Polyethylene composition for having high impact and stress cracking resistance

Patent metadata

Field	Value
Publication number	US-9969898-B2
Application number	US-201715660653-A
Country	US
Kind code	B2
Filing date	Jul 26, 2017
Priority date	Jun 25, 2013
Publication date	May 15, 2018
Grant date	May 15, 2018

Abstract

Polyethylene composition with improved balance of impact resistance at low temperatures and Environmental Stress Cracking Resistance (ESCR), particularly suited for producing protective coatings on metal pipes, said composition having the following features:
1) density from 0.938 to 0.948 g/cm 3 ; 2) ratio MIF/MIP from 15 to 25; 3) MIF from 30 to 45 g/10 min.; 4) Mz equal to or greater than 1000000 g/mol; 5) LCBI equal to or greater than 0.55.

First claim

What is claimed is:

1. A polyethylene composition comprising:
1) a density from 0.940 to 0.948 g/cm 3 as determined according to ISO 1183 at 23° C.;
2) a MIF/MIP ratio from 15 to 25, where MIF is the melt flow index at 190° C. with a load of 21.60 kg, and MIP is the melt flow index at 190° C. with a load of 5 kg, both determined according to ISO 1133;
3) a MIF value from 30 to 45 g/10 min;
4) a M z value equal to or greater than 1000000 g/mol;
5) a long-chain branching index, LCBI, equal to or greater than 0.55;
wherein LCBI is the ratio of the measured mean-square radius of gyration R g , measured by GPC-MALLS, to the mean-square radius of gyration for a linear PE having the same molecular weight.

2. The polyethylene composition of claim 1 , having at least one of the following additional features:
a Mw value equal to or lower than 300000 g/mol;
a Mw/Mn value from 15 to 30;

a MW value from 1.2-2.5 g/10 min;
a SIC Index value from 3 to 5;
wherein the SIC Index is the Shear-Induced Crystallization Index, determined according to the following relation:
SIC Index=( t onset,SIC @1000 ×t onset,quiescent )/(MIF)

where t onset,SIC @1000 is measured in seconds and is the time required for crystallization onset under a shear rate of 1000 s −1 , the t onset,quiescent is measured in seconds and is the crystallization onset time at temperature of 125° C. under no shear, as determined in isothermal mode by differential scanning calorimetry.

3. The polyethylene composition of claim 1 , comprising:
A) 40-60 % by weight of an ethylene homopolymer or copolymer with a density equal to or greater than 0.960 g/cm 3 and melt flow index MIE at 190° C. with a load of 2.16 kg, according to ISO 1133, of 40-250 g/10 min;
B)40-60% by weight of an ethylene copolymer having a MIE value lower than the MIE value of A).

4. A metal pipe coated with the polyethylene composition of claim 1 .

5. The polyethylene of claim 1 , wherein the MIF/MIP ratio is from 19 to 23.

6. The polyethylene of claim 1 , wherein the MIF value is from 35 to 40 g/10 min.

7. The polyethylene of claim 1 , wherein the LCBI is greater than 0.60.

8. The polyethylene of claim 1 , wherein the M w value is from 180,000 to 250,000 g/mol.

9. The polyethylene of claim 1 , wherein the M w /M n , value is from 15 to 25.

10. The polyethylene of claim 1 , wherein the SIC Index value is from 3.5 to 4.5.

11. The polyethylene of claim 1 , wherein the density is from 0.940 to 0.945 g/cm 3 .

12. The polyethylene composition of claim 1 , further comprising:
6) eta (0.02) from 25,000 to 35,000 Pa·s;
wherein eta (0.02) is the complex shear viscosity at an angular frequency of 0.02 rad/s, measured with dynamic oscillatory shear in a plate-plate rotational rheometer at a temperature of 190° C.

13. The polyethylene of claim 12 , where the eta (0.02) is from 28,000 to 33,000 Pa·s.

14. The polyethylene composition of claim 1 , comprising one or more ethylene copolymers.

15. The polyethylene composition of claim 14 , comprising a comonomer content of 1.5 to 6% by weight.

16. The polyethylene composition of claim 1 , where the composition is obtained by using a Ziegler-Natta polymerization catalyst.

17. The polyethylene composition of claim 16 , where the Ziegler-Natta polymerization catalyst comprises the product of reaction of:
a) a solid catalyst component comprising a Ti compound supported on MgCl 2 , the component being obtained by contacting the titanium compound with the MgCl 2 , or a precursor Mg compound, optionally in the presence of an inert medium, for obtaining an intermediate product a′), then subjecting a′) to prepolymerization and contact with an electron donor compound;
b) an organo-Al compound; and
c) optionally an external electron donor compound.

18. A process for coating metal pipes, comprising a step wherein the polyethylene composition of claim 1 is molten in an extruder and extruded onto the pipe surface, where the pipe surface being optionally pretreated.

19. A process for preparing the polyethylene composition of claim 1 , where all the polymerization steps are carried out in the presence of a Ziegler-Natta polymerization catalyst supported on MgCl 2 .

20. The process of claim 19 , comprising the following steps, in any mutual order:
a) polymerizing ethylene, optionally together with one or more comonomers, in a gas-phase reactor in the presence of hydrogen;
b) copolymerizing ethylene with one or more comonomers in another gas-phase reactor in the presence of an amount of hydrogen less than step a);
where in at least one of said gas-phase reactors the growing polymer particles flow upward through a first polymerization zone under fast fluidization or transport conditions, leave the riser and enter a second polymerization zone through which they flow downward under the action of gravity, leave the second polymerization zone and are reintroduced into the first polymerization zone for establishing a circulation of polymers between the two polymerization zones.

Assignees

• Basell Polyolefine Gmbh

Inventors

• Meier Gerhardus
• Schuller Ulf
• Dotsch Diana
• Marczinke Bernd Lothar
• Vogt Heinz

Classifications

• C09D123/06

  Polyethylene · CPC title

• C08L23/0815

  with aliphatic 1-olefins containing one carbon-to-carbon double bond · CPC title

• C08F210/16

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

• C08L2205/025

  containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure · CPC title

• C08L2314/02

  Ziegler natta catalyst · CPC title