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Número de publicaciónUS20090068429 A1
Tipo de publicaciónSolicitud
Número de solicitudUS 12/065,215
Número de PCTPCT/US2007/010796
Fecha de publicación12 Mar 2009
Fecha de presentación2 May 2007
Fecha de prioridad2 May 2006
También publicado comoCA2621688A1, CA2621688C, CA2623750A1, CA2623750C, CN101356225A, CN101356225B, CN101356226A, CN101356226B, DE602007005363D1, DE602007007931D1, EP2016127A2, EP2016127B1, EP2016128A2, EP2016128B1, US8445594, US8697806, US9181421, US20080221273, US20130237670, US20140256883, WO2007130515A2, WO2007130515A3, WO2007130553A2, WO2007130553A3
Número de publicación065215, 12065215, PCT/2007/10796, PCT/US/2007/010796, PCT/US/2007/10796, PCT/US/7/010796, PCT/US/7/10796, PCT/US2007/010796, PCT/US2007/10796, PCT/US2007010796, PCT/US200710796, PCT/US7/010796, PCT/US7/10796, PCT/US7010796, PCT/US710796, US 2009/0068429 A1, US 2009/068429 A1, US 20090068429 A1, US 20090068429A1, US 2009068429 A1, US 2009068429A1, US-A1-20090068429, US-A1-2009068429, US2009/0068429A1, US2009/068429A1, US20090068429 A1, US20090068429A1, US2009068429 A1, US2009068429A1
InventoresChester J. Kmiec, William J. Michie, Jr.
Cesionario originalKmiec Chester J, Michie Jr William J
Exportar citaBiBTeX, EndNote, RefMan
Enlaces externos: USPTO, Cesión de USPTO, Espacenet
High-density polyethylene compositions, method of making the same, wire and cable jackets made therefrom, and method of making such wire and cable jackets
US 20090068429 A1
Resumen
The instant invention is a high-density polyethylene composition, method of producing the same, wire and cable jackets made therefrom, and method of making such wire and cable jackets. The high-density polyethylene composition of the instant invention includes a first component, and a second component. The first component is a high molecular weight ethylene alpha-olefin copolymer having a density in the range of 0.915 to 0.940 g/cm3, and a melt index (I21.6) in the range of 0.5 to 10 g/10 minutes. The second component is a low molecular weight ethylene polymer having a density in the range of 0.965 to 0.980 g/cm3, and a melt index (I2) in the range of 50 to 1500 g/10 minutes. The high-density polyethylene composition has a melt index (I2) of at least 1, a density in the range of 0.950 to 0.960 g/cm3, and g′ of equal or greater than 1. The method of producing a high-density polyethylene composition includes the following steps: (1) introducing ethylene, and one or more alpha-olefin comonomers into a first reactor; (2) (co)polymerizing the ethylene in the presence of one or more alpha-olefin comonomers in the first reactor thereby producing a first component, wherein the first component being a high molecular weight ethylene alpha-olefin copolymer having a density in the range of 0.915 to 0.940 g/cm3, and a melt index (I21.6) in the range of 0.5 to 10 g/10 minutes; (3) introducing the first component and additional ethylene into a second reactor; (4) polymerizing the additional ethylene in the second reactor thereby producing a second component, wherein the second component being a low molecular weight ethylene polymer having a density in the range of 0.965 to 0.980 g/cm3, and a melt index (I2) in the range of 50 to 1500 g/10 minutes; and (5) thereby producing the high-density polyethylene composition, wherein the high-density polyethylene composition having a melt index (I2) of at least 1, a density in the range of 0.950 to 0.960 g/cm3, and g′ of equal or greater than 1. The wire and cable jackets according to instant invention comprise the above-described inventive high-density polyethylene composition, and such wire and cable jackets may be made via extrusion.
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Reclamaciones(51)
1. A power or communication cable jacket comprising:
an outer sheath layer comprising:
a high-density polyethylene composition comprising:
a first component, said first component being a high molecular weight ethylene alpha-olefin copolymer having a density in the range of 0.915 to 0.940 g/cm3, and a melt index (I21.6) in the range of 0.5 to 10 g/10 minutes; and
a second component, said second component being a low molecular weight ethylene polymer having a density in the range of 0.965 to 0.980 g/cm3, and a melt index (I2) in the range of 50 to 1500 g/10 minutes;
wherein said high-density polyethylene composition having a melt index (I2) of at least 1 g/10 minutes, a density in the range of 0.940 to 0.960 g/cm3, and g′ of equal or greater than 1.
2. The power or communication cable jacket according to claim 1, wherein said high-density polyethylene composition having a density in the range of 0.950 to 0.960 g/cm3.
3. The power or communication cable jacket according to claim 1, wherein said first component having a density in the range of 0.920 to 0.940 g/cm3.
4. The power or communication cable jacket according to claim 1, wherein said power or communication cable jacket having an average smoothness of equal or less than 18 micro-inches.
5. The power or communication cable jacket according to claim 1, wherein said power or communication cable jacket having an average surface smoothness of equal or less than 15 micro-inches.
6. The power or communication cable jacket according to claim 1, wherein said power or communication cable jacket having shrink on-wire after at least 24 hours of equal or less than 1.3 percent.
7. The power or communication cable jacket according to claim 1, wherein said power or communication cable jacket having shrink back off-wire after at least 24 hours of equal or less than 3.39 percent.
8. The power or communication cable jacket according to claim 1, wherein said first component having a density in the range of 0.921 to 0.936 g/cm3.
9. The power or communication cable jacket according to claim 1, wherein said first component having a melt index (I21.6) in the range of 1 to 7 g/10 minutes.
10. The power or communication cable jacket according to claim 1, wherein said first component having a melt index (I21.6) in the range of 1.3 to 5 g/10 minutes.
11. The power or communication cable jacket according to claim 1, wherein said second component having a density in the range of 0.970 to 0.975 g/cm3.
12. The power or communication cable jacket according to claim 1, wherein said second component having a melt index (I2) in the range of 100 to 1500 g/10 minutes.
13. The power or communication cable jacket according to claim 1, wherein said second component having a melt index (I2) in the range of 200 to 1500 g/10 minutes.
14. The power or communication cable jacket according to claim 1, wherein said high-density polyethylene composition having a melt index (I2) in the range of 1 to 2 g/10 minutes.
15. The power or communication cable jacket according to claim 1, wherein said high-density polyethylene composition having a melt index (I2) of at least 2 g/10 minutes.
16. The power or communication cable jacket according to claim 1, wherein said first component having a molecular weight in the range of 150,000 to 375,000.
17. The power or communication cable jacket according to claim 1, wherein said second component having a molecular weight in the range of 12,000 to 40,000.
18. The power or communication cable jacket according to claim 1, wherein said first component having a density in the range of 0.921 to 0.936 g/cm3, and a melt index (I21.6) in the range of 1.3 to 5 g/10 minutes; wherein said second component having a density in the range of 0.970 to 0.975 g/cm3, and a melt index (I2) in the range of 200 to 1500 g/10 minutes.
19. The power or communication cable jacket according to claim 1, wherein said first component being substantially free of any long chain branching, and said second component being substantially free of any long chain branching.
20. The power or communication cable jacket according to claim 14, wherein said high-density polyethylene composition being substantially free of any long chain branching.
21. The power or communication cable jacket according to claim 1, wherein said high-density polyethylene composition having a single ATREF temperature peak, wherein said ATREF temperature peak having a temperature peak maximum between 90° C. to 105° C.
wherein said high-density polyethylene composition having a calculated high density fraction in the range of 20 percent to 50 percent, said calculated high density fraction being defined as [(2)×(the weight ratio of the high-density polyethylene that elutes in ATREF-DV at temperatures greater than or equal to said temperature peak maximum)],
wherein said high-density polyethylene composition having a relative minimum in the log of the relative viscosity average molecular weight at about 90° C. in ATRF-DV;
wherein said high-density polyethylene composition having a regression slop of the log of the relative viscosity average molecular weight versus the ATREF-DV viscosity versus temperature plot of less than about 0, said elution temperature measured between 70° C. to 90° C.
22. The power or communication cable jacket according to claim 1, wherein said high-density polyethylene composition having a comonomer content in weight percent of equal or greater that [(−228.41*density of said high-density polyethylene composition)+219.36)]*[1(weight percent)/(g/cm3)], wherein the density being measured in g/cm3.
23. The power or communication cable jacket according to claim 1, wherein said high-density polyethylene composition having an ATREF high-density fraction in percent of equal or less than [(2750*density of the high-density polyethylene composition)−2552.2]*[1(percent)/(g/cm3)], where the density being measured in g/cm3.
24. A method of making a power or communication cable jacket comprising the steps of:
providing a high-density polyethylene composition comprising;
a first component, said first component being a high molecular weight ethylene alpha-olefin copolymer having a density in the range of 0.915 to 0.940 g/cm3, and a melt index (I21.6) in the range of 0.5 to 10 g/10 minutes; and
a second component, said second component being a low molecular weight ethylene polymer having a density in the range of 0.965 to 0.980 g/cm3, and a melt index (I2) in the range of 50 to 1500 g/10 minutes;
wherein said high-density polyethylene composition having a melt index (I2) of at least 1 μl 0 minutes, a density in the range of 0.940 to 0.960 g/cm3, and g′ of equal or greater than 1;
extruding said high-density polyethylene composition over a power or communication cable;
thereby forming said power or communication cable jacket.
25. The method of making a power or communication cable jacket composition according to claim 24, wherein said high-density polyethylene composition being extruded over a power or communication cable at a rate of at least 200 ft/minute.
26. The method of making a power or communication cable jacket composition according to claim 25, wherein said power or communication cable jacket having an average smoothness of equal or less than 18 micro-inches.
27. The method of making a power or communication cable jacket composition according to claim 25, wherein said power or communication cable jacket having an average surface smoothness of equal or less than 15 micro-inches.
28. The method of making a power or communication cable jacket composition according to claim 25, wherein said power or communication cable jacket having shrink on-wire after at least 24 hours of equal or less than 1.3 percent.
29. The power or communication cable jacket according to claim 25, wherein said power or communication cable jacket having shrink back off-wire after at least 24 hours of equal or less than 3.39 percent.
30. The method of making a power or communication cable jacket composition according to claim 24, wherein said high-density polyethylene composition being extruded over a power or communication cable at a rate of at least 300 ft/minute.
31. The method of making a power or communication cable jacket composition according to claim 30, wherein said power or communication cable jacket having an average smoothness of equal or less than 18 micro-inches.
32. The method of making a power or communication cable jacket composition according to claim 30, wherein said power or communication cable jacket having an average surface smoothness of equal or less than 15 micro-inches.
33. The method of making a power or communication cable jacket composition according to claim 30, wherein said power or communication cable jacket having shrink on-wire after at least 24 hours of equal or less than 1.3 percent.
34. The power or communication cable jacket according to claim 30, wherein said power or communication cable jacket having shrink back off-wire after at least 24 hours of equal or less than 3.39 percent.
35. The method of making a power or communication cable jacket composition according to claim 34, wherein said first component having a density in the range of 0.920 to 0.940 g/cm3.
36. The method of making a power or communication cable jacket composition according to claim 34, wherein said first component having a density in the range of 0.921 to 0.936 g/cm3.
37. The method of making a power or communication cable jacket composition according to claim 34, wherein said first component having a melt index (I21.6) in the range of 1 to 7 g/10 minutes.
38. The method of making a power or communication cable jacket composition according to claim 34, wherein said first component having a melt index (I21.6) in the range of 1.3 to 5 g/10 minutes.
39. The method of making a power or communication cable jacket composition according to claim 34, wherein said second component having a density in the range of 0.970 to 0.975 g/cm3.
40. The method of making a power or communication cable jacket composition according to claim 34, wherein said second component having a melt index (I2) in the range of 100 to 1500 g/10 minutes.
41. The method of making a power or communication cable jacket composition according to claim 34, wherein said second component having a melt index (I2) in the range of 200 to 1500 g/10 minutes.
42. The method of making a power or communication cable jacket according to claim 34, wherein said high-density polyethylene composition having a melt index (I2) in the range of 1 to 2 g/10 minutes.
43. The method of making a power or communication cable jacket according to claim 34, wherein said high-density polyethylene composition having a melt index (I2) of at least 2 g/10 minutes.
44. The method of making a power or communication cable jacket according to claim 34, wherein said first component having a molecular weight in the range of 150,000 to 375,000.
45. The method of making a power or communication cable jacket according to claim 34, wherein said second component having a molecular weight in the range of 12,000 to 40,000.
46. The method of making a power or communication cable jacket according to claim 34, wherein said first component having a density in the range of 0.921 to 0.936 g/cm3, and a melt index (I21.6) in the range of 1.3 to 5 g/10 minutes; wherein said second component having a density in the range of 0.970 to 0.975 g/cm3, and a melt index (I2) in the range of 200 to 1500 g/10 minutes.
47. The method of making a power or communication cable jacket according to claim 34, wherein said first component being substantially free of any long chain branching, and said second component being substantially free of any long chain branching.
48. The method of making a power or communication cable jacket according to claim 47, wherein said high-density polyethylene composition being substantially free of any long chain branching.
49. The method of making a power or communication cable jacket according to claim 34, wherein said high-density polyethylene composition having a single ATREF temperature peak, wherein said ATREF temperature peak having a temperature peak maximum between 90° C. to 105° C.;
wherein said high-density polyethylene composition having a calculated high density fraction in the range of 20 percent to 50 percent, said calculated high density fraction being defined as [(2)*(the weight ratio of the high-density polyethylene that elutes in ATREF-DV at temperatures grater than or equal to said temperature peak maximum)],
wherein said high-density polyethylene composition having a relative minimum in the log of the relative viscosity average molecular weight at about 90° C. in ATRF-DV;
wherein said high-density polyethylene composition having a regression slop of the log of the relative viscosity average molecular weight versus the ATREF-DV viscosity versus temperature plot of less than about 0, said elution temperature measured between 70° C. to 90° C.
