Bimodal polyethylene resins and pipes produced therefrom

Patent metadata

Field	Value
Publication number	US-11225538-B2
Application number	US-202016774061-A
Country	US
Kind code	B2
Filing date	Jan 28, 2020
Priority date	Mar 13, 2018
Publication date	Jan 18, 2022
Grant date	Jan 18, 2022

Abstract

Disclosed herein are ethylene-based polymers generally characterized by a density of at least 0.94 g/cm3, a high load melt index from 4 to 20 g/10 min, a zero-shear viscosity at 190° C. from 20,000 to 400,000 kPa-sec, and a relaxation time at 190° C. from 225 to 3000 sec. These ethylene polymers can be produced by peroxide-treating a broad molecular weight distribution Ziegler-catalyzed resin, and can be used in large diameter, thick wall pipes and other end-use applications.

First claim

We claim:

1. A process for preparing an ethylene polymer, the process comprising:
contacting a base resin with a peroxide compound to produce the ethylene polymer, wherein the ethylene polymer is characterized by:
a density of at least about 0.94 g/cm 3 ;
a HLMI (I 21 ) in a range from about 4 to about 20 g/10 min;
a zero-shear viscosity (η 0 ) at 190° C. in a range from about 20,000 to about 400,000 kPa-sec; and
a relaxation time (τ η ) at 190° C. in a range from about 225 to about 3000 sec.

2. The process of claim 1 , wherein the base resin is characterized by:
a density of at least about 0.94 g/cm 3 ;
a HLMI (I 21 ) in a range from about 4 to about 25 g/10 min;
a Mw in a range from about 200,000 to about 500,000 g/mol; and
a ratio of Mw/Mn in a range from about 12 to about 40.

3. The process of claim 2 , wherein:
the base resin has:
a Mn in a range from about 8,000 to about 20,000 g/mol;
a Mz in a range from about 1,000,000 to about 2,500,000 g/mol; and
a ratio of HLMI/I 5 in a range from about 20 to about 45; and

the base resin comprises an ethylene homopolymer, an ethylene/1-butene copolymer, an ethylene/1-hexene copolymer, an ethylene/1-octene copolymer, or a combination thereof.

4. The process of claim 3 , wherein:
the base resin is produced using a Ziegler-Natta catalyst system; and
the base resin comprises a higher molecular weight component and a lower molecular weight component; wherein:
the higher molecular weight component is characterized by:
a density in a range from about 0.915 to about 0.94 g/cm 3 ;
a ratio of Mw/Mn in a range from about 4 to about 8; and
a Mw in a range from about 425,000 to about 650,000 g/mol; and

the lower molecular weight component is characterized by:
a ratio of Mw/Mn in a range from about 4 to about 8; and
a Mw in a range from about 20,000 to about 40,000 g/mol.

5. The process of claim 1 , wherein an amount of the peroxide compound is from about 60 to about 200 ppm by weight of peroxide groups, based on the weight of the base resin.

6. The process of claim 1 , wherein the step of contacting the base resin with the peroxide compound comprises melt processing a mixture of the base resin and the peroxide compound in a twin screw extrusion system.

7. The process of claim 1 , wherein:
the step of contacting the base resin with the peroxide compound comprises melt processing a mixture of the base resin, the peroxide compound, and an additive at a melt processing temperature in a range from about 120 to about 300° C.; and
the additive comprises an antioxidant, an acid scavenger, an antiblock additive, a slip additive, a colorant, a filler, a processing aid, a UV inhibitor, or any combination thereof.

8. A process for preparing an ethylene polymer, the process comprising:
contacting a base resin with a peroxide compound to produce the ethylene polymer, wherein the ethylene polymer is characterized by:
a density in a range from about 0.94 to about 0.96 g/cm 3 ;
a HLMI (I 21 ) in a range from about 4 to about 20 g/10 min;
a ratio of Mw/Mn in a range from about 13 to about 38;
a zero-shear viscosity (η 0 ) at 190° C. in a range from about 20,000 to about 400,000 kPa-sec; and
a relaxation time (τ η ) at 190° C. in a range from about 225 to about 3000 sec.

