Polyethylene composition having high swell ratio, fnct and impact resistance

Patent metadata

Field	Value
Publication number	US-11236183-B2
Application number	US-201917053633-A
Country	US
Kind code	B2
Filing date	May 14, 2019
Priority date	May 14, 2018
Publication date	Feb 1, 2022
Grant date	Feb 1, 2022

Abstract

A polyethylene composition for producing blow-molded hollow articles, having the following features:
1) a density from 0.945 to 0.958 g/cm 3 , determined according to ISO 1183 at 23° C.;
2) a ratio MIF/MI10 from 2 to 10;
3) a η 0.02 from 200,000 to 800,000 Pa·s;
4) a LCBI equal to or lower than 0.80; and
5) a ratio (η 0.02 /1000)/LCBI equal to or greater than 350.

First claim

What is claimed is:

1. A polyethylene composition having the following features:
1) a density from 0.945 to 0.958 g/cm 3 determined according to ISO 1183 at 23° C.;
2) a ratio MIF/MI10 from 2 to 10, where MIF is the melt flow index at 190° C. with a load of 21.60 kg, and MI10 is the melt flow index at 190° C. with a load of 10 kg, both determined according to ISO 1133;
3) a η 0.02 from 200,000 to 800,000 Pa·s, wherein η 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.;
4) a long-chain branching index, LCBI equal to or lower than 0.80, 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, at a molecular weight of 1,000,000 g/mol; and
5) a ratio η 0.02 /1000)/LCBI, which is between η 0.02 divided by 1000 and LCBI, equal to or greater than 350.

2. The polyethylene composition of claim 1 comprising;
one or more ethylene copolymers derived from ethylene and one or more comonomers.

3. The polyethylene composition of claim 2 , wherein the comonomer or comonomers present in the ethylene copolymers are selected from olefins having formula CH2═CHR wherein R is an alkyl radical, linear or branched, having from 1 to 10 carbon atoms.

4. The polyethylene composition of claim 1 obtained by using a Ziegler-Natta polymerization catalyst.

5. The polyethylene composition of claim 4 , wherein the Ziegler-Natta polymerization catalyst comprises:
the product of a reaction of:
A) a solid catalyst component comprising Ti, Mg, chlorine and one internal electron donor ED selected from esters of aliphatic monocarboxylic acids (EAA) and another internal donor ED I selected from cyclic ethers (CE) in an amount such that the EAA/CE molar ratio ranges from 0.02 to less than 20;
B) an organo-Al compound; and optionally
C) an external electron donor compound.

6. The polyethylene composition of claim 1 , having at least one of the following additional features:
a Mz from 1,500,000 to 8,000,000 g/mol;
a MIF from 0.5 to 10 g/10 min.;
a comonomer content equal to or less than 2% by weight, with respect to the total weight of the composition;
a HMWcopo index from 1 to 15;
wherein the HMWcopo index is determined according to the following formula:
HMWcopo=(η 0.02 ×t maxDSC )/(10{circumflex over ( )}5)

where the tmaxDSC—is the time, in minutes, to reach the maximum value of heat flow (in mW) of crystallization (time at which the maximum crystallization rate is achieved, equivalent to the t1/2 crystallization half-time) at a temperature of 124° C. under quiescent conditions, measured in isothermal mode in a differential scanning calorimetry apparatus, DSC;
a ET higher than 30,
wherein ET is calculated from:
ET=C 2 /G *at tan δ= C 3

wherein:
G*=[(G′) 2 +(G″) 2 ] 1/2 ;
tan δ=G″/G′;
C 2 =10 6 dyn/cm 2
C 3 =1.5,
G′=storage-modulus, and
G″=loss-modulus,

both G′ and G″ being measured with dynamic oscillatory shear in a plate-plate rotational rheometer at a temperature of 190° C.; or
Mz/Mw*LCBI of lower than 10.

7. The polyethylene composition of claim 1 , comprising:
A) 30-70% by weight of an ethylene homopolymer or copolymer with density equal to or greater than 0.956 g/cm 3 and melt flow index MIE at 190° C. with a load of 2.16 kg, according to ISO 1133, of 0.5 g/10 min. or higher; and
B) 30-70% by weight of an ethylene copolymer having a MIE value lower than the MIE value of A).

8. An article of manufacturing comprising:
the polyethylene composition of claim 1 .

9. The article of manufacture according to claim 8 , wherein the article is a blow-molded hollow article.

10. The article of manufacture according to claim 9 , wherein the article is a L-Ring Drum or an Open Top Drum.

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

12. The process of claim 11 , comprising the following steps, in any order:
a) polymerizing ethylene, optionally together with one or more comonomers, in a gas-phase reactor in the presence of hydrogen; and
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 the gas-phase reactors, the growing polymer particles flow upward through a first polymerization zone under fast fluidization or transport conditions, leave the first polymerization zone and enter a second polymerization zone through which the polymer particles flow downward under the action of gravity, leave the second polymerization zone and are reintroduced into the first polymerization zone, thereby establishing a circulation of polymer between the two polymerization zones.

Assignees

• Basell Polyolefine Gmbh

Inventors

• Doetsch Diana
• Marczinke Bernd Lothar
• Meier Gerhardus
• Schueller Ulf
• Fibla Claudio

Classifications

• C08F2/001

  Multistage polymerisation processes characterised by a change in reactor conditions without deactivating the intermediate polymer (C08F295/00, C08F297/00 take precedence) · CPC title

• C08F2500/09

  Long chain branches · CPC title

• C08F2500/05

  Bimodal or multimodal molecular weight distribution · CPC title

• C08F4/6543

  halides of magnesium · CPC title

• C08F4/6492

  containing aliphatic unsaturation · CPC title