50. The method of making a power or communication cable jacket according to claim 34, wherein said high-density polyethylene composition having an ATREF high-density fraction in percent of equal or less than [(2750*density of the high-density polyethylene composition)−2552.2]*[1(percent)/(g/cm3)], where density is measured in g/cm3.
51. The method of making a power or communication cable jacket according to claim 34, wherein said high-density polyethylene composition having a comonomer content in weight percent equal or greater that [(−228.41*density of high-density polyethylene composition)+219.36)]*[1(weight percent)/(g/cm3)], where density is measured in g/cm3.
Descripción
    CROSS-REFERENCE TO RELATED APPLICATIONS
  • [0001]
    This application is a non-provisional application claiming priority from the U.S. Provisional Patent Application Ser. No. 60/796,809, filed on May 2, 2006 entitled “High-Density Polyethylene Compositions and Method of Making the Same,” the teachings of which are herein as if reproduced in fill hereinbelow.
  • FIELD OF INVENTION
  • [0002]
    The instant invention relates a high-density polyethylene composition, method of producing the same, wire and cable jackets made therefrom, and method of making such wire and cable jackets.
  • BACKGROUND OF THE INVENTION
  • [0003]
    Cables, such as power or communication cables, typically include an inner, which comprises a conducting element such as a metal wire or a glass fiber, and one or more outer layers for shielding and protecting purposes. The outermost layer of these layers having mainly protective purpose is usually referred to as the outer sheath or outer jacket.
  • [0004]
    The use of polymeric materials, such as polyolefins, to manufacture outermost protective layers is generally known. In particular, it is well known to produce outermost protective layers from polyethylenes.
  • [0005]
    In general, the polymeric material used to manufacture cable jackets should possess good processability, such as good extrusion properties at broad processing temperature ranges. Furthermore, such cable jackets should generally possess good mechanical properties, such as good environmental stress crack resistance (ESCR), high mechanical strength, high surface finish, and low shrinkage.
  • [0006]
    Despite the research efforts in developing and improving cable jackets, there is still a need for a polymeric composition with improved processability and cable jackets made therefrom having improved mechanical properties, such as improved environmental stress crack resistance (ESCR), high mechanical strength, high surface finish, and low shrinkage. The inventive high-density polyethylene composition provides improved surface smoothness, shrink-back and extrusion processing characteristics without loss of other critical wire coating performance properties, for example ESCR.
  • SUMMARY OF THE INVENTION
  • [0007]
    The instant invention is a high-density polyethylene composition, method of producing the same, wire and cable jackets made therefrom, and method of making such wire and cable jackets. The high-density polyethylene composition of the instant invention includes a first component, and a second component. The first component is a high molecular weight ethylene alpha-olefin copolymer having a density in the range of 0.915 to 0.940 g/cm3, and a melt index (I21.6) in the range of 0.5 to 10 g/10 minutes. The second component is a low molecular weight ethylene polymer having a density in the range of 0.965 to 0.980 g/cm3, and a melt index (I2) in the range of 50 to 1500 g/10 minutes. The high-density polyethylene composition has a melt index (I2) of at least 1, a density in the range of 0.940 to 0.960 g/cm3, and g′ of equal or greater than 1. The method of producing a high-density polyethylene composition includes the following steps: (1) introducing ethylene, and one or more alpha-olefin comonomers into a first reactor; (2) (co)polymerizing the ethylene in the presence of one or more alpha-olefin comonomers in the first reactor thereby producing a first component, wherein the first component being a high molecular weight ethylene alpha-olefin copolymer having a density in the range of 0.915 to 0.940 g/cm3, and a melt index (I21.6) in the range of 0.5 to 10 g/10 minutes; (3) introducing the first component and additional ethylene into a second reactor; (4) polymerizing the additional ethylene in the second reactor thereby producing a second component, wherein the second component being a low molecular weight ethylene polymer having a density in the range of 0.965 to 0.980 g/cm3, and a melt index (I2) in the range of 50 to 1500 g/110 minutes; and (5) thereby producing the high-density polyethylene composition, wherein the high-density polyethylene composition having a melt index (I2) of at least 1, a density in the range of 0.940 to 0.960 g/cm3, and g′ of equal or greater than 1. The wire and cable jackets according to instant invention comprise the above-described inventive high-density polyethylene composition, and such wire and cable jackets may be made via extrusion process.
  • [0008]
    In one embodiment, the instant invention provides a high-density polyethylene composition comprising a high molecular weight polyethylene alpha-olefin copolymer having a density in the range of 0.915 to 0.940 g/cm3, and a melt index (I21.6) in the range of 0.5 to 10 g/10 minutes, and a low molecular weight ethylene polymer having a density in the range of 0.965 to 0.980 g/cm3, and a melt index (I2) in the range of 50 to 1500 g/10 minutes, wherein the inventive high-density polyethylene composition having a melt index (I2) of at least 1 g/10 minutes, a density in the range of 0.940 to 0.960 g/cm3, and g′ of equal or greater than 1.
  • [0009]
    In an alternative embodiment, the instant invention further provides a method for producing a high-density polyethylene composition comprising the steps of: (1) introducing ethylene, and one or more alpha-olefin comonomers into a first reactor; (2) (co)polymerizing the ethylene in the presence of one or more alpha-olefin comonomers in the first reactor thereby producing a high molecular weight ethylene alpha-olefin copolymer having a density in the range of 0.915 to 0.940 g/cm3, and a melt index (I21) in the range of 0.5 to 10 g/10 minutes; (3) introducing the high molecular weight ethylene alpha-olefin copolymer and additional ethylene into a second reactor; (4) polymerizing the additional ethylene in the second reactor thereby producing a low molecular weight ethylene polymer having a density in the range of 0.965 to 0.980 g/cm3, and a melt index (I2) in the range of 50 to 1500 g/10 minutes; and (5) thereby producing the high-density polyethylene composition, wherein the high-density polyethylene composition having a melt index (I2) of at least 1, a density in the range of 0.940 to 0.960 g/cm3, and g′ of equal or greater than 1.
  • [0010]
    In another alternative embodiment, the instant invention provides wire and cable jackets comprising a high-density polyethylene composition, wherein the high-density polyethylene composition comprising a high molecular weight polyethylene alpha-olefin copolymer having a density in the range of 0.915 to 0.940 g/cm3, and a melt index (I21.6) in the range of 0.5 to 10 g/10 minutes, and a low molecular weight ethylene polymer having a density in the range of 0.965 to 0.980 g/cm3, and a melt index (I2) in the range of 50 to 1500 g/10 minutes, wherein the inventive high-density polyethylene composition having a melt index (I2) of at least 1 g/10 minutes, a density in the range of 0.940 to 0.960 g/cm3, and g′ of equal or greater than 1.
  • [0011]
    In another alternative embodiment, the instant invention provides a method of making wire and cable jackets comprising the steps of: (1) providing a high-density polyethylene composition comprising a high molecular weight ethylene alpha-olefin copolymer having a density in the range of 0.915 to 0.940 g/cm3, and a melt index (I21.6) in the range of 0.5 to 10 g/10 minutes; and a low molecular weight ethylene polymer having a density in the range of 0.965 to 0.980 g/cm3, and a melt index (I2) in the range of 50 to 1500 g/10 minutes; wherein the high-density polyethylene composition having a melt index (I2) of at least 1 g/10 minutes, a density in the range of 0.940 to 0.960 g/cm3, and g′ of equal or greater than 1; (2) extruding said high-density polyethylene composition over a power or communication cable, and (3) thereby forming the power or communication cable jacket.
  • [0012]
    In an alternative embodiment, the instant invention provides a method for producing a high-density polyethylene composition, method of producing the same, wire and cable jackets made therefrom, and method of making such wire and cable jackets, in accordance with any of the preceding embodiments except that the high density polyethylene having a density in the range of 0.950 to 0.96 g/cm3.
  • [0013]
    In an alternative embodiment, the instant invention provides a high-density polyethylene composition, method of producing the same, wire and cable jackets made therefrom, and method of making such wire and cable jackets, in accordance with any of the preceding embodiments, except that the high molecular weight polyethylene alpha-olefin copolymer having a density in the range of 0.920 to 0.940 g/cm3.
  • [0014]
    In another alternative embodiment, the instant invention provides a high-density polyethylene composition, method of producing the same, wire and cable jackets made therefrom, and method of making such wire and cable jackets, in accordance with any of the preceding embodiments, except that the high molecular weight polyethylene alpha-olefin copolymer having a density in the range of 0.921 to 0.936 g/cm3.
  • [0015]
    In another alternative embodiment, the instant invention provides a high-density polyethylene composition, method of producing the same, wire and cable jackets made therefrom, and method of making such wire and cable jackets, in accordance with any of the preceding embodiments, except that the high molecular weight polyethylene alpha-olefin copolymer having a melt index (I21.6) in the range of 1 to 7 g/10 minutes.
  • [0016]
    In another alternative embodiment, the instant invention provides a high-density polyethylene composition, method of producing the same, wire and cable jackets made therefrom, and method of making such wire and cable jackets, in accordance with any of the preceding embodiments, except that the high molecular weight polyethylene alpha-olefin copolymer having a melt index (I21.6) in the range of 1.3 to 5 g/1 minutes.
  • [0017]
    In another alternative embodiment, the instant invention provides a high-density polyethylene composition, method of producing the same, wire and cable jackets made therefrom, and method of making such wire and cable jackets, in accordance with any of the preceding embodiments, except that the low molecular weight ethylene polymer having a density in the range of 0.970 to 0.975 g/cm3.
  • [0018]
    In another alternative embodiment, the instant invention provides a high-density polyethylene composition, method of producing the same, wire and cable jackets made therefrom, and method of making such wire and cable jackets, in accordance with any of the preceding embodiments, except that the low molecular weight ethylene polymer having a melt index (I2) in the range of 100 to 1500 g/10 minutes.
  • [0019]
    In another alternative embodiment, the instant invention provides a high-density polyethylene composition, method of producing the same, wire and cable jackets made therefrom, and method of making such wire and cable jackets, in accordance with any of the preceding embodiments, except that the low molecular weight ethylene polymer having a melt index (I2) in the range of 200 to 1500 g/10 minutes.
  • [0020]
    In another alternative embodiment, the instant invention provides a high-density polyethylene composition, method of producing the same, wire and cable jackets made therefrom, and method of making such wire and cable jackets, in accordance with any of the preceding embodiments, except that the high-density polyethylene composition having a melt index (I2) in the range of 1 to 2 g/10 minutes; or in the alternative, having a melt index (I2) of at least 2 g/10 minutes.
  • [0021]
    In another alternative embodiment, the instant invention provides a high-density polyethylene composition, method of producing the same, wire and cable jackets made therefrom, and method of making such wire and cable jackets, in accordance with any of the preceding embodiments, except that the high molecular weight ethylene alpha-olefin copolymer having a molecular weight in the range of 150,000 to 375,000.
  • [0022]
    In another alternative embodiment, the instant invention provides a high-density polyethylene composition, method of producing the same, wire and cable jackets made therefrom, and method of making such wire and cable jackets, in accordance with any of the preceding embodiments, except that the low molecular weight ethylene polymer having a molecular weight in the range of 12,000 to 40,000.
  • [0023]
    In another alternative embodiment, the instant invention provides a high-density polyethylene composition, method of producing the same, wire and cable jackets made therefrom, and method of making such wire and cable jackets, in accordance with any of the preceding embodiments, except that the high molecular weight polyethylene alpha-olefin copolymer having a density in the range of 0.921 to 0.936 g/cm3, and a melt index (I21.6) in the range of 1.3 to 5 g/10 minutes, and the low molecular weight ethylene polymer having a density in the range of 0.970 to 0.975 g/cm3, and a melt index (I2) in the range of 200 to 1500 g/10 minutes.
  • [0024]
    In another alternative embodiment, the instant invention provides a high-density polyethylene composition, method of producing the same, wire and cable jackets made therefrom, and method of making such wire and cable jackets, in accordance with any of the preceding embodiments, except that both the high molecular weight polyethylene alpha-olefin copolymer and the low molecular weight ethylene polymer being substantially free of any long chain branching.
  • [0025]
    In another alternative embodiment, the instant invention provides a high-density polyethylene composition, method of producing the same, wire and cable jackets made therefrom, and method of making such wire and cable jackets, in accordance with any of the preceding embodiments, except that the high-density polyethylene composition being substantially free of any long chain branching.
  • [0026]
    In another alternative embodiment, the instant invention provides a high-density polyethylene composition, method of producing the same, wire and cable jackets made therefrom, and method of making such wire and cable jackets, in accordance with any of the preceding embodiments, except that the high-density polyethylene composition having a single ATREF temperature peak, wherein the ATREF temperature peak having a temperature peak maximum between 90° C. to 105° C.; and wherein the high-density polyethylene composition having a calculated high density fraction in the range of 20 percent to 50 percent, said calculated high density fraction being defined as [(2)×(the weight ratio of the high-density polyethylene that elutes in ATREF-DV at temperatures greater than or equal to the temperature peak maximum)]; and wherein the high-density polyethylene composition having a relative minimum in the log of the relative viscosity average molecular weight at about 90° C. in ATRF-DV; and wherein the high-density polyethylene composition having a regression slope of the log of the relative viscosity average molecular weight versus the ATREF-DV viscosity v. temperature plot of less than about 0, where the elution temperature measured between 70° C. to 90° C.
  • [0027]
    In another alternative embodiment, the instant invention provides a high-density polyethylene composition, method of producing the same, wire and cable jackets made therefrom, and method of making such wire and cable jackets, in accordance with any of the preceding embodiments, except that the high-density polyethylene composition having a comonomer content in weight percent equal or greater that [(−228.41*density of high-density polyethylene composition)+219.36)]*[1(weight percent)/(g/cm3)], where density is measured in g/cm3.