9. The process of claim 8 , wherein the ratio of Mw/Mn is in a range from about 16 to about 37.

10. The process of claim 8 , wherein the ethylene polymer has a Mn in a range from about 10,200 to about 16,100 g/mol.

11. The process of claim 8 , wherein:
the HLMI (I 21 ) is in a range from about 4 to about 18 g/10 min;
the zero-shear viscosity (η 0 ) at 190° C. is in a range from about 30,000 to about 300,000 kPa-sec;
the relaxation time (τ η ) at 190° C. is in a range from about 250 to about 2500 sec; and
the ethylene polymer comprises an ethylene/1-butene copolymer, an ethylene/1-hexene copolymer, an ethylene/1-octene copolymer, an ethylene homopolymer, or a combination thereof.

12. The process of claim 11 , wherein the ratio of Mw/Mn is in a range from about 18 to about 35.

13. The process of claim 11 , wherein the ethylene polymer has:
a CY-a parameter at 190° C. in a range from about 0.1 to about 0.18;
a number of long chain branches (LCB) in a range from about 7 to about 20 LCB per million total carbon atoms;
a viscosity at 0.01 sec −1 at 190° C. in a range from about 450 to about 750 kPa-sec; and
a viscosity at 0.001 sec −1 at 190° C. in a range from about 1200 to about 2100 kPa-sec.

14. The process of claim 8 , wherein the base resin is characterized by:
a density in a range from about 0.94 to about 0.955 g/cm 3 ;
a HLMI (I 21 ) in a range from about 4 to about 25 g/10 min;
a Mw in a range from about 200,000 to about 500,000 g/mol; and
a ratio of Mw/Mn in a range from about 12 to about 40.

15. The process of claim 8 , wherein:
the base resin has:
a Mn in a range from about 8,000 to about 20,000 g/mol;
a Mz in a range from about 1,000,000 to about 2,500,000 g/mol; and
a ratio of HLMI/I 5 in a range from about 20 to about 45; and

the base resin comprises an ethylene homopolymer, an ethylene/1-butene copolymer, an ethylene/1-hexene copolymer, an ethylene/1-octene copolymer, or a combination thereof.

16. The process of claim 15 , wherein the ratio of HLMI/I 5 is in a range from about 25 to about 40.

17. The process of claim 15 , wherein the step of contacting the base resin with the peroxide compound comprises melt processing a mixture of the base resin and the peroxide compound in a twin screw extrusion system.

18. The process of claim 8 , wherein:
the base resin comprises an ethylene homopolymer, an ethylene/1-butene copolymer, an ethylene/1-hexene copolymer, an ethylene/1-octene copolymer, or a combination thereof; and
the base resin comprises a higher molecular weight component and a lower molecular weight component; wherein:
the higher molecular weight component is characterized by:
a density in a range from about 0.915 to about 0.94 g/cm 3 ;
a ratio of Mw/Mn in a range from about 4 to about 8; and
a Mw in a range from about 425,000 to about 650,000 g/mol; and

the lower molecular weight component is characterized by:
a ratio of Mw/Mn in a range from about 4 to about 8; and
a Mw in a range from about 20,000 to about 40,000 g/mol.

19. The process of claim 8 , wherein:
the base resin is produced using a Ziegler-Natta catalyst system; and
an amount of the peroxide compound is from about 60 to about 200 ppm by weight of peroxide groups, based on the weight of the base resin.

20. The process of claim 8 , wherein:
the step of contacting the base resin with the peroxide compound comprises melt processing a mixture of the base resin, the peroxide compound, and an additive at a melt processing temperature in a range from about 120 to about 300° C.; and
the additive comprises an antioxidant, an acid scavenger, an antiblock additive, a slip additive, a colorant, a filler, a processing aid, a UV inhibitor, or any combination thereof.

Assignees

• Chevron Phillips Chemical Co Lp

Inventors

• Rohatgi Vivek
• Sukhadia Ashish M
• Inn Yongwoo
• Lanier Elizabeth M

Classifications

• F16L9/12

  of plastics with or without reinforcement (F16L9/16 - F16L9/22 take precedence) · CPC title

• C08L23/08

  Copolymers of ethene (C08L23/16 takes precedence) · CPC title

• C08F210/16 Primary

  Copolymers of ethene with alpha-alkenes, e.g. EP rubbers · CPC title

• C08F10/02

  Ethene · CPC title

• C08L2205/03

  containing three or more polymers in a blend · CPC title