FAZLE; BROWN, STEPHEN; KLECZEK, MONIKA
To: NOVA CHEMICALS (INTERNATIONAL) S.A.
Reel/Frame 062409/0406 →
Continuity (2)
Provisional Application 63070448 · Aug 26, 2020
Related Publication 20230279166A1 · Sep 7, 2023
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