  • [0028]
    In another alternative embodiment, the instant invention provides a high-density polyethylene composition, method of producing the same, wire and cable jackets made therefrom, and method of making such wire and cable jackets, in accordance with any of the preceding embodiments, except that the high-density polyethylene composition having an ATREF high-density fraction in percent of equal or less than [(2750*density of the high-density polyethylene composition)−2552.2]*[1(percent)/(g/cm3)], where density is measured in g/cm3.
  • [0029]
    In another alternative embodiment, the instant invention provides wire and cable jackets and a method of making such wire and cable jackets, in accordance with any of the preceding embodiments, except that the high-density polyethylene composition being extruded over a power or communication cable at a rate of at least 200 ft/minute.
  • [0030]
    In another alternative embodiment, the instant invention provides wire and cable jackets and a method of making such wire and cable jackets, in accordance with any of the preceding embodiments, except that jacket having an average smoothness of equal or less than 18 micro-inches.
  • [0031]
    In another alternative embodiment, the instant invention provides wire and cable jackets and a method of making such wire and cable jackets, in accordance with any of the preceding embodiments, except that jacket having an average surface smoothness of equal or less than 15 micro-inches.
  • [0032]
    In another alternative embodiment, the instant invention provides wire and cable jackets and a method of making such wire and cable jackets, in accordance with any of the preceding embodiments, except that jacket having shrink on-wire after at least 24 hours of equal or less than 1.3 percent.
  • [0033]
    In another alternative embodiment, the instant invention provides wire and cable jackets and a method of making such wire and cable jackets, in accordance with any of the preceding embodiments, except that jacket having shrink back off-wire after at least 24 hours of equal or less than 3.39 percent.
  • [0034]
    In another alternative embodiment, the instant invention provides wire and cable jackets and a method of making such wire and cable jackets, in accordance with any of the preceding embodiments, except that the composition being extruded over a power or communication cable at a rate of at least 300 ft/minute.
  • [0035]
    In another alternative embodiment, the instant invention provides wire and cable jackets and a method of making such wire and cable jackets, in accordance with any of the preceding embodiments, except that jacket having an average smoothness of equal or less than 18 micro-inches.
  • [0036]
    In another alternative embodiment, the instant invention provides wire and cable jackets and a method of making such wire and cable jackets, in accordance with any of the preceding embodiments, except that jacket having an average surface smoothness of equal or less than 15 micro-inches.
  • [0037]
    In another alternative embodiment, the instant invention provides wire and cable jackets and a method of making such wire and cable jackets, in accordance with any of the preceding embodiments, except that jacket having shrink on-wire after at least 24 hours of equal or less than 1.3 percent.
  • [0038]
    In another alternative embodiment, the instant invention provides wire and cable jackets and a method of making such wire and cable jackets, in accordance with any of the preceding embodiments, except that jacket having shrink back off-wire after at least 24 hours of equal or less than 3.39 percent.
  • BRIEF DESCRIPTION OF THE DRAWINGS
  • [0039]
    For the purpose of illustrating the instant invention, there is shown in the drawings a form that is presently preferred; it being understood, however, that this invention is not limited to the precise arrangements and instrumentalities shown.
  • [0040]
    FIG. 1 is a graph illustrating the relationship between the comonomer content and the density of the high-density polyethylene composition of the instant invention;
  • [0041]
    FIG. 2 is a graph illustrating the relationship between high density fraction measured via analytical temperature raising elution fractionation analysis (ATREF) and density of the inventive high-density polyethylene composition;
  • [0042]
    FIG. 3 is a graph illustrating the relationship between the calculated high density fraction measured via analytical temperature raising elution fractionation analysis (ATREF) and the density of the high molecular weight polyethylene component of the inventive high-density polyethylene composition; and
  • [0043]
    FIG. 4 illustrates how the calculated ATREF high-density fraction of the high molecular weight polyethylene component of the inventive Example 1 was determined.
  • DETAILED DESCRIPTION OF THE INVENTION
  • [0044]
    The high-density polyethylene composition of the instant invention includes a first component, and a second component. The first component is preferably a high molecular weight ethylene alpha-olefin copolymer having a density in the range of 0.915 to 0.940 g/cm3, and a melt index (I21) of 0.5 to 10 g/10 minutes. The second component is preferably a low molecular weight ethylene polymer having a density in the range of 0.965 to 0.980 g/cm3, and a melt index (I2) in the range of 50 to 1500 g/10 minutes. The high-density polyethylene composition has a melt index (I2) of at least 1 g/10 minutes, a density in the range of 0.950 to 0.960 g/cm3, and g′ of equal or greater than 1. The high-density polyethylene composition may further include additional components, additives, or adjuvants. The high-density polyethylene composition is a bimodal polymer, or in the alternative, the high-density polyethylene is a multimodal polymer.
  • [0045]
    The term “bimodal,” as used herein, means that the molecular weight distribution (MWD) in a Gel Permeation Chromatography (GPC) curve exhibits two component polymers, for example, two peaks or wherein one component polymer may even exist as a hump, shoulder, or tail relative to the MWD of the other component polymer; or in the alternative, for example, wherein the two components may have only one single peak with no bumps, shoulders, or tails.
  • [0046]
    The term “multimodal” as used herein means that the MWD in a GPC curve exhibits more than two component polymers, for example, three or more peaks or wherein one component polymer may even exist as a hump, shoulder, or tail, relative to the MWD of the other component polymers; or in the alternative, wherein three or more components may have only one single pick with no bumps, shoulders, or tails.
  • [0047]
    The term “polymer” is used herein to indicate a homopolymer, an interpolymer (or copolymer), or a terpolymer. The term “polymer,” as used herein, includes interpolymers, such as, for example, those made by the copolymerization of ethylene with one or more C3-C20 alpha-olefin(s).
  • [0048]
    The term “interpolymer,” as used herein, refers to polymers prepared by the polymerization of at least two different types of monomers. The generic term interpolymer thus includes copolymers, usually employed to refer to polymers prepared from two different types of monomers, and polymers prepared from more than two different types of monomers.
  • [0049]
    The term (co)polymerization, as used herein, refers to polymerization of ethylene in the presence of one or more alpha-olefin comonomers.
  • [0050]
    The first component is a polymer; for example, a polyolefin. The first component is preferably be an ethylene polymer; for example, first component is preferably a high molecular weight ethylene alpha-olefin copolymer. The first component is substantially free of any long chain branching. Substantially free of any long chain branching, as used herein, refers to an ethylene polymer preferably substituted with less than about 0.1 long chain branch per 1000 total carbons, and more preferably, less than about 0.01 long chain branch per 1000 total carbons. The presence of long chain branches is typically determined according to the methods known in the art, such as gel permeation chromatography coupled with low angle laser light scattering detector (GPC-LALLS) and gel permeation chromatography coupled with a differential viscometer detector (GPC-DV). The first component has a density in the range of 0.915 to 0.940 g/cm3. All individual values and subranges from 0.915 to 0.940 g/cm3 are included herein and disclosed herein; for example, the first component has a density in the range of 0.920 to 0.940 g/cm3, or in the alternative, the first component has a density in the range of 0.921 to 0.936 g/cm3. The first component has a melt index (I21.6) in the range of 0.5 to 10 g/10 minutes. All individual values and subranges from 0.5 to 10 g/10 minutes are included herein and disclosed herein; for example, the first component has a melt index (I21.6) in the range of 1 to 7 g/10 minutes, or in the alternative, the first component has a melt index (I21.6) in the range of 1.3 to 5 g/10 minutes. The first component has molecular weight in the range of 150,000 to 375,000. All individual values and subranges from 150,000 to 375,000 are included herein and disclosed herein; for example, the first component has a molecular weight in the range of 175,000 to 375,000; or in the alternative, the first component has a molecular weight in the range of 200,000 to 375,000. The first component may comprise any amount of one or more alpha-olefin copolymers; for example, the first component comprises about less than 10 percent by weight of one or more alpha-olefin comonomers, based on the weight of the first component. All individual values and subranges less than 10 weight percent are included herein and disclosed herein. The first component may comprise any amount of ethylene; for example, the first component comprises at least about 90 percent by weight of ethylene, based on the weight of the first component. All individual values and subranges above 90 weight percent are included herein and disclosed herein; for example, the first component comprises at least 95 percent by weight of ethylene, based on the weight of the first component.
  • [0051]
    The alpha-olefin comonomers typically have no more than 20 carbon atoms. For example, the alpha-olefin comonomers may preferably have 3 to 10 carbon atoms, and more preferably 3 to 8 carbon atoms. Exemplary alpha-olefin comonomers include, but are not limited to, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, and 4-methyl-1-pentene. The alpha-olefin comonomers are preferably selected from the group consisting of propylene, 1-butene, 1-hexene, and 1-octene, and more preferably from the group consisting of 1-hexene and 1-octene.
  • [0052]
    The second component is a polymer; for example, a polyolefin. The second component is preferably an ethylene polymer; for example, second component is preferably a low molecular weight ethylene homopolymer. The ethylene homopolymer may contain trace amounts of contaminate comonomers, for example alpha-olefin comonomers. The term ethylene homopolymer, as used herein, refers to an ethylene polymer containing at least 99 percent by weight of ethylene units. The second component is preferably substantially free of any long chain branching. Substantially free of any long chain branching, as used herein, refers to an ethylene polymer preferably substituted with less than about 0.1 long chain branch per 1000 total carbons, and more preferably, less than about 0.01 long chain branch per 1000 total carbons. The presence of long chain branches is typically determined according to the methods known in the art, as mentioned above. The second component has a density in the range of 0.965 to 0.980 g/cm3. All individual values and subranges from 0.965 to 0.980 g/cm3 are included herein and disclosed herein; for example, the second component has a density in the range of 0.970 to 0.975 g/cm3. The second component has a melt index (I2) in the range of 50 to 1500 g/10 minutes. All individual values and subranges from 50 to 1500 g/10 minutes are included herein and disclosed herein; for example, the second component has a melt index (I2) in the range of 200 to 1500 g/10 minutes; or in the alternative, the second component has a melt index (I2) in the range of 500 to 1500 g/10 minutes. The second component has a molecular weight in the range of 12,000 to 40,000. All individual values and subranges from 12,000 to 40,000 are included herein and disclosed herein; for example, the second component has a molecular weight in the range of 15,000 to 40,000; or in the alternative, the second component has a molecular weight in the range of 20,000 to 40,000. The second component comprises less than 1.00 percent by weight of one or more alpha-olefin copolymers, based on the weight of the second component. All individual values and subranges from less than 1.00 weight percent are included herein and disclosed herein; for example, the second component may comprise 0.0001 to 1.00 percent by weight of one or more alpha-olefin copolymers; the second component may comprise 0.001 to 1.00 percent by weight of one or more alpha-olefin copolymers. The second component comprises at least about 99 percent by weight of ethylene, based on the weight of the second component. All individual values and subranges from 99 to 100 weight percent are included herein and disclosed herein; for example, the second component comprises 99.5 to 100 percent by weight of ethylene, based on the weight of the second component.
  • [0053]
    The high-density polyethylene composition has a density in the range of 0.940 to 0.960 g/cm3. All individual values and subranges from 0.940 to 0.960 g/cm3 are included herein and disclosed herein; for example, the high-density polyethylene composition has a density in the range of 0.950 to 0.960 g/cm3. The high-density polyethylene composition has a melt index (I2) of at least 1 g/10 minutes. All individual values and subranges equal or greater than 1 g/10 minutes are included herein and disclosed herein; for example, the high-density polyethylene composition has a melt index (I2) in the range of 1 to 2 g/10 minutes; or in the alternative, the high-density polyethylene composition has a melt index (I2) of at least 2 g/10 minutes. The high-density polyethylene composition is substantially free of any long chain branching. Substantially free of any long chain branching, as used herein, refers to a polyethylene composition preferably substituted with less than about 0.1 long chain branch per 1000 total carbons, and more preferably, less than about 0.01 long chain branch per 1000 total carbons. The presence of long chain branches is typically determined according to the methods known in the art, as mentioned above. The high-density polyethylene composition has a molecular weight distribution in the range of 6 to 25. All individual values and subranges from 6 to 25 are included herein and disclosed herein; for example, the high-density polyethylene composition has a molecular weight distribution in the range of 7 to 20; or in the alternative, the high-density polyethylene composition has a molecular weight distribution in the range of 7 to 17. The term molecular weight distribution or “MWD,” as used herein, refers to the ratio of weight average molecular weight (Mw) to number average molecular weight (Mn), that is (Mw/Mn), described in further details hereinbelow. The high-density polyethylene composition has an environmental stress crack resistance of at least 150 hours measured via ASTM D-1693, Condition B, 10 percent Igepal, or preferably at least 200 hours measured via ASTM D-1693, Condition B, 10% Igepal, or more preferably, at least 250 hours measured via ASTM D-1693, Condition B, 10 percent Igepal. In the alternative, the high-density polyethylene composition has an environmental stress crack resistance of at least 300 hours measured via ASTM D-1693, Condition B, 100 percent Igepal, or preferably, at least 400 hours measured via ASTM D-1693, Condition B, 100 percent Igepal, or more preferably, at least 500 hours measured via ASTM D-1693, Condition B, 100 percent Igepal. The high-density polyethylene composition may comprise any amounts of first component, second component, or combinations thereof. The high-density polyethylene composition comprises 40 to 60 percent by weight of the first component, based on the total weight of the first and second components. All individual values and subranges from 40 to 60 weight percent are included herein and disclosed herein; for example, the high-density polyethylene composition comprises 42 to 55 percent by weight of the first component, based on the total weight of first and second components. The high-density polyethylene composition further comprises 40 to 60 percent by weight of the second component, based on the total weight of the first and second components. All individual values and subranges from 40 to 60 weight percent are included herein and disclosed herein; for example, the high-density polyethylene composition further comprises 48 to 55 percent by weight of the second component, based on the total weight of the first and second components. Preferably, the high-density polyethylene composition has a single ATREF temperature peak, wherein the ATREF temperature peak having a temperature peak maximum between 90° C. to 105° C., as described hereinbelow in further details. The high-density polyethylene composition further has a calculated high-density fraction in the range of 20 percent to 50 percent. All individual values and subranges from 20 percent to 50 percent are included herein and disclosed herein. The calculated high-density fraction, as used herein, refers to [(2)×(the weight ratio of the high-density polyethylene that elutes in ATREF-DV at temperatures greater than or equal to the temperature peak maximum]. Additionally, the high-density polyethylene composition has a relative minimum in the log of the relative viscosity average molecular weight at about 90° C. in ATRF-DV, and a regression slope of the log of the relative viscosity average molecular weight versus the ATREF-DV viscosity versus temperature plot of less than about 0, where the elution temperature is measured between 70° C. to 90° C.
