Broad orthogonal distribution polyethylenes for films

Patent metadata

Field	Value
Publication number	US-12344686-B2
Application number	US-202017756997-A
Country	US
Kind code	B2
Filing date	Nov 18, 2020
Priority date	Dec 17, 2019
Publication date	Jul 1, 2025
Grant date	Jul 1, 2025

Abstract

A polyethylene comprising of ethylene derived units and 0.5 wt % to 10 wt % C3 to C12 α-olefin derived units may be synthesized using a mixed catalyst that comprises rac-dimethylsilylbis(tetrahydroindenyl)zirconium dichloride and a zirconium co-catalyst in a mole ratio of 50:50 to 90:10, and wherein the zirconium co-catalyst is a poor comonomer incorporator as compared to the rac-dimethylsilylbis(tetrahydroindenyl)zirconium dichloride catalyst. Such a polyethylene may have a density of 0.91 g/cm3 to 0.93 g/cm3, an I2 value of 0.5 g/10 min to 2 g/10 min, an I21 value of 25 g/10 min to 75 g/10 min, an I21/I2 ratio of 25 to 75, a molar reversed-co-monomer index (RCI,m) of 30 to 180, a phase angle equal or lower than 70° at complex modulus G* of 10,000 Pa, a Θ2 of 1.5 radians to −1.5 radians, and a low density population of 50% and 70% by weight of the polyethylene.

First claim

The invention claimed is:

1. A composition comprising:
polyethylene comprising ethylene derived units and C 3 to C 12 α-olefin derived units at 0.5 wt % to 10 wt % of the polyethylene; and having a density of 0.91 g/cm 3 to 0.93 g/cm 3 , an I 2 value within a range from 0.5 g/10 min to 2 g/10 min, an I 21 value within a range from 25 g/10 min to 75 g/10 min, an I 21 /I 2 ratio of 25 to 75, a molar reversed-co-monomer index (RCI,m) of 30 to 180, a phase angle equal or lower than 70° at complex modulus G* of 10,000 Pa, a θ 2 within a range from 1.5 radians to −1.5 radians, and a low density population within a range from 50% and 70% by weight of the polyethylene.

2. A film comprising:
polyethylene comprising ethylene derived units and C 3 to C 12 α-olefin derived units at 0.5 wt % to 10 wt % of the polyethylene; and having:
a density of 0.91 g/cm 3 to 0.93 g/cm 3 ,
an I 2 value within a range from 0.5 g/10 min to 2 g/10 min,
an I 21 value within a range from 25 g/10 min to 75 g/10 min,
an I 21 /I 2 ratio of 25 to 75,
a molar reversed-co-monomer index (RCI,m) of 30 to 180,
a phase angle equal or lower than 70° at complex modulus G* of 10,000 Pa,
a θ 2 within a range from 1.5 radians to −1.5 radians, and
a low density population within a range from 50% and 70% by weight of the polyethylene; and
wherein the film has a 1% secant flexural modulus in a machine direction (MD) of 25,000 psi to 45,000 psi, an Elmendorf tear in the MD of 200 g to 350 g, and a dart drop value of 200 g/mil to 1,000 g/mil.

3. The film of claim 2 , wherein the film has one or more of the following properties:
(A) a tensile yield strength in the MD of 1,000 psi to 2,000 psi;
(B) a 1% secant flexural modulus in the TD of 30,000 psi to 60,000 psi;
(C) a tensile yield strength in the TD of 1,000 psi to 2,500 psi;
(D) an elongation at yield in the MD of 5% to 12%;
(E) a tensile strength in the MD of 5,000 psi to 10,000 psi; and
(F) an elongation at break in the MD of 400% to 550%.

4. The film of claim 3 , having all of the properties (A)-(F).

5. A method comprising: reacting ethylene, a C 3 to C 12 α-olefin comonomer, and hydrogen in the presence of a mixed catalyst to form a polyethylene, wherein the polyethylene comprises: ethylene derived units and C 3 to C 12 α-olefin derived units at 0.5 wt % to 10 wt % of the polyethylene; wherein the polyethylene has:
a density of 0.91 g/cm 3 to 0.93 g/cm 3 ,
an I 2 value within a range from 0.5 g/10 min to 2 g/10 min,
an I 21 value within a range from 25 g/10 min to 75 g/10 min,
an I 21 /I 2 ratio of 25 to 75,
a molar reversed-co-monomer index (RCI,m) of 30 to 180,
a phase angle equal to or lower than 70° at complex modulus G* of 10,000 Pa,
a θ 2 within a range from 1.5 radians to −1.5 radians, and
a low density population within a range from 50% and 70% by weight of the polyethylene; and
wherein the mixed catalyst comprises rac-dimethylsilylbis(tetrahydroindenyl)zirconium dichloride (Compound I) and a zirconium co-catalyst (Compound II) in a Compound I to Compound II mole ratio of 50:50 to 90:10, and wherein the zirconium co-catalyst is a poor comonomer incorporator as compared with rac-dimethylsilylbis(tetrahydroindenyl)zirconium dichloride.

6. The method of claim 5 , wherein the reacting takes place at a temperature of 66° C. (150° F.) to 93° C. (200° F.) and/or at a pressure of 200 psig to 400 psig.

7. The method of claim 6 , wherein the reacting takes place in a reactor in which mole % ratio of comonomer to ethylene is 0.005 to 0.030 and/or ratio of hydrogen to ethylene (ppm/mol %) is 3.0 to 5.5.

8. The method of claim 5 , wherein the polyethylene has one or more of the following properties:
(a) a weight average molecular weight (Mw) of 95,000 g/mol to 125,000 g/mol;
(b) a number average molecular weight (Mn) of 10,000 g/mol to 25,000 g/mol;
(c) a Z-average molecular weight (Mz) of 200,000 g/mol to 500,000 g/mol;
(d) a Mw to Ma ratio of 4.0 to 9.0;
(e) a Mz to Mn ratio of 8 to 30; and
(f) a mole % comonomer distribution ratio (CDR2,m) of 1.0 to 2.0.

9. The method of claim 8 , wherein the polyethylene has all of the properties (a)-(f).

10. The method of claim 5 further comprising forming a film with a compound comprising the polyethylene.

Assignees

• Exxonmobil Chemical Patents Inc

Inventors

• Holtcamp Matthew W
• Bedoya Matthew S
• Boller Timothy M
• Rangwalla Hasnain
• Sanders David F
• Lue Ching-Tai
• Li Dongming
• Silva Adriana S
• Xie Ru
• Moebus Joseph A

Classifications

• C08F4/659

  Component covered by group C08F4/64 containing a transition metal-carbon bond {(C08F4/64003 - C08F4/64196 take precedence)} · CPC title

• C08F4/65927

  two cyclopentadienyl rings being mutually bridged · CPC title

• C08F2420/12

  Long bridge, i.e. Cp or analog where the bridging unit linking the two Cps or analogs is composed of at least two atoms which are not part of a cycle and which are not an ethylene bridge · CPC title

• C08L2203/16

  used for films · CPC title

• C09D123/08

  Copolymers of ethene (C09D123/16 takes precedence) · CPC title