CA2459552A1 - Bimodal polyethylene composition and articles made therefrom - Google Patents

Bimodal polyethylene composition and articles made therefrom Download PDF

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Publication number
CA2459552A1
CA2459552A1 CA002459552A CA2459552A CA2459552A1 CA 2459552 A1 CA2459552 A1 CA 2459552A1 CA 002459552 A CA002459552 A CA 002459552A CA 2459552 A CA2459552 A CA 2459552A CA 2459552 A1 CA2459552 A1 CA 2459552A1
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Prior art keywords
pipe
polyethylene composition
less
component
molecular weight
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CA002459552A
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French (fr)
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CA2459552C (en
Inventor
Jozef J. Vandun
Patrick J. Schouterden
Kalyan Sehanobish
Peter F. M. Van Den Berghen
Noorallah Jivraj
Johan Vanvoorden
Ravi S. Dixit
Ruddy Nicasy
Frederik E. Gemoets
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Dow Global Technologies LLC
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F10/02—Ethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F210/16—Copolymers of ethene with alpha-alkenes, e.g. EP rubbers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/06—Polyethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/08—Copolymers of ethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/08—Copolymers of ethene
    • C08L23/0807—Copolymers of ethene with unsaturated hydrocarbons only containing more than three carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/08—Copolymers of ethene
    • C08L23/0807—Copolymers of ethene with unsaturated hydrocarbons only containing more than three carbon atoms
    • C08L23/0815—Copolymers of ethene with aliphatic 1-olefins
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F16—ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
    • F16L—PIPES; JOINTS OR FITTINGS FOR PIPES; SUPPORTS FOR PIPES, CABLES OR PROTECTIVE TUBING; MEANS FOR THERMAL INSULATION IN GENERAL
    • F16L9/00—Rigid pipes
    • F16L9/12—Rigid pipes of plastics with or without reinforcement
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F110/02—Ethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/62—Refractory metals or compounds thereof
    • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
    • C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
    • C08F4/65908—Component covered by group C08F4/64 containing a transition metal-carbon bond in combination with an ionising compound other than alumoxane, e.g. (C6F5)4B-X+
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/62—Refractory metals or compounds thereof
    • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
    • C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
    • C08F4/65916—Component covered by group C08F4/64 containing a transition metal-carbon bond supported on a carrier, e.g. silica, MgCl2, polymer
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2308/00—Chemical blending or stepwise polymerisation process with the same catalyst
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2314/00—Polymer mixtures characterised by way of preparation
    • C08L2314/06—Metallocene or single site catalysts

Abstract

The invention relates to a polyethylene composition with a bimodal molecular weight distribution and articles made therefrom, such as high topload blow moldings and transmission and distribution pipes. The composition comprises a low-molecular-weight (LMW) ethylene homopolymer component and a homogeneous, high-molecular-weight (HMW) ethylene interpolymer component, wherein the LMW
component is characterized as having a molecular weight distribution, MWD L, of less than about 8. The composition is characterized as having a bimodal molecular weight distribution, and a ductile-brittle transition temperature, Tdb, of less than -20 ~C. In some embodiments, the HMW component is characterized by a reverse comonomer distribution.

Claims (53)