  • [0054]
    The ATREF high-density fraction (percent) of the polyethylene composition is calculated by integrating the area under the curve from 86° C. and higher as long as there is no relative minimum in the curve. None of the inventive or comparative samples measured and reported in the tables had a relative minimum in the curve from 86° C. and higher temperatures.
  • [0055]
    The high-density polyethylene composition has a g′ average of equal or greater than 1 measured by triple detector gel permeation chromatography (GPC), described in further details herein below. g′ is expressed as the ratio of intrinsic viscosity of the instant high-density polyethylene composition to the intrinsic viscosity of a linear polymer reference. If the g′ is equal or greater than 1 then the sample being analyzed is considered linear, and if g′ is less than 1, it is, then, by definition a branched polymer as compared to a linear polymer. However, current testing methods may be subject to errors in their precision and accuracy; thus, proper steps must be taken into account for such precision errors. Therefore, small deviations, for example values of less than or equal to 0.012, from unity, that is 0.988 to 1.012, would still be defined as linear polymers. In the alternative, small deviation, for example values of less than or equal to 0.025, from unity, that is 0.975 to 1.025, would still be defined as linear polymers.
  • [0056]
    Referring to FIG. 1, the high-density polyethylene composition has an ATREF high-density fraction in percent of equal or less than [(2750*density of the high-density polyethylene composition)−2552.2]*[1(percent)/(g/cm3)], where density is measured in g/cm3.
  • [0057]
    Referring to FIG. 2, the high-density polyethylene composition has a comonomer content in weight percent equal or greater that [(−228.41*density of high-density polyethylene composition)+219.36)]*[1(weight percent)/(g/cm3)], where density is measured in g/cm3.
  • [0058]
    Referring to FIG. 3, the calculated high density fraction in percent is equal to [1107.4*(density of the high molecular weight polyethylene component)−992.56]*[1(percent/(g/cm3).
  • [0059]
    Referring to FIG. 4, FIG. 4 illustrates the relationship between the elution temperatures in ° C. and viscosity average in Log[MV(g/Mole)].
  • [0060]
    The high-density polyethylene composition may further include additional components such as other polymers, adjuvants, and/or additives. Such adjuvants or additives include, but are not limited to, antistatic agents, color enhancers, dyes, lubricants, fillers, pigments, primary antioxidants, secondary antioxidants, processing aids, UV stabilizers, nucleators, viscosity control agents, tackifiers, anti-blocking agents, surfactants, extender oils, metal deactivators, flame retardants, smoke suppressants, and combinations thereof. The high-density polyethylene composition compromises about less than 10 percent by the combined weight of one or more additives, based on the weight of the high-density polyethylene composition. All individual values and subranges from about less than 10 weight percent are included herein and disclosed herein; for example, the high-density polyethylene composition comprises about less than 5 percent by the combined weight of one or more additives, based on the weight of the high-density polyethylene composition; or in the alternative, the high-density polyethylene composition comprises about less than 1 percent by the combined weight of one or more additives, based on the weight of the high-density polyethylene composition; or in another alternative, the high-density polyethylene composition may compromise about less than 0.5 percent by the combined weight of one or more additives, based on the weight of the high-density polyethylene composition. Antioxidants, such as Irgafos® 168 and Irganox® 1010, are commonly used to protect the polymer from thermal and/or oxidative degradation. Irganox® 1010 is tetrakis (methylene (3,5-di-tert-butyl-4-hydroxyhydrocinnamate), which is commercially available from Ciba Geigy Inc. Irgafos® 168 is tris (2,4 di-tert-butylphenyl) phosphite, which is commercially available from Ciba Geigy Inc.
  • [0061]
    The inventive high-density polyethylene composition may further be blended with other polymers. Such other polymers are generally known to a person of ordinary skill in the art. Blends comprising the inventive high-density polyethylene composition is formed via any conventional methods. For example, the selected polymers are melt blended via a single or twin screw extruder, or a mixer, for example a Banbury mixer, a Haake mixer, a Barbender internal mixer.
  • [0062]
    In general, blends containing the inventive high-density polyethylene composition comprises at least 40 percent by weight of the inventive high-density polyethylene composition, based on the total weight of the blend. All individual values and subranges in the range of at least 40 weight percent are included herein and disclosed herein; for example, the blend comprises at least 50 percent by weight of the inventive high-density polyethylene composition, based on the total weight of the blend; or in the alternative, the blend comprises at least 60 percent by weight of the inventive high-density polyethylene composition, based on the total weight of the blend; or in the alternative, the blend comprises at least 70 percent by weight of the inventive high-density polyethylene composition, based on the total weight of the blend; or in the alternative, the blend comprises at least 80 percent by weight of the inventive high-density polyethylene composition, based on the total weight of the blend; or in the alternative, the blend comprises at least 90 percent by weight of the inventive high-density polyethylene composition, based on the total weight of the blend; or in the alternative, the blend comprises at least 95 percent by weight of the inventive high-density polyethylene composition, based on the total weight of the blend; or in the alternative, the blend comprises at least 99.99 percent by weight of the inventive high-density polyethylene composition, based on the total weight of the blend.
  • [0063]
    Different polymerization reactions and catalyst systems may be employed to produce the inventive high-density polyethylene composition. Typical transition metal catalyst systems used to prepare the high-density polyethylene composition are magnesium/titanium based catalyst systems, exemplified by the catalyst system described in U.S. Pat. No. 4,302,565; vanadium based catalyst systems, such as those described in U.S. Pat. No. 4,508,842; U.S. Pat. No. 5,332,793; U.S. Pat. No. 5,342,907; and U.S. Pat. No. 5,410,003; and a metallocene catalyst system, such as those described in U.S. Pat. No. 4,937,299; U.S. Pat. No. 5,317,036; and U.S. Pat. No. 5,527,752. Catalyst systems that use molybdenum oxides on silica-alumina supports are also useful. Preferred catalyst systems for preparing the components for the inventive high-density polyethylene composition are Ziegler-Natta catalyst systems and metallocene catalyst systems.
  • [0064]
    In some embodiments, preferred catalysts used in the process to make the high-density polyethylene compositions are of the magnesium/titanium type. In particular, for the gas phase polymerizations, the catalyst is made from a precursor comprising magnesium and titanium chlorides in an electron donor solvent. This solution is often either deposited on a porous catalyst support, or a filler is added, which, on subsequent spray drying, provides additional mechanical strength to the particles. The solid particles from either support methods are often slurried in a diluent producing a high viscosity mixture, which is then used as catalyst precursor. Exemplary catalyst types are described in U.S. Pat. No. 6,187,866 and U.S. Pat. No. 5,290,745, the entire contents of both of which are herein. Precipitated/crystallized catalyst systems, such as those described in U.S. Pat. No. 6,511,935 and U.S. Pat. No. 6,248,831, the entire contents of both of which are herein, may also be used. Such catalysts may further be modified with one precursor activator. Such further modifications are described in US patent publication No.: US2006/0287445 A1.
  • [0065]
    Preferably the catalyst precursor has the formula MgdTi(OR)eXf(ED)g wherein R is an aliphatic or aromatic hydrocarbon radical having 1 to 14 carbon atoms or COR′ wherein R′ is a aliphatic or aromatic hydrocarbon radical having 1 to 14 carbon atoms; each OR group is the same or different; X is independently chlorine, bromine or iodine; ED is an electron donor; d is 0.5 to 56; e is 0, 1, or 2; f is 2 to 116; and g is >2 and up to 1.5*d+3. It is prepared from a titanium compound, a magnesium compound, and an electron donor.
  • [0066]
    The electron donor is an organic Lewis base, liquid at temperatures in the range of 0° C. to 200° C., in which the magnesium and titanium compounds are soluble. The electron donor compounds are sometimes also referred to as Lewis bases. The electron donor can be an alkyl ester of an aliphatic or aromatic carboxylic acid, an aliphatic ketone, an aliphatic amine, an aliphatic alcohol, an alkyl or cycloalkyl ether, or mixtures thereof, each electron donor having 2 to 20 carbon atoms. Among these electron donors, the preferred are alkyl and cycloalkyl ethers having 2 to 20 carbon atoms; dialkyl, diaryl, and alkylaryl ketones having 3 to 20 carbon atoms; and alkyl, alkoxy, and alkylalkoxy esters of alkyl and aryl carboxylic acids having 2 to 20 carbon atoms. The most preferred electron donor is tetrahydrofuran. Other examples of suitable electron donors are methyl formate, ethyl acetate, butyl acetate, ethyl ether, dioxane, di-n-propyl ether, dibutyl ether, ethanol, 1-butanol, ethyl formate, methyl acetate, ethyl anisate, ethylene carbonate, tetrahydropyran, and ethyl propionate.
  • [0067]
    While a large excess of electron donor may be used initially to provide the reaction product of titanium compound and electron donor, the final catalyst precursor contains approximately 1 to approximately 20 moles of electron donor per mole of titanium compound and preferably approximately 1 to approximately 10 moles of electron donor per mole of titanium compound.
  • [0068]
    Since the catalyst will act as a template for the growth of the polymer, it is essential that the catalyst precursor be converted into a solid. It is also essential that the resultant solid has the appropriate particle size and shape to produce polymer particles with relatively narrow size distribution, low amounts of fines and good fluidization characteristics. Although this solution of Lewis Base, magnesium and titanium compounds may be impregnated into a porous support and dried to form a solid catalyst; it is preferred that the solution be converted into a solid catalyst via spray drying. Each of these methods thus forms a “supported catalyst precursor.”
  • [0069]
    The spray dried catalyst product is then preferentially placed into a mineral oil slurry. The viscosity of the hydrocarbon slurry diluent is sufficiently low, so that the slurry can be conveniently pumped through the pre-activation apparatus, and eventually into the polymerization reactor. The catalyst is fed using a slurry catalyst feeder. A progressive cavity pump, such as a Moyno pump is typically used in commercial reaction systems, while a dual piston syringe pump is typically used in pilot scale reaction systems, where the catalyst flows are less than, or equal to, 10 cm3/hour (2.78×10−9 m3/s) of slurry.
  • [0070]
    A cocatalyst, or activator, is also fed to the reactor to effect the polymerization. Complete activation by additional cocatalyst is required to achieve full activity. The complete activation normally occurs in the polymerization reactor, although the techniques taught in EP 1,200,483 may also be used.
  • [0071]
    The cocatalysts, which are reducing agents, conventionally used, are comprised of aluminum compounds, but compounds of lithium, sodium and potassium, alkaline earth metals, as well as compounds of other earth metals than aluminum are possible. The compounds are usually hydrides, organometal or halide compounds. Butyl lithium and dibutyl magnesium are examples of useful compounds of other than aluminum.
  • [0072]
    An activator compound, which is generally used with any of the titanium based catalyst precursors, can have the formula AlRaXbHc, wherein each X is independently chlorine, bromine, iodine, or OR′; each R and R′ is independently a saturated aliphatic hydrocarbon radical having 1 to 14 carbon atoms; b is 0 to 1.5; c is 0 or 1; and a+b+c=3. Preferred activators include alkylaluminum mono- and dichlorides, wherein each alkyl radical has 1 to 6 carbon atoms and the trialkylaluminums. Examples are diethylaluminum chloride and tri-n-hexylaluminum. About 0.10 to 10 moles, and preferably 0.15 to 2.5 moles, of activator are used per mole of electron donor. The molar ratio of activator to titanium is in the range from 1:1 to 10:1, and is preferably in the range from 2:1 to 5:1.
  • [0073]
    The hydrocarbyl aluminum cocatalyst can be represented by the formula R3Al or R2AlX, wherein each R is independently alkyl, cycloalkyl, aryl, or hydrogen; at least one R is hydrocarbyl; and two or three R radicals can be joined to form a heterocyclic structure. Each R, which is a hydrocarbyl radical, can have 1 to 20 carbon atoms, and preferably has 1 to 10 carbon atoms. X is a halogen, preferably chlorine, bromine, or iodine. Examples of hydrocarbyl aluminum compounds are as follows: triisobutylaluminum, tri-n-hexylaluminum, di-isobutyl-aluminum hydride, dihexylaluminum hydride, di-isobutylhexylaluminum, isobutyl dihexylaluminum, trimethylaluminum, triethylaluminum, tripropylaluminum, triisopropylaluminum, tri-n-butylaluminum, trioctylaluminum, tridecylaluminum, tridodecylaluminum, tribenzylaluminum, triphenylaluminum, trinaphthylaluminum, tritolylaluminum, dibutylaluminum chloride, diethylaluminum chloride, and ethylaluminum sesquichloride. The cocatalyst compounds can also serve as activators and modifiers.
  • [0074]
    Activators can be added to the precursor either before and/or during polymerization. In one procedure, the precursor is fully activated before polymerization. In another procedure, the precursor is partially activated before polymerization, and activation is completed in the reactor. Where a modifier is used instead of an activator, the modifiers are usually dissolved in an organic solvent such as isopentane and, where a support is used, impregnated into the support following impregnation of the titanium compound or complex, after which the supported catalyst precursor is dried. Otherwise, the modifier solution is added by itself directly to the reactor. Modifiers are similar in chemical structure and function to the activators as are cocatalysts. For variations, see for example, U.S. Pat. No. 5,106,926, incorporated herein by reference in its entirety. The cocatalyst is preferably added separately neat or as a solution in an inert solvent, such as isopentane, to the polymerization reactor at the same time as the flow of ethylene is initiated.
