Ethylene/1-butene copolymers with enhanced resin processability

• US 9,815,925 B2
• Filed: 05/24/2016
• Issued: 11/14/2017
• Est. Priority Date: 05/27/2015
• Status: Active Grant

• Current Assignee: Nova Chemicals
• Original Assignee: Nova Chemicals
• Inventors: Lam, Patrick, Ker, Victoria, Quaiattini, Robert
• Primary Examiner(s): LU, C CAIXIA
• Application Number:
  US15/163,266
• Publication Number:
  US 20160347891A1
• Time in Patent Office: 539 Days
• CPC Class Codes: B32B 2250/24 All layers being polymeric
• CPC Class Codes: B32B 2307/4026 within the layer by addition of a colorant, e.g. pigments, dyes
• CPC Class Codes: B32B 2307/54 Yield strength; Tensile strength
• CPC Class Codes: B32B 2307/558 Impact strength, toughness
• CPC Class Codes: B32B 2307/5825 Tear resistant
• CPC Class Codes: B32B 27/08 of synthetic resin
• CPC Class Codes: B32B 27/32 comprising polyolefins comprising vinyl (co)polymers or acrylic (co)polymers B32B27/30
• CPC Class Codes: B32B 27/327 comprising polyolefins obtained by a metallocene or single-site catalyst
• CPC Class Codes: B32B 7/12 using interposed adhesives or interposed materials with bonding properties
• CPC Class Codes: C08F 210/08 Butenes
• CPC Class Codes: C08F 210/16 Copolymers of ethene with alpha-alkenes, e.g. EP rubbers
• CPC Class Codes: C08F 2410/02 Anti-static agent incorporated into the catalyst
• CPC Class Codes: C08F 2420/04 Cp or analog not bridged to a non-Cp X ancillary anionic donor
• CPC Class Codes: C08F 2500/06 Comonomer distribution, e.g. normal, reverse or narrow
• CPC Class Codes: C08F 2500/10 Short chain branches
• CPC Class Codes: C08F 2500/11 Melt tension or melt strength
• CPC Class Codes: C08F 2500/12 Melt flow index or melt flow ratio
• CPC Class Codes: C08F 2500/19 Shear ratio or shear ratio index
• CPC Class Codes: C08F 2500/26 Use as polymer for film forming
• CPC Class Codes: C08F 4/65912 in combination with an organoaluminium compound
• CPC Class Codes: C08F 4/65916 : supported on a carrier, e.g. silica, MgCl2, polymer
• CPC Class Codes: C08F 4/6592 : containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring
• CPC Class Codes: C08J 2323/08 : Copolymers of ethene C08J2323/16 takes precedence
• CPC Class Codes: C08J 5/18 : Manufacture of films or sheets

Abstract

Ethylene/1-butene copolymers made with a single site catalyst system have high melt strength and good processability.

Claims

1. An ethylene copolymer made by polymerizing ethylene and 1-butene with a single site catalyst system in a polymerization reactor, the ethylene copolymer having a density of from 0.912 to 0.94 g/cm³, a melt index (I₂) of from 0.5 to 10 g/10 min, a melt flow ratio (I₂₁/I₂) of from 20 to 35, a molecular weight distribution (M_w/M_n) of from 2.0 to 4.5, a shear thinning index of 0.75 or less, and an accelerated haul-off melt, strength (σ

^MS) as determined by Rosand capillary rheometry at 190°

C., of at least 3.0 cN.

2. The ethylene copolymer of claim 1 having a CY a parameter of 0.40 or less.

3. The ethylene copolymer of claim 1 which satisfies the following relationship:

(CDBI₅₀/δ

_XO)^3.0≦

6.5−

5.7 Log [a(1.5(I₂₁/I₂)+(M_w/M_n))];

where CDBI₅₀ is the composition distribution breadth index, δ

_XO is the crossover phase angle at a frequency of 1.0 rad/s and a is the CY a parameter.

4. The ethylene copolymer of claim 1 further satisfying the relationship:

σ

^MS≧

5.0×

10<sup>−

4</sup>×

G*_XO;

where σ

^MS is the accelerated haul-off melt strength determined at 190°

C.; and

G*_XO is the crossover complex modulus at a frequency of 1.0 rad/s.

5. The ethylene copolymer of claim 3 further satisfying the relationship:

σ

^MS≧

5.0×

10<sup>−

4</sup>×

G*_XO;

where σ

^MS is the accelerated haul-off melt strength determined at 190°

C.; and

G*_XO is the crossover complex modulus at a frequency of 1.0 rad/s.

6. A film structure comprising a film layer made from an ethylene/1-butene copolymer wherein the ethylene/1-butene copolymer is made by polymerizing ethylene and 1-butene with a single site catalyst system in a polymerization reactor, the ethylene/1-butene copolymer having density of from 0.912 to 0.94 g/cm³, a melt index (I₂) of from 0.5 to 10 g/10 min, a melt flow ratio (I₂₁/I₂) of from 20 to 35, a molecular weight distribution (M_w/M_n) of from 2.0 to 4.5, a shear thinning index of 0.75 or less, and an accelerated haul-off melt strength (σ

^MS) as determined by Rosand capillary rheometry at 190°

C., of at least 3.0 cN.