1. A pipe comprising a polyethylene composition comprising a low-molecular-weight (LMW) ethylene homopolymer component and a homogeneous, high-molecular-weight (HMW) ethylene interpolymer component wherein the LMW component is characterized as having a molecular weight distribution, MWD L, of less than about 8 and a weight average molecular weight, M~, and wherein the polyethylene composition is characterized as having a bimodal molecular weight distribution, and a ductile-brittle transition temperature, T dh, of less than -20°C.
2. The pipe or claim 1, wherein the LMW component of the polyethylene composition has a density of greater than about 0.965 g/cm3.
3. The pipe of claim 1, wherein the LMW component of the polyethylene composition has an I2 value ranging from about 30 to about 1000 g/10 minutes as determined in accordance with ASTM D-1238 (Condition 2.16 kg/190°C).
4. The pipe composition of claim 1, wherein the HMW component or the polyethylene composition has a density ranging from about 0.905 to about 0.955 g/cm3.
5. The pipe of claim 1, wherein the HMW component of the polyethylene composition has an I21.6 value ranging from about 0.1 to about 1.0 as determined in accordance with ASTM D-1238 (Condition 21.6kg/190°C).
6. The pipe of claim 1, wherein the HMW component of the polyethylene composition has an I21.6 value ranging from about 0.1 to about 0.6 as determined in accordance wish ASTM D-1238 (Condition 21.6kg/190°C).
7. The pipe of claim 1, wherein the HMW component of the polyethylene composition has an I21.6 value ranging from greater than 0.6 is about 1.0 as determined in accordance with ASTM D-1238 (Condition 21.6 kg/190°C).
8. The pipe of claim 1, wherein the IIMW of the polyethylene composition is characterized by a unimodal molecular weight distribution, MWD H of about 8 or less and a weight average molecular weight M~.
9. The pipe of claim 8, wherein M~/M~ is about 1.3 or higher.
10. The pipe of claim 1, wherein the MWD L of the LMW component of the polyethylene composition is about 5 or less.
11. The pipe of claim 1, wherein the MWD L of the LMW component of the polyethylene composition is about 3 or less.
12. The pipe of claim 1, wherein the MWD L of the LMW component of the polyethylene composition is about 2.
13. The pipe of claim 8, wherein the MWD II of the HMW component of the polyethylene composition is about 5 or less.
14. The pipe of claim 8, wherein the MWD H of the HMW component of the polyethylene composition is about 3 or less.
15. The pipe of claim 8, wherein the MWD H of the HMW component of the polyethylene composition is about 2.
16. The pipe of claim 1, wherein the polyethylene composition is characterized as a molecular weight distribution (MWD) as defined by the ratio of M w/M n of about 30 or less, and the HMW component is characterized as having a substantially uniform comonomer distribution or a reverse comonomer distribution.
17. The pipe of claim 16, wherein the HMW component of the polyethylene composition has a substantially uniform comonomer distribution characterized by a SCBDI
of greater than 70 percent.
18. The pipe of claim 16, wherein the HMW component of the polyethylene composition has a reverse comonomer distribution characterized as the molar comonomer content of interpolymer fractions having a M w greater than or equal to 300,000 g/mole being at least 25 percent higher than the molar comonomer content of interpolymer fractions having a M w of less than or equal to 100,000 g/mole.
19. The pipe of claim 1, wherein the T db is less than about -25°C,
20. The pipe of claim 1, wherein the T db, is less than about -30°C.
21. The pipe of claim 1, wherein the T db, is less than about -40°C.
22. The pipe of claim 1, wherein the T db is less than about -50°C.
23. The pipe of claim 1, wherein the molecular weight distribution, M w/M o, of the polyethylene composition is less than or equal to 20, as determined using gel permeation chromatography.
24. The pipe - of claim 1, wherein tile polyethylene composition is characterized as having an I21.6/I5 ratio of less than or equal to 22.5, as determined in accordance with ASTM D-1238 (Condition 21.6 kg/190°C and Condition 5 kg/190°C).
25. The pipe of claim 1, wherein the polyethylene composition is characterized as having an I21.6 ranging from about 3 to less than about 50 g/10 min., as determined in accordance with ASTM D-1233 (Condition 21.6 kg/190°C).
26. The pipe of claim 1, wherein the polyethylene composition is characterized as having an I21.6 ranging from about 3 to about 12 g/10 min., as determined in accordance with ASTM D-1238 (Condition 21.6 kg/190°C).
27. The pipe of claim 1, wherein the polyethylene composition is characterized as having an I21.6 ranging from about 12 to less than about 50 g/10 min., as determined in accordance with ASTM D-1238 (Condition 21.6 kg/190°C).