  • [0075]
    In those embodiments that use a support, the precursor is supported on an inorganic oxide support such as silica, aluminum phosphate, alumina, silica/alumina mixtures, silica that has been modified with an organoaluminum compound such as triethyl aluminum, and silica modified with diethyl zinc. In some embodiments silica is a preferred support. A typical support is a solid, particulate, porous material essentially inert to the polymerization. It is used as a dry powder having an average particle size of 10 to 250 μm and preferably 30 to 100 μm; a surface area of at least 200 m2/g and preferably at least 250 m2/g; and a pore size of at least 100×10−10 m and preferably at least 200×10−10 m. Generally, the amount of support used is that which will provide 0.1 to 1.0 millimole of titanium per gram of support and preferably 0.4 to 0.9 millimole of titanium per gram of support. Impregnation of the above mentioned catalyst precursor into a silica support can be accomplished by mixing the precursor and silica gel in the electron donor solvent or other solvent followed by solvent removal under reduced pressure. When a support is not desired, the catalyst precursor can be used in liquid form.
  • [0076]
    In another embodiment, metallocene catalysts, single-site catalysts and constrained geometry catalysts may be used in the practice of the invention. Generally, metallocene catalyst compounds include half and full sandwich compounds having one or more π-bonded ligands including cyclopentadienyl-type structures or other similar functioning structure such as pentadiene, cyclooctatetraendiyl and imides. Typical compounds are generally described as containing one or more ligands capable of π-bonding to a transition metal atom, usually, cyclopentadienyl derived ligands or moieties, in combination with a transition metal selected from Group 3 to 8, preferably 4, 5 or 6 or from the lanthanide and actinide series of the Periodic Table of Elements.
  • [0077]
    Exemplary of metallocene-type catalyst compounds are described in, for example, U.S. Pat. Nos. 4,530,914; 4,871,705; 4,937,299; 5,017,714; 5,055,438; 5,096,867; 5,120,867; 5,124,418; 5,198,401; 5,210,352; 5,229,478; 5,264,405; 5,278,264; 5,278,119; 5,304,614; 5,324,800; 5,347,025; 5,350,723; 5,384,299; 5,391,790; 5,391,789; 5,399,636; 5,408,017; 5,491,207; 5,455,366; 5,534,473; 5,539,124; 5,554,775; 5,621,126; 5,684,098; 5,693,730; 5,698,634; 5,710,297; 5,712,354; 5,714,427; 5,714,555; 5,728,641; 5,728,839; 5,753,577; 5,767,209; 5,770,753 and 5,770,664; European publications: EP-A-0 591 756; EP-A-0 520 732; EP-A-0 420 436; EP-A-0 485 822; EP-A-0 485 823; EP-A-0 743 324; EP-A-0 518 092; and PCT publications: WO 91/04257; WO 92/00333; WO 93/08221; WO 93/08199; WO 94/01471; WO 96/20233; WO 97/15582; WO 97/19959; WO 97/46567; WO 98/01455; WO 98/06759 and WO 98/011144. All of these references are incorporated herein, in their entirety, by reference.
  • [0078]
    Suitable catalysts for use herein, preferably include constrained geometry catalysts as disclosed in U.S. Pat. Nos. 5,272,236 and 5,278,272, which are both incorporated, in their entirety, by reference.
  • [0079]
    The monocyclopentadienyl transition metal olefin polymerization catalysts taught in U.S. Pat. No. 5,026,798, the teachings of which are incorporated herein by reference, are also suitable as catalysts of the invention.
  • [0080]
    The foregoing catalysts may be further described as comprising a metal coordination complex comprising a metal of groups 3-10 or the Lanthanide series of the Periodic Table of the Elements, and a delocalized π-bonded moiety, substituted with a constrain-inducing moiety. Such a complex has a constrained geometry about the metal atom. The catalyst further comprises an activating cocatalyst.
  • [0081]
    Any conventional ethylene homopolymerization or (co)polymerization reactions may be employed to produce the inventive high-density polyethylene composition. Such conventional ethylene homopolymerization or (co)polymerization reactions include, but are not limited to, gas phase polymerization, slurry phase polymerization, liquid phase polymerization, and combinations thereof using conventional reactors, for example gas phase reactors, loop reactors, stirred tank reactors, and batch reactors in series, or in series and parallel. The polymerization system of the instant invention is a dual sequential polymerization system or a multi-sequential polymerization system. Examples of dual sequential polymerization system include, but are not limited to, gas phase polymerization/gas phase polymerization; gas phase polymerization/liquid phase polymerization; liquid phase polymerization/gas phase polymerization; liquid phase polymerization/liquid phase polymerization; slurry phase polymerization/slurry phase polymerization; liquid phase polymerization/slurry phase polymerization; slurry phase polymerization/liquid phase polymerization; slurry phase polymerization/gas phase polymerization; and gas phase polymerization/slurry phase polymerization. The multi-sequential polymerization systems includes at least three polymerization reactions. The catalyst system, described above, may also be a conventional catalyst system. The inventive high-density polyethylene composition is preferably produced via a dual gas phase polymerization process, for example gas phase polymerization/gas phase polymerization; however, the instant invention is not so limited, and any of the above combinations may be employed.
  • [0082]
    In production, a dual sequential polymerization system connected in series, as described above, may be used. The first component, that is the high molecular weight ethylene polymer, can be produced in the first stage of the dual sequential polymerization system, and the second component, that is the low molecular weight ethylene polymer, can be prepared in the second stage of the dual sequential polymerization system. Alternatively, the second component, that is the low molecular weight ethylene polymer, can be made in the first stage of the dual sequential polymerization system, and the first component, that is the high molecular weight ethylene polymer, can be made in the second stage of the dual sequential polymerization system.
  • [0083]
    For purposes of the present disclosure, the reactor, in which the conditions are conducive to making the first component is known as the first reactor. Alternatively, the reactor in which the conditions are conducive to making the second component is known as the second reactor.
  • [0084]
    In production, a catalyst system including a cocatalyst, ethylene, one or more alpha-olefin comonomers, hydrogen, and optionally inert gases and/or liquids, for example N2, isopentane, and hexane, are continuously fed into a first reactor, which is connected to a second reactor in series; the first component/active catalyst mixture is then continuously transferred, for example, in batches from the first reactor to the second reactor. Ethylene, hydrogen, cocatalyst, and optionally inert gases and/or liquids, for example N2, isopentane, hexane, are continuously fed to the second reactor, and the final product, that is the inventive high-density polyethylene composition, is continuously removed, for example, in batches from the second reactor. A preferred mode is to take batch quantities of first component from the first reactor, and transfer these to the second reactor using the differential pressure generated by a recycled gas compression system. The inventive high-density polyethylene composition is then transferred to a purge bin under inert atmosphere conditions. Subsequently, the residual hydrocarbons are removed, and moisture is introduced to reduce any residual aluminum alkyls and any residual catalysts before the inventive high-density polyethylene composition is exposed to oxygen. The inventive high-density polyethylene composition is then transferred to an extruder to be pelletized. Such pelletization techniques are generally known. The inventive high-density polyethylene composition may further be melt screened. Subsequent to the melting process in the extruder, the molten composition is passed through one or more active screens (positioned in series of more than one) with each active screen having a micron retention size of from 2 to 400 (2 to 4×10−5 m), and preferably 2 to 300 (2 to 3×10−5 m), and most preferably 2 to 70 (2 to 7×10−6 m), at a mass flux of 5 to 100 lb/hr/in2 (1.0 to about 20 kg/s/m2). Such further melt screening is disclosed in U.S. Pat. No. 6,485,662, which is incorporated herein by reference to the extent that it discloses melt screening.
  • [0085]
    In an alternative production, a multi-sequential polymerization system connected in series and parallel, as described above, may be used. In one embodiment of the instant invention, a catalyst system including a cocatalyst, ethylene, one or more alpha-olefin comonomers, hydrogen, and optionally inert gases and/or liquids, for example N2, isopentane, and hexane, are continuously fed into a first reactor, which is connected to a second reactor, wherein the second reactor is connected to a third reactor in series; the first component/active catalyst mixture is then continuously transferred, for example, in batches from the first reactor to the second reactor, and then to the third reactor. Ethylene, hydrogen, cocatalyst, and optionally inert gases and/or liquids, for example N2, isopentane, and hexane, are continuously fed to the second and third reactors, and the final product, that is high-density polyethylene composition, is continuously removed, for example, in batches from the third reactor. A preferred mode is to take batch quantities of first component from the first reactor, and transfer these to the second reactor, and then take batches from the second reactor and transfer these to the third reactor in series using the differential pressure generated by a recycled gas compression system. Alternatively, the first reactor may feed to both a second reactor and a third reactor in parallel, and the product from first reactor may be transferred to either second or third reactor. The high-density polyethylene composition is then transferred to a purge bin under inert atmosphere conditions. Subsequently, the residual hydrocarbons are removed, and moisture may be introduced to reduce any residual aluminum alkyls and any residual catalysts before the polymer, that is the inventive high-density polyethylene composition, is exposed to oxygen. The inventive high-density polyethylene composition is then transferred to an extruder to be pelletized. Such pelletization techniques are generally known. The inventive high-density polyethylene composition may further be melt screened. Subsequent to the melting process in the extruder, the molten composition is passed through one or more active screens (positioned in series of more than one) with each active screen having a micron retention size of from 2 to 400 (2 to 4×10−5 m), and preferably 2 to 300 (2 to 3×10−5 m), and most preferably 2 to 70 (2 to 7×10−6 m), at a mass flux of 5 to 100 lb/hr/in2 (1.0 to about 20 kg/s/m2). Such further melt screening is disclosed in U.S. Pat. No. 6,485,662, which is incorporated herein by reference to the extent that it discloses melt screening.
  • [0086]
    In another alternative production, the inventive high-density polyethylene composition may be produced from polymers made in two independent reactors (each using the same or different catalyst) with post reaction blending.
  • [0087]
    In application, the inventive high-density polyethylene composition may be used to manufacture shaped articles. Such articles may include, but are not limited to, power or communication cable jackets, or power or communication cable insulation products. Different methods may be employed to manufacture articles such as power or communication cable jackets, or power or communication cable insulation products. Suitable conversion techniques include, but are not limited to, wire coating via extrusion. Such techniques are generally well known.
  • [0088]
    In extrusion process, the high-density polyethylene composition is applied on a conducting element, for example glass fiber, copper wire, or cable core construction, via extrusion process. The extruder is usually a conventional one using a crosshead die, which provides the desired layer (wall or coating) thickness. An example of an extruder, which can be used is the single screw type modified with a crosshead die, cooling through and continuous take-up equipment. A typical single screw type extruder can be described as one having a hopper at its upstream end and a die at its downstream end. The hopper feeds into the barrel, which contains a screw. At the downstream end, between the end of the screw and the die is a screen pack and a breaker plate. The screw portion of the extruder is considered to be divided up into three sections, the feed section, the compression section, and the metering section, and multiple heating zones from the rear heating zone to the front heating zone with the multiple sections running from upstream to downstream. The length to diameter ratio of the barrel is in the range of 16:1 to 30:1. Grooved barrel extruders or twin screw extruders can also be employed in the wire coating process. The jacketing extrusion can take place at temperatures in the range of 160° C. to about 260° C., and it is typically carried out at temperatures in the range of 180° C. to 240° C. The crosshead die distributes the polymer melt in a flow channel such that the material exits with a uniform velocity. The conducting elements, for example single fiber, wire or core passes through the center of the crosshead, and as it exits a uniform layer is circumferentially applied using either pressure, or semi-pressure of tube-on tooling. Several layers can be applied using a multiple crosshead. The cable is then cooled in water trough sufficiently to prevent deformation of the applied layer on the take-up reel. In cable jacketing applications, the jacketing layer thickness can be about 20 to 100 mils with the preferred range of about 30-80 mils. The line speeds can be equal or greater than 150 ft/minute. All individual values and subranges equal or greater than 150 ft/minute are included herein and disclosed herein; for example, the line speeds can be equal or greater than 200 ft/minute; or in the alternative, the line speeds can be equal or greater than 300 ft/minute.
  • EXAMPLES
  • [0089]
    It is understood that the present invention is operable in the absence of any component, which has not been specifically disclosed. The following examples are provided in order to further illustrate the invention and are not to be construed as limiting.
  • [0090]
    The following examples illustrate that the inventive high-density polyethylene composition has significant improvements in processing, that is achieving significantly lower extrusion pressures at both the breaker plate and the head. The inventive high-density polyethylene composition further requires lower power usage as shown by the extruder amperage. Additional significant improvements were achieved in average surface smoothness. Improved average surface smoothness is important because such improvements provide for better aesthetic and customer satisfaction. Such improvements further minimize diameter variations of the cable jackets or installations. Where multiple extrusion layers are involved, improved average surface smoothness can minimize the defects at the internal interfaces. Not only did the unexpected results of the instant invention show that inventive high-density polyethylene composition had improved average surface smoothness, but they have also exhibited lower shrinkage on both off-wire and on-wire testing. Shrink-back occurs when the polymeric material cools and the material shrinks inwards, thus exposing the end of the metal conductor or core. Minimization of shrink-back allows for ease of connectability by the cable installers. The following examples show that inventive high-density polyethylene composition possesses significant improvements over commercially available bimodal resins as well as unimodal resins. The following examples show that the inventive high-density polyethylene composition possesses improved processability, smoother surface, and less shrinkage than materials currently employed in these applications, while maintaining at least an equal ESCR.