7. An ethylene copolymer made by polymerizing ethylene and 1-butene with a single site catalyst system in a polymerization reactor, the ethylene copolymer having density of from 0.912 to 0.94 g/cm³, a melt index (I₂) of from 0.5 to 10 g/10 min, a melt flow ratio (I₂₁/I₂) of from 20 to 35, a molecular weight distribution (M_w/M_n) of from 2.0 to 4.5, and which satisfies the following relationship:

(CDBI₅₀/δ

_XO)^3.0≦

6.5−

5.7 log [a(1.5(I₂₁/I₂)+(M_w/M_n))];

where CDBI₅₀ is the composition distribution breadth index, δ

_XO is the crossover phase angle at a frequency of 1.0 rad/s and a is the CY a parameter.

8. The ethylene copolymer of claim 7 further satisfying the relationship:

σ

^MS≧

5.0×

10<sup>−

4</sup>×

G*_XO;

where σ

^MS is the accelerated haul-off melt strength determined at 190°

C.; and

G*_XO is the crossover complex modulus at a frequency of 1.0 rad/s.

9. A film structure comprising a film layer made from an ethylene/1-butene copolymer wherein the ethylene/1-butene copolymer is made by polymerizing ethylene and 1-butene with a single site catalyst system in a polymerization reactor, the ethylene/1-butene copolymer having density of from 0.912 to 0.94 g/cm³, a melt index (I₂) of from 0.5 to 10 g/10 min, a melt flow ratio (I₂₁/I₂) of from 20 to 35, a molecular weight distribution (M_w/M_n) of from 2.0 to 4.5, and which satisfies the following relationship:

(CDBI₅₀/δ

_XO)^3.0≦

6.5−

5.7 log [a(1.5(I₂₁/I₂)+(M_w/M_n))];

where CDBI₅₀ is the composition distribution breadth index, δ

_XO is the crossover phase angle at a frequency of 1.0 rad/s and a is the CY a parameter.

10. An ethylene copolymer made by polymerizing ethylene and 1-butene with a single site catalyst system in a polymerization reactor, the ethylene copolymer having a density of from 0.912 to 0.94 g/cm³, a melt index (I₂) of from 0.5 to 10 g/10 min, a melt flow ratio (I₂₁/I₂) of from 20 to 35, a molecular weight distribution (M_w/M_n) of from 2.0 to 4.5, a shear thinning index of 0.75 or less, a CY a parameter of 0.40 or less, an accelerated haul-off melt strength (σ

^MS) as determined by Rosand capillary rheometry at 190°

C., of at least 3.0 cN and which satisfies the following relationship;

(CDBI₅₀/δ

_XO)^3.0≦

6.5−

5.7 log [a(1.5(I₂₁/I₂)+(M_w/M_n))];

where CDBI₅₀ is the composition distribution breadth index, δ

_XO is the crossover phase angle at a frequency of 1.0 rad/s and a is the CY a parameter.

11. The ethylene copolymer of claim 10 further satisfying the relationship:

σ

^MS≧

5.0×

10<sup>−

4</sup>×

G*_XO;

where σ

^MS is the accelerated haul-off melt strength determined at 190°

C.; and

G*_XO is the crossover complex modulus at a frequency of 1.0 rad/s.

12. A film structure comprising a film layer made from an ethylene/1-butene copolymer wherein the ethylene/1-butene copolymer is made by polymerizing ethylene and 1-butene with a single site catalyst system in a polymerization reactor, the ethylene copolymer having a density of from 0.912 to 0.94 g/cm³, a melt index (I₂) of from 0.5 to 10 g/10 min, a melt flow ratio (I₂₁/I₂) of from 20 to 35, a molecular weight distribution (M_w/M_n) of from 2.0 to 4.5, a shear thinning index of 0.75 or less, a CY a parameter of 0.40 or less, an accelerated haul-off melt strength (σ

^MS) as determined by Rosand capillary rheometry at 190°

C., of at least 3.0 cN and which satisfies the following relationship;

(CDBI₅₀/δ

_XO)^3.0≦

6.5−

5.7 log [a(1.5(I₂₁/I₂)+(M_w/M_n))];

where CDBI₅₀ is the composition distribution breadth index, δ

_XO is the crossover phase angle at a frequency of 1.0 rad/s and a is the CY a parameter.

13. The film structure of claim 12 wherein the ethylene/1-butene copolymer further satisfies the relationship:

σ

^MS≧

5.0×

10<sup>−

4</sup>×

G*_XO;

where σ

^MS is the accelerated haul-off melt strength determined at 190°

C.; and

G*_XO is the crossover complex modulus at a frequency of 1.0 rad/s.