28. The pipe of claim 1, wherein the polyethylene composition is characterised as having an I5 ranging front about 0.1 to about 2 g/10 min., as determined in accordance with ASTM D-1238 (Condition 3 kg/190°C).
29. The pipe of claim 1, wherein the polyethylene composition is characterized as having a density greater than about 0.938 g/cm3.
30. The pipe of claim 1, wherein the polyethylene composition is characterized as having a M v1/M v2 ratio of less than or equal to 0.6, where M v1 is the viscosity average molecular weight of the LMW high density component and M v2 is the viscosity average molecular weight of the LMW interpolymer component, as determined using ATREF-DV
analysis.
31. The pipe of claim 1, wherein the polyethylene composition is manufactured using a multiple reactor slurry polymerization system.
32. The pipe of claim 31, wherein the polymerization system comprises two autoclave reactors.
33. The pipe of claim 32, wherein the two reactors are configured in series.
34. The pipe of claim 33. wherein a supported metallocene catalyst system is used.
35. The pipe of claim 34, wherein catalyst is separately injected into each reactor.
36. The pipe of claim 34, wherein the catalyst system is injected into the first reactor and no catalyst is injected into the second reactor such that polymerization in the second reactor is accomplished from carry-over catalyst or live polymer or both from the first reactor.
37. The pipe of claim 34, wherein the metallocene catalyst is a constrained geometry catalyst.
38. The pine of claim 35, wherein the catalyst is a constrained geometry catalyst system.
39. The pipe of claim 34, wherein the same catalyst is separately injected into each reactor.
40. The pipe of claim 39, wherein the catalyst is a constrained geometry catalyst system.
41. The pipe of claim 34, wherein the catalyst system comprises an activator which has been bonded or fixed to the support prior to the addition of the metallocene catalyst.
42. The pipe of claim 41, wherein the activator is a boron-containing compound.
43. The pipe of claim 41, wherein the activator is an alumoxane.
44. The pipe of claim 1, wherein the HMW component is characterized as having a reverse comonomer distribution.
45. The pipe of claim 44, wherein the reverse comonomer distribution is characterized by a comonomer distribution gradient in the range from about 0.0001 to about 0.1.
46. The pipe of claim 44, wherein the reverse comonomer distribution of the polyethylene composition is characterized by a comonomer distribution gradient in the range from about 0.0005 to about 0.05.
47. The pipe of claim 44, wherein the reverse comonomer distribution of the polyethylene composition is characterized by a comonomer distribution gradient in the range from about 0.001 to about 0.02.
48. The pipe of claim 1, wherein the M w/M n of the polyethylene composition is about 25 or less.
49. The pipe of claim 1, wherein the M w/M n of the polyethylene composition is between about 5 and about 20.
50. The pipe of claim 1, wherein the pipe is a water pipe.
51. The pipe of claim 1, wherein the pipe is a gas pipe.
52. A method of increasing the service life of a pipe comprising using the polyethylene composition claim 1 to form the pipe.
53. A polyethylene composition comprising a low-molecular-weight (LMW) ethylene homopolymer component and a high-molecular-weight (HMW) ethylene interpolymer component, wherein the polyethylene composition is characterized as having a bimodal molecular weight distribution, the molecular weight distribution as defined by the ratio of M w/M n is about 30 or less, and the HMW component is characterized as having a reverse comonomer distribution.
CA2459552A 2001-08-17 2002-08-16 Bimodal polyethylene composition and articles made therefrom Expired - Lifetime CA2459552C (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
US31335701P 2001-08-17 2001-08-17
US60/313,357 2001-08-17
PCT/US2002/026161 WO2003016396A1 (en) 2001-08-17 2002-08-16 Bimodal polyethylene composition and articles made therefrom

Publications (2)

Publication Number Publication Date
CA2459552A1 true CA2459552A1 (en) 2003-02-27
CA2459552C CA2459552C (en) 2011-07-19

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ID=23215394

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CA2459552A Expired - Lifetime CA2459552C (en) 2001-08-17 2002-08-16 Bimodal polyethylene composition and articles made therefrom

Country Status (12)

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US (6) US6787608B2 (en)
EP (1) EP1417260B1 (en)
JP (2) JP5153989B2 (en)
KR (2) KR20080077284A (en)
CN (2) CN1982361B (en)
AT (1) ATE301163T1 (en)
BR (1) BR0211959A (en)
CA (1) CA2459552C (en)
DE (1) DE60205387T2 (en)
MX (1) MXPA04001496A (en)
PL (1) PL203864B1 (en)
WO (1) WO2003016396A1 (en)

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