  • Inventive Samples Resins 1-6
  • [0091]
    Inventive Sample Resins 1-6 were prepared according to the following procedures: a dual-sequential polymerization system, for example a first gas phase reactor and a second gas phase reactor operating in series, was provided. Ethylene, one or more alpha-olefin comonomers, hydrogen, catalyst, for example Ziegler-Natta catalyst, slurried in mineral oil, N2, and isopentane were fed continuously into the first reactor. Subsequently, a cocatalyst, for example triethylaluminum (TEAL), was fed continuously into the first reactor to activate the catalyst. The first polymerization reaction of the ethylene in the presence of 1-hexene was carried out in the first reactor under the conditions shown below in Table I thereby producing first component-catalyst complex. The first component-catalyst complex was continuously transferred to the second reactor. Additional, ethylene, hydrogen, cocatalyst, for example TEAL, N2, and isopentane were fed continuously into the second reactor. No additional catalyst was added to the second reactor. The second polymerization reaction of ethylene was carried out in the second reactor under the conditions shown below in Table I thereby producing the first component-catalyst-second component complex. The first component-catalyst-second component complex was continuously removed from the second reactor in batches into the product chamber, where it was purged to remove residual hydrocarbons, and then transferred to a fiberpak drum. The fiberpak drum was continuously purged with humidified nitrogen. The polymer, that is the inventive high-density polyethylene composition, was further processed in a mixer/pelletizer. Additional additives, as shown in Table III, were added to the polymer, that is the inventive high-density polyethylene composition. The polymer, that is the inventive high-density polyethylene composition, was melted in the mixer, and additives were dispersed therein the polymer, inventive high-density polyethylene composition, matrix. The inventive high-density polyethylene composition was extruded through a die plate, pelletized, and cooled. The Inventive Sample Resins 1-6 were tested for their properties from pellets, or were formed into testing plaques according to ASTM D-4703-00 and then were tested for their properties. Such properties are shown in Tables I and II, and FIGS. 1-4.
  • Inventive Examples 1a and 1b
  • [0092]
    The inventive high-density polyethylene composition, a natural bimodal resin, was utilized to make the Inventive Examples 1a and 1b. The inventive high-density polyethylene composition was applied onto 14AWG (1.6256 mm) copper wire with a targeted thickness of 0.762 mm via extrusion process. The extruder was a Davis-Standard wire line equipped with a 63.5 mm extruder, a 2.286 mm polyethylene metering screw, a 1.701 mm tip, and a 20/40/60/20 screen pack. The extrusion conditions are listed on Table IV. The properties of the final cable jackets are also shown on Tables IV, and V.
  • Comparative Examples A-D
  • [0093]
    Comparative Example A is a unimodal high-density polyethylene, which is commercially available under the tradename DGDL-3364 Natural from The Dow Chemical Company, USA. Comparative Example B is a unimodal high-density polyethylene, which is commercially available under the tradename DFNA-4518 natural from The Dow Chemical Company, USA. Comparative Example C is bimodal high-density polyethylene, which is commercially available under the tradename DGDA 2490 Natural from The Dow Chemical Company, USA. Comparative Example D is a bimodal high-density polyethylene, which is commercially available under the tradename DGDA-1310 Natural from The Dow Chemical Company, USA. Comparative Example A-D were applied onto 14AWG (1.6256 mm) copper wire with a targeted thickness of 0.762 mm via extrusion process. The extruder was a Davis-Standard wire line equipped with a 63.5 mm extruder, a 2.286 mm polyethylene metering screw, a 1.701 mm tip, and a 20/40/60/20 screen pack. The extrusion conditions are listed on Table IV. The properties of the final comparative cable jackets are also shown on Tables IV and V.
  • Inventive Examples 1a-b Versus Comparative Examples A-D
  • [0094]
    The results shown on Tables IV and V are unexpected. Inventive Examples 1a-b showed significantly lower extrusion pressures at the breaker plate and the head at a line rate of 200 rpm than the Comparative Examples A, B, C, or D. Furthermore, increasing the line rate by 50 percent to 300 rpm showed only a marginal increase in pressures; however, the extrusion pressure was still significantly lower than the Comparative Examples A, B, C, or D, which were made at 200 rpm.
  • [0095]
    Additionally, extrusion amperage showed significantly less power is required to process the inventive high-density polyethylene composition even when the line rate was increased by 50 percent to 300 rpm.
  • [0096]
    The surface smoothness of Inventive Examples 1a-b, and Comparative Examples A-D was measured according to ANSI 1995 via a Surftest SV-400 Series 178 Surface Texture Measuring Instrument. Wire sample was placed in a V-Block and the stylus (10 um) was lowered down to a specific start position (approx. 1 gram force was applied to wire). At a fixed rate of 2 mm/sec the stylus moved in the transverse direction taking measurements. Four readings per wire sample and four samples were tested which were then averaged.
  • [0097]
    In addition, the shrink-back on-wire and off-wire was measured. The shrink-back test was conducted by cutting 10 six inch length samples from a wire sample 24 hours after extrusion. The samples were then put on a tray which contains a layer of Talc. The tray was then placed in an oven, which was set at a temperature of 115° C. After four hours, the samples were then removed, and allowed to cool to room temperature. The samples were then measured, and then, the shrink-back was calculated in terms of percentage difference from the initial six inch length. The 10 samples were then averaged. In on-wire shrinkage testing, the copper wire was left in the test sample. In off-wire shrink-back testing, the copper wire was removed prior to testing. The results for the Inventive Examples 1a-b and Comparative Examples A-D are shown in Tables IV and V.
  • [0098]
    Finally, surface average smoothness and shrink-back were further improved when the line speed was increased by 50 percent to 300 rpm.
  • Inventive Example 2
  • [0099]
    The inventive high-density polyethylene composition was dry blended with a 45 percent containing carbon black masterbatch, which is commercially available under the tradename DFNA-0037 BN from The Dow Chemical Company, to achieve a cable jacket comprising 2.5 percent by weight of carbon black based on the weight of the compounded inventive high-density polyethylene composition. The blend was applied onto 14AWG (1.6256 mm) copper wire with a targeted thickness of 0.762 mm via extrusion process thereby producing Inventive Example 2. The extruder was a Davis-Standard wire line equipped with a 63.5 mm extruder, a 2.286 mm polyethylene metering screw, a 1.701 mm tip, and a 20/40/60/20 screen pack. The extrusion conditions are listed on Table VI. The properties of the final cable jackets are also shown on Tables VI and VII.
  • Comparative Examples E1-G2
  • [0100]
    Comparative Examples E1-2 include a unimodal high-density polyethylene, which was dry blended with a 45 percent containing carbon black masterbatch, commercially available under the tradename DFNA-0037 BN from The Dow Chemical Company, USA, to achieve a cable jacket comprising 2.5 percent by weight of carbon black based on the weight of the compounded unimodal high-density polyethylene. Comparative Examples F1-2 include a bimodal high-density polyethylene, commercially available under the tradename DGDA 2490 Natural from The Dow Chemical Company, USA, which was dry blended with a 45 percent containing carbon black masterbatch, commercially available under the tradename DFNA-0037 BN from The Dow Chemical Company, USA, to achieve a cable jacket comprising 2.5 percent by weight of carbon black based on the weight of the compounded unimodal high-density polyethylene. Comparative Examples G1-2 include a bimodal high-density polyethylene, which is commercially available under the tradename DGDA-1310 Natural from The Dow Chemical Company, which was dry blended with a 45 percent containing carbon black masterbatch, commercially available under the tradename DFNA-0037 BN from The Dow Chemical Company, USA, to achieve a cable jacket comprising 2.5 percent by weight of carbon black based on the weight of the compounded unimodal high-density polyethylene. The blends as described above were applied onto 14AWG (1.6256 mm) copper wire with a targeted thickness of 0.762 mm via extrusion process thereby forming Comparative Examples E1-G2. The extruder was a Davis-Standard wire line equipped with a 63.5 mm extruder, a 2.286 mm polyethylene metering screw, a 1.701 mm tip, and a 20/40/60/20 screen pack. The extrusion conditions are listed on Table VI. The properties of the final comparative cable jackets are also shown on Tables VI and VII.
  • Inventive Example 2 Versus Comparative Examples E1-G2
  • [0101]
    The results shown on Tables VI and VII are unexpected. Inventive Example 2 showed significantly lower extrusion pressures at the breaker plate and the head at a line rate of 200 rpm than the Comparative Examples E1-G2. Furthermore, decreasing the line rate by 50 percent to 100 rpm for the Comparative Examples E2, F2, and G3 did not lower the extruder amperage to the level of Example 2.
  • [0102]
    The surface smoothness of Inventive Example 2, and Comparative Examples E1-G2 was measured according to ANSI 1995 via a Surftest SV-400 Series 178 Surface Texture Measuring Instrument. Wire sample was placed in a V-Block and the stylus (10 um) was lowered down to a specific start position (approx. 1 gram force was applied to wire). At a fixed rate of 2 mm/sec the stylus moved in the transverse direction taking measurements. Four readings per wire sample and four samples were tested which were then averaged.
  • [0103]
    In addition the shrink-back on-wire and off-wire was measured. The shrink-back test was conducted by cutting 10 six inch length samples from a wire sample 24 hours after extrusion. The samples were then put on a tray which contains a layer of Talc. The tray was then placed in an oven, which was set at a temperature of 115° C. After four hours, the samples were then removed, and allowed to cool to room temperature. The samples were then measured, and then, the shrink-back was calculated in terms of percentage difference from the initial six inch length. The 10 samples were then averaged. In on-wire shrinkage testing, the copper wire was left in the test sample. In off-wire shrink-back testing, the copper wire was removed prior to testing. The results for the Inventive Example 2 and Comparative Examples E1-G2 are shown in Table V.
  • Inventive Example 3
  • [0104]
    The inventive high-density polyethylene composition was dry blended with a 45 percent containing carbon black masterbatch, commercially available under the tradename DFNA-0037 BN from The Dow Chemical Company, to achieve cable jacket comprising 2.5 percent by weight of carbon black based on the weight of the compounded Inventive high-density polyethylene composition. The blend was applied onto 14 AWG (1.6256 mm) copper wire with a targeted thickness of 0.762 mm via extrusion process thereby producing Inventive Example 3. The extruder was a Davis-Standard wire line equipped with a 63.5 mm extruder, a 2.286 mm polyethylene metering screw, a 1.701 mm tip, and a 20/40/60/20 screen pack. The extrusion conditions are listed on Table VIII. The properties of the final cable jackets are also shown on Table VIII.
  • Comparative Examples H-J
  • [0105]
    Comparative Example H is a high-density polyethylene jacket compound, which is commercially available under the tradename DGDA-6318 Black from The Dow Chemical Company, USA. Comparative Example I is a black bimodal high-density polyethylene compound, commercially available under the tradename Borstar HE6062 from Borealis, Denmark. Comparative Example J is a black bimodal high-density polyethylene jacket compound, which is commercially available under the tradename DGDK-3479 Black from The Dow Chemical Company, USA. Comparative Examples H-I were applied onto 14AWG (1.6256 mm) copper wire with a targeted thickness of 0.762 mm via extrusion process. The extruder was a Davis-Standard wire line equipped with a 63.5 mm extruder, a 2.286 mm polyethylene metering screw, a 1.701 mm tip, and a 20/40/60/20 screen pack. The extrusion conditions are listed on Table VI. The properties of the final comparative cable jackets are also shown on Table VI.
  • Inventive Example 3 Versus Comparative Examples H-J
  • [0106]
    The results shown on Table VIII are unexpected. Inventive Example 3 showed significantly lower extrusion pressures at the breaker plate and the head at a line rate of 200 rpm than the Comparative Examples H-J.
  • [0107]
    The surface smoothness of Inventive Example 3, and Comparative Examples H-J was measured according to ANSI 1995 via a Surftest SV-400 Series 178 Surface Texture Measuring Instrument, as described above.
  • [0108]
    In addition, the shrink-back on-wire and off-wire was measured, as described above. The results for the Inventive Example 3 and Comparative Examples H-J are shown in Table VIII.
  • Test Methods
  • [0109]
    Unless otherwise noted, the values reported herein were determined according to the following test methods.
  • [0110]
    Density (g/cm3) was measured according to ASTM-D 792-03, Method B, in isopropanol. Specimens were measured within 1 hour of molding after conditioning in the isopropanol bath at 23° C. for 8 min to achieve thermal equilibrium prior to measurement. The specimens were compression molded according to ASTM D-4703-00 Annex A with a 5 min initial heating period at about 190° C. and a 15° C./min cooling rate per Procedure C. The specimen was cooled to 45° C. in the press with continued cooling until “cool to the touch.”
  • [0111]
    Melt index (I2) was measured at 190° C. under a load of 2.16 kg according to ASTM D-1238-03.
  • [0112]
    Melt index (I5) was measured at 190° C. under a load of 5.0 kg according to ASTM D-1238-03.
  • [0113]
    Melt index (I10) was measured at 190° C. under a load of 10.0 kg according to ASTM D-1238-03.
  • [0114]
    Melt index (I21.6) was measured at 190° C. under a load of 21.6 kg according to ASTM D-1238-03.
  • [0115]
    Weight average molecular weight (Mw) and number average molecular weight (Mw) were determined according to methods known in the art using conventional GPC, as described herein below.
  • [0116]
    The molecular weight distributions of ethylene polymers were determined by gel permeation chromatography (GPC). The chromatographic system consisted of a Waters (Millford, Mass.) 150° C. high temperature gel permeation chromatograph, equipped with a Precision Detectors (Amherst, Mass.) 2-angle laser light scattering detector Model 2040. The 15° angle of the light scattering detector was used for calculation purposes. Data collection was performed using Viscotek TriSEC software version 3 and a 4-channel Viscotek Data Manager DM400. The system was equipped with an on-line solvent degas device from Polymer Laboratories. The carousel compartment was operated at 140° C. and the column compartment was operated at 150° C. The columns used were four Shodex HT 806M 300 mm, 13 μm columns and one Shodex HT803M 150 mm, 12 μm column. The solvent used was 1,2,4 trichlorobenzene. The samples were prepared at a concentration of 0.1 grams of polymer in 50 milliliters of solvent. The chromatographic solvent and the sample preparation solvent contained 200 μg/g of butylated hydroxytoluene (BHT). Both solvent sources were nitrogen sparged. Polyethylene samples were stirred gently at 160° C. for 4 hours. The injection volume used was 200 microliters, and the flow rate was 0.67 milliliters/min. Calibration of the GPC column set was performed with 21 narrow molecular weight distribution polystyrene standards, with molecular weights ranging from 580 to 8,400,000 g/mol, which were arranged in 6 “cocktail” mixtures with at least a decade of separation between individual molecular weights. The standards were purchased from Polymer Laboratories (Shropshire, UK). The polystyrene standards were prepared at 0.025 grams in 50 milliliters of solvent for molecular weights equal to, or greater than, 1,000,000 g/mol, and 0.05 grams in 50 milliliters of solvent for molecular weights less than 1,000,000 g/mol. The polystyrene standards were dissolved at 80° C. with gentle agitation for 30 minutes. The narrow standards mixtures were run first, and in order of decreasing highest molecular weight component, to minimize degradation. The polystyrene standard peak molecular weights were converted to polyethylene molecular weights using the following equation (as described in Williams and Ward, J. Polym. Sci., Polym. Let., 6, 621 (1968)):
  • [0000]

    Mpolyethylene=A×(Mpolystyrene)B,
  • [0000]
    where M is the molecular weight, A has a value of 0.41 and B is equal to 1.0. The Systematic Approach for the determination of multi-detector offsets was done in a manner consistent with that published by Balke, Mourey, et al. (Mourey and Balke, Chromatography Polym. Chpt 12, (1992) and Balke, Thitiratsakul, Lew, Cheung, Mourey, Chromatography Polym. Chpt 13, (1992)), optimizing dual detector log results from Dow broad polystyrene 1683 to the narrow standard column calibration results from the narrow standards calibration curve using in-house software. The molecular weight data for off-set determination was obtained in a manner consistent with that published by Zimm (Zimm, B. H., J. Chem. Phys., 16, 1099 (1948)) and Kratochvil (Kratochvil, P., Classical Light Scattering from Polymer Solutions, Elsevier, Oxford, NY (1987)). The overall injected concentration used for the determination of the molecular weight was obtained from the sample refractive index area and the refractive index detector calibration from a linear polyethylene homopolymer of 115,000 g/mol molecular weight, which was measured in reference to NIST polyethylene homopolymer standard 1475. The chromatographic concentrations were assumed low enough to eliminate addressing 2nd Virial coefficient effects (concentration effects on molecular weight). Molecular weight calculations were performed using in-house software. The calculation of the number-average molecular weight, weight-average molecular weight, and z-average molecular weight were made according to the following equations, assuming that the refractometer signal is directly proportional to weight fraction. The baseline-subtracted refractometer signal can be directly substituted for weight fraction in the equations below. Note that the molecular weight can be from the conventional calibration curve or the absolute molecular weight from the light scattering to refractometer ratio. An improved estimation of z-average molecular weight, the baseline-subtracted light scattering signal can be substituted for the product of weight average molecular weight and weight fraction in equation (2) below:
  • [0000]
    a ) Mn _ = i Wf i i ( Wf i / M i ) b ) Mw _ = i ( Wf i * M i ) i Wf i c ) Mz _ = i ( Wf i * M i 2 ) i ( Wf i * M i ) ( 2 )
  • [0117]
    Bimodality of distributions was characterized according to the weight fraction of the highest temperature peak in temperature rising elution fractionation (typically abbreviated as “TREF”) data as described, for example, in Wild et al., Journal of Polymer Science, Poly. Phys. Ed., Vol. 20, p. 441 (1982), in U.S. Pat. No. 4,798,081 (Hazlitt et al.), or in U.S. Pat. No. 5,089,321 (Chum et al.), the disclosures of all of which are incorporated herein by reference. In analytical temperature rising elution fractionation analysis (as described in U.S. Pat. No. 4,798,081 and abbreviated herein as “ATREF”), the composition to be analyzed is dissolved in a suitable hot solvent (for example, 1,2,4 trichlorobenzene), and allowed to crystallized in a column containing an inert support (for example, stainless steel shot) by slowly reducing the temperature. The column was equipped with both an infra-red detector and a differential viscometer (DV) detector. An ATREF-DV chromatogram curve was then generated by eluting the crystallized polymer sample from the column by slowly increasing the temperature of the eluting solvent (1,2,4 trichlorobenzene). The ATREF-DV method is described in further detail in WO 99/14271, the disclosure of which is incorporated herein by reference.
  • [0118]
    High Density Fraction (percent) was measured via analytical temperature rising elution fractionation analysis (as described in U.S. Pat. No. 4,798,081 and abbreviated herein as “ATREF”), which is described in further details hereinafter. Analytical temperature rising elution fractionation (ATREF) analysis was conducted according to the method described in U.S. Pat. No. 4,798,081 and Wilde, L.; Ryle, T. R.; Knobeloch, D. C.; Peat, I. R.; Determination of Branching Distributions in Polyethylene and Ethylene Copolymers, J. Polym. Sci., 20, 441-455 (1982), which are herein in their entirety. The composition to be analyzed was dissolved in trichlorobenzene and allowed to crystallize in a column containing an inert support (stainless steel shot) by slowly reducing the temperature to 20° C. at a cooling rate of 0.1° C./min. The column was equipped with an infrared detector. An ATREF chromatogram curve was then generated by eluting the crystallized polymer sample from the column by slowly increasing the temperature of the eluting solvent (trichlorobenzene) from 20 to 120° C. at a rate of 1.5° C./min.
  • [0119]
    Branching distributions were determined via crystallization analysis fractionation (CRYSTAF); described herein below. Crystallization analysis fractionation (CRYSTAF) was conducted via a CRYSTAF 200 unit commercially available from PolymerChar, Valencia, Spain. The samples were dissolved in 1,2,4 trichlorobenzene at 160° C. (0.66 mg/mL) for 1 hr and stabilized at 95° C. for 45 minutes. The sampling temperatures ranged from 95 to 30° C. at a cooling rate of 0.2° C./min. An infrared detector was used to measure the polymer solution concentrations. The cumulative soluble concentration was measured as the polymer crystallizes while the temperature was decreased. The analytical derivative of the cumulative profile reflects the short chain branching distribution of the polymer.
  • [0120]
    The CRYSTAF temperature peak and area are identified by the peak analysis module included in the CRYSTAF Software (Version 2001.b, PolymerChar, Valencia, Spain). The CRYSTAF peak finding routine identifies a temperature peak as a maximum in the dW/dT curve and the area between the largest positive inflections on either side of the identified peak in the derivative curve. To calculate the CRYSTAF curve, the preferred processing parameters are with a temperature limit of 70° C. and with smoothing parameters above the temperature limit of 0.1, and below the temperature limit of 0.3.
  • [0121]
    Solubility Distribution Breadth Index (SDBI) is the statistical value for the breadth of the CRYSTAF method which is calculated based on the following formula:
  • [0000]

    SDBI=∫{square root over ((T−T w)4 ·w(T)dT)}{square root over ((T−T w)4 ·w(T)dT)}
  • [0000]

    T w =∫T·w(T)dT
  • [0000]

    w(T)dT=1
  • [0000]
    wherein T is temperature, W is weight fraction, and Tw weight average temperature.
  • [0122]
    Long Chain Branching was determined according to the methods known in the art, such as gel permeation chromatography coupled with low angle laser light scattering detector (GPC-LALLS) and gel permeation chromatography coupled with a differential viscometer detector (GPC-DV).
  • [0123]
    Resin stiffness was characterized by measuring the Flexural Modulus at 5 percent strain and Secant Modulii at 1 percent and 2 percent strain, and a test speed of 0.5 inch/min (13 mm/min) according to ASTM D 790-99 Method B.
  • [0124]
    Tensile strength at yield and elongation at break were measured according to ASTM D-638-03 employing Type IV Specimen at 2 inch/minute (50 mm/minute).
  • [0125]
    The environmental stress crack resistance (ESCR) was measured according to ASTM-D 1693-01, Condition B. The susceptibility of the resin to mechanical failure by cracking was measured under constant strain conditions, and in the presence of a crack accelerating agent such as soaps, wetting agents, etc. Measurements were carried out on notched specimens, in a 10 percent, by volume, Igepal CO-630 (vendor Rhone-Poulec, NJ) aqueous solution, maintained at 50° C., and a 100 percent, by volume, Igepal CO-630 (vendor Rhone-Poulec, NJ) aqueous solution, maintained at 50° C. The ESCR value was reported as F50, the calculated 50 percent failure time from the probability graph, and F0, where there are no failures in the trial.
  • [0126]
    Short chain branching distribution and comonomer content was measured using C13 NMR, as discussed in Randall, Rev. Macromol. Chem. Chys., C29 (2&3), pp. 285-297, and in U.S. Pat. No. 5,292,845, the disclosures of which are incorporated herein by reference to the extent related to such measurement. The samples were prepared by adding approximately 3 g of a 50/50 mixture of tetrachloroethane-d2/orthodichlorobenzene that was 0.025M in chromium acetylacetonate (relaxation agent) to 0.4 g sample in a 10 mm NMR tube. The samples were dissolved and homogenized by heating the tube and its contents to 150° C. The data was collected using a JEOL Eclipse 400 MHz NMR spectrometer, corresponding to a 13C resonance frequency of 100.6 MHz. Acquisition parameters were selected to ensure quantitative 13C data acquisition in the presence of the relaxation agent. The data was acquired using gated 1H decoupling, 4000 transients per data file, a 4.7 sec relaxation delay and 1.3 second acquisition time, a spectral width of 24,200 Hz and a file size of 64K data points, with the probe head heated to 130° C. The spectra were referenced to the methylene peak at 30 ppm. The results were calculated according to ASTM method D5017-91.
  • [0127]
    The resin rheology was measured on the ARES I (Advanced Rheometric Expansion System) Rheometer. The ARES I was a strain controlled rheometer. A rotary actuator (servomotor) applied shear deformation in the form of strain to a sample. In response, the sample generated torque, which was measured by the transducer. Strain and torque were used to calculate dynamic mechanical properties, such as modulus and viscosity. The viscoelastic properties of the sample were measured in the melt using a 25 mm in diameter parallel plate set up, at constant strain (5 percent) and temperature (190° C.) and N2 purge, and as a function of varying frequency (0.01 to 500 s−1). The storage modulus, loss modulus, tan delta, and complex viscosity of the resin were determined using Rheometrics Orchestrator software (v. 6.5.8). The viscosity ratio (0.1 rad*s−1/100 rad*s−1) was determined to be the ratio of the viscosity measured at a shear rate of 0.1 rad/s to the viscosity measured at a shear rate of 100 rad/s.
  • [0128]
    Vinyl unsaturations were measured according to ASTM D-6248-98.
  • [0129]
    Low shear rheological characterization is performed on a Rheometrics SR5000 in stress controlled mode, using a 25 mm parallel plates fixture. This type of geometry is preferred to cone and plate because it requires only minimal squeezing flow during sample loading, thus reducing residual stresses.
  • [0130]
    g′ average was determined according to the following procedure. The chromatographic system consisted of a Waters (Millford, Mass.) 150° C. high temperature chromatograph equipped with a Precision Detectors (Amherst, Mass.) 2-angle laser light scattering detector Model 2040, an IR4 infra-red detector from Polymer Char (Valencia, Spain), and a Viscotek (Houston, Tex.) 150R 4-capillary viscometer. The 15-degree angle of the light scattering detector was used for calculation purposes. Data collection was performed using Viscotek TriSEC software version 3 and a 4-channel Viscotek Data Manager DM400. The system was equipped with an on-line solvent degas device from Polymer Laboratories. The carousel compartment was operated at 140° C. and the column compartment was operated at 150° C. The columns used were 4 20-micron mixed-bed light scattering “Mixed A-LS” columns from Polymer Laboratories. The solvent used was 1,2,4 trichlorobenzene. The samples were prepared at a concentration of 0.1 grams of polymer in 50 milliliters of solvent. The chromatographic solvent and the sample preparation solvent contained 200 ppm of butylated hydroxytoluene (BHT). Both solvent sources were nitrogen sparged. Polyethylene samples were stirred gently at 160 degrees Celsius for 4 hours. The injection volume used was 200 microliters and the flow rate was 1 milliliters/minute.
  • [0131]
    Calibration of the GPC column set was performed with 21 narrow molecular weight distribution polystyrene standards with molecular weights ranging from 580 to 8,400,000, and were arranged in 6 “cocktail” mixtures with at least a decade of separation between individual molecular weights. The standards were purchased from Polymer Laboratories (Shropshire, UK). The polystyrene standards were prepared at 0.025 grams in 50 milliliters of solvent for molecular weights equal to or greater than 1,000,000, and 0.05 grams in 50 milliliters of solvent for molecular weights less than 1,000,000. The polystyrene standards were dissolved at 80° C. with gentle agitation for 30 minutes. The narrow standards mixtures were run first and in order of decreasing highest molecular weight component to minimize degradation. The polystyrene standard peak molecular weights were converted to polyethylene molecular weights using the following equation (as described in Williams and Ward, J. Polym. Sci., Polym. Let., 6, 621 (1968)).:
  • [0000]

    Mpolyethylene=A×(Mpolystyrene)B
  • [0000]
    Where M is the molecular weight, A has a value of 0.43 and B is equal to 1.0.
  • [0132]
    The Systematic Approach for the determination of multi-detector offsets was done in a manner consistent with that published by Balke, Mourey, et. al. (Mourey and Balke, Chromatography Polym. Chpt 12, (1992)) (Balke, Thitiratsakul, Lew, Cheung, Mourey, Chromatography Polym. Chpt 13, (1992)), optimizing triple detector log (MW and IV) results from Dow Broad Polystyrene 1683 to the narrow standard column calibration results from the narrow standards calibration curve using a software. The molecular weight data for off-set determination was obtained in a manner consistent with that published by Zimm (Zimm, B. H., J. Chem. Phys., 16, 1099 (1948)) and Kratochvil (Kratochvil, P., Classical Light Scattering from Polymer Solutions, Elsevier, Oxford, NY (1987)). The overall injected concentration used for the determination of the molecular weight was obtained from the sample refractive index area and the refractive index detector calibration from a linear polyethylene homopolymer of 115,000 molecular weight. The chromatographic concentrations were assumed low enough to eliminate addressing 2nd Virial coefficient effects (concentration effects on molecular weight).
  • [0133]
    g′ average was calculated for the samples as follow:
  • [0134]
    1. The light scattering, viscosity, and concentration detectors were calibrated with NBS 1475 homopolymer polyethylene (or equivalent reference);
  • [0135]
    2. The light scattering and viscometer detector offsets relative to the concentration detector was corrected as described in the calibration section;
  • [0136]
    3. Baselines were subtracted from the light scattering, viscometer, and concentration chromatograms and set integration windows making certain to integrate all of the low molecular weight retention volume range in the light scattering chromatogram that were observable from the refractometer chromatogram;
  • [0137]
    4. A linear homopolymer polyethylene Mark-Houwink reference line was established by injecting a standard with a polydispersity of at least 3.0, and the data file (from above calibration method), was calculated and the intrinsic viscosity and molecular weight from the mass constant corrected data for each chromatographic slice was recorded;
  • [0138]
    5. The HDPE sample of interest was injected and the data file (from above calibration method), was calculated and the intrinsic viscosity and molecular weight from the mass constant corrected data for each chromatographic slice was recorded;
  • [0139]
    6. The homopolymer linear reference intrinsic viscosity was shifted by the following factor: IV=IV+1/(1+2*SCB/1,000 C*branch point length) where IV is the intrinsic viscosity of the HDPE sample of interest, SCB/1,000 C was determined from C13 NMR, and the branch point length is 2 for butene, 4 for hexene, or 6 for octene);
  • [0140]
    7. g′ average was calculated according to the following equation.
  • [0000]
    g = j = WhereM > 40 , 000 HighestM [ c j × ( IV j IV Lj ) M ] + j = LowestM WhereM > 40 , 000 c j j = LowestM HighestM c j
  • [0000]
    Where c is the concentration of the slice, IV is the intrinsic viscosity of the HDPE, and IVL is the intrinsic viscosity of the linear homopolymer polyethylene reference (corrected for SCB of the HDPE sample of interest) at the same molecular weight (M). The IV ratio was assumed to be one at molecular weights less than 40,000 to account for natural scatter in the light scattering data.
  • [0141]
    Surface average smoothness was determined via a Surftest SV-400 Series 178 Surface Texture Measuring Instrument according to ANSI 1995. The wire sample was placed in a V-Block and the stylus (10 um) was lowered down to a specific start position (approx. 1 gram force was applied to wire). At a fixed rate of 2 mm/sec the stylus moved in the transverse direction taking measurements. Four readings per wire sample and four samples were tested which are then averaged.
  • [0142]
    The shrink-back on-wire and off-wire was determined according to the following procedure. The shrink-back test was conducted by cutting 10 six inch length samples from a wire sample 24 hours after extrusion. The samples were then put on a tray which contains a layer of Talc. The tray was then placed in an oven, which was set at a temperature of 115° C. After four hours, the samples were then removed, and allowed to cool to room temperature. The samples were then measured, and then, the shrink-back was calculated in terms of percentage difference from the initial six inch length. The 10 samples were then averaged. In on-wire shrinkage testing, the copper wire was left in the test sample. In off-wire shrink-back testing, the copper wire was removed prior to testing.
  • [0143]
    The present invention may be embodied in other forms without departing from the spirit and the essential attributes thereof, and, accordingly, reference should be made to the appended claims, rather than to the foregoing specification, as indicating the scope of the invention.
  • [0000]
    TABLE I
    Inventive Sample Resin No.
    1 2 3 4 5 6
    Co-Monomer Type 1-hexene 1-hexene 1-hexene 1-hexene 1-hexene 1-hexene
    Catalyst Ziegler-Natta Ziegler-Natta Ziegler-Natta Ziegler-Natta Ziegler-Natta Ziegler-Natta
    Co-Catalyst 2.5% TEAL 2.5% TEAL 2.5% TEAL 2.5% TEAL 2.5% TEAL 2.5% TEAL
    1st Reactor Type Gas Phase Gas Phase Gas Phase Gas Phase Gas Phase Gas Phase
    2nd Reactor Type Gas Phase Gas Phase Gas Phase Gas Phase Gas Phase Gas Phase
    1st Reaction Temperature (° C.) 85 85 85 85 85 85
    2nd Reaction Temperature (° C.) 109.9 110 110 110 110 110
    1st Reaction Pressure (psi) 349 349 349 349 348 348
    2nd Reaction Pressure (psi) 403 405 405 402 404 394
    1st Reactor C2 Partial Pressure (psi) 23.2 22.6 26.3 24.9 20.7 26.1
    2nd Reactor C2 Partial Pressure (psi) 93.7 97.2 100.6 100.8 104.1 81.1
    1st Reactor H2/C2 Molar Ratio 0.082 0.060 0.093 0.080 0.052 0.115
    2nd Reactor H2/C2 Molar Ratio 1.80 1.802 1.805 1.127 1.799 1.799
    1st Reactor C6/C2 Molar Ratio 0.062 0.1049 0.0253 0.0635 0.0918 0.0463
    2nd Reactor C6/C2 Molar Ratio 0.004 0.0051 0.0050 0.0036 0.0021 0.0029
    Catalyst Feed Rate (cc/hr) 3.2 5.2 5.7 5.4 7.2 6
    (First Reactor Only)
    1st Reactor Isopentane (Mole %) 8.6 8.7 8.0 7.4 7.4 8.8
    2nd Reactor Isopentane (Mole %) 4.0 4.4 3.5 2.8 2.6 3.4
  • [0000]
    TABLE II
    Inventive Sample Resin No.
    1 2 3 4 5 6
    Split (1st reactor/2nd reactor) 0.448/0.552 0.472/0.528 0.484/0.516 0.460/0.540 0.427/0.573 0.559/0.441
    Cocatalyst Feed Rate (cc/hr) (1st reactor/ 161/161 161/158 162/154 162/154 171/170 162/134
    2nd reactor)
    Production Rate (lb/hr) (1st reactor/2nd 24.0/21.3 24/21 24/21 24/23 25/27 25/17
    reactor)
    Bed Weight (lbs) (1st reactor/2nd reactor)  75.6/135.7  76/122  75/119  75/120  76/120  78/137
    FBD (lb/ft3) (1st reactor/2nd reactor) 11.1/16.3 11.1/16.4 11.7/17.4 11.3/16.5 11.1/17.0 11.6/16.4
    Bed Volume (ft3) (1st reactor/2nd reactor) 6.8/8.3 6.8/7.4 6.4/6.8 6.7/7.3 6.8/7.1 6.8/8.3
    Residence Time (hr) (1st reactor/2nd reactor) 3.1/3.0 3.2/2.7 3.1/2.6 3.1/2.6 3.1/2.3 3.1/3.3
    STY (lb/hr/ft3) (1st reactor/2nd reactor) 3.5/2.6 3.5/2.8 3.7/3.1 3.6/3.2 3.6/3.8 3.7/2.0
    Melt index (I21) (1st Component) (~) (g/10 2.28 2.25 2.04 2.41 1.36 3.96
    minutes)
    Density (1st Component) (~) (g/cm3) 0.9282 0.9221 0.9360 0.9292 0.9227 0.9336
    Residual Ti (ppm) (1st component/2nd component) 3.76/1.63 3.15/1.61 3.66/1.61 3.33/1.52 3.99/1.56 3.66/1.99
    Residual Al (ppm) (1st component/2nd component) 97.5/48.2 99.63/58.37 101.00/49.25  94.30/49.42 105.69/48.22  102.34/56.70 
    Al/Ti Molar Residual Ti (ppm) (1st component/ 47.4/52.8 56/65 49/55 51/54 47/56 50/51
    2nd component)
    Bulk Density (lb/ft3) Residual Ti (ppm) (1st 17.8/25.0 16.7/24.1 20.1/25.6 17.6/24.5 17.0/24.8 18.3/24.8
    component/2nd component)
    H-D Polyethylene Composition Melt Index (I2) 1.48 1.46 1.39 1.66 1.31 1.58
    (2.16 g/10 minutes)
    H-D Polyethylene Composition Melt Index (I5) 5.89 5.99 4.96 6.06 5.69 5.58
    (5.0 g/10 minutes)
    H-D Polyethylene Composition Melt Index (I10) 26.3 23.5 20.1 20.6 23.5 19.6
    (10.0 g/10 minutes)
    H-D Polyethylene Composition Melt Index (I21.6) 139.7 162.0 133.6 108.6 179.5 108.0
    (21.6 g/10 minutes)
    H-D Polyethylene Composition Melt Flow Ratio 94.2 111.0 96.5 65.3 137.1 68.5
    (MI21/MI2)
    H-D Polyethylene Composition Melt Flow Ratio 23.7 27.0 26.9 17.9 31.5 19.3
    (MI21/MI5)
    H-D Polyethylene Composition Melt Flow Ratio 17.7 16.1 14.5 12.4 17.9 12.5
    (MI10/MI2)
    H-D Polyethylene Composition Density (g/cm3) 0.9548 0.9506 0.9591 0.9548 0.9546 0.955
    ASTM Slow cooled
    C13 NMR Hexene Content (Weight Percent) 1.5 2.9 0.9 1.3 1.8 1.4
    H-D Polyethylene Composition (Mn) 8,125 8,920 9,310 14,500 10,500 11,700
    H-D Polyethylene Composition (Mw) 124,600 133,300 135,000 136,000 130,400 133,000
    H-D Polyethylene Composition (Mw/Mn) 15.3 14.9 14.5 9.4 12.4 11.4
    g′ 1.007
    Atref HD Fraction (%) 70.8 58.4 74.1 67.4 55.9 71
    Calculated Atref HD Fraction (%) 36.8 28.9 43.3 36.7 27.7 41.3
    Atref Purge fraction (%) 15.2 21.4 21 27.4 19.6 18.3
    Atref SCBD Fraction (%) (27 to 86° C.) 14 20.2 4.9 5.2 24.5 10.7
    Atref MV average 58,100 53,800 63,000 63,400 49,400 56,700
    Atref SCBD Mv 58,100 56,600 68,600 68,400 51,100 60,400
    Atref Purge Mv 58,050 43,600 41,800 46,700 42,750 40,200
    Viscosity at 10 − 2 sec − 1 Shear Rate 11,580 13,700 12,900 11,200 17,000 11,200
    (Pa · S)
    Viscosity at 10 + 2 sec − 1 Shear Rate 805 834 903 918 828 952
    (Pa · S)
    Ratio 10 − 2/10 + 2 14.4 16.4 14.3 12.2 20.5 11.8
    Tan Delta @ 10 − 2 7.6 6.98 7.61 8.1 5.67 8.51
    Tan Delta @ 10 + 2 0.828 0.79 0.81 0.94 0.76 0.88
    Rheotens Melt Strength (cN) 2.5 2.5 2.5 2.5 3 2.5
    Rheotens Melt Strength (velocity mm/s) 212 200 210 205 170-200 225
    Flexural Modulus (0.5 in/min) (psi) 218,000 187,000 243,000 217,000 221,000 236,000
    Standard Deviation (+/−) 7,723 9,400 15,000 10,000 13,400 10,000
    2% Secant Modulus (psi) 163,000 138,000 169,000 157,000 157,000 160,000
    Standard Deviation (+/−) 3,470 5,660 3,300 6,900 1,900 4,400
    1% Secant Modulus (psi) 193,500 164,000 203,000 186,400 188,000 193,000
    Standard Deviation (+/−) 5,246 8,570 5,700 9,550 1,500 5,250
    Tensile Properties (ave thickness, mils)
    Tensile Strength (psi) 2,600 2,500 2,550 3,250 3,050 2,650
    Standard Deviation (+/−) 307 160 260 630 440 100
    Elongation at Break (%) 510 480 720 720 630 740
    Standard Deviation (+/−) 227 145 200 225 85
    Yield Strength (psi) 3,535 3,048 3,750 3,500 3,600 3,600
    Standard Deviation (+/−) 135 160 150 140 220 105
    Elongation at Yield (%) 3.44 3.89 3.58 3.68 3.36 3.67
    Standard Deviation (+/−) 0.68 0.41 0.33 0.41 0.49 0.28
    ESCR Test Data
    50° C.; 10% Igepal; 75 mil plaque, 12 mil F50 = F0 > F50 = F50 = F0 > F50 =
    slit (F50 hours) 509 1,188 239.9 329.4 1,188 247.1
    50° C.; 100% Igepal; 75 mil plaque, 12 mil F0 > F0 > F50 = F0 > F0 > F0 >
    slit (F50 hours) 2,000 1,188 1,071 1,188 1,188 1,188
    Extrudability Good
  • [0000]
    TABLE III
    Inventive Sample Resin No.
    1 2 3 4 5 6
    Irganox 1076 (ppm) 0 0 0 0 0 0
    Irganox 1010 (ppm) 420 536 465 486 481 412
    Irgafos 168 Active (ppm) 353 366 393 360 363 268
    Irgafos 168 Oxidized (ppm) 120 174 114 159 158 195
    Irgafos 168 Total (ppm) 473 540 507 519 521 463
  • [0000]
    TABLE IV
    Inventive Inventive Comparative Comparative Comparative Comparative
    Example 1a Example 1b Example A Example B Example C Example D
    Temperature (° F.)
    Zone 1 360 360 360 360 360 360
    Zone 2 380 380 380 380 380 380
    Zone 3 410 410 410 410 410 410
    Zone 4 420 420 420 420 420 420
    Zone 5 433 440 440 440 440 440
    Head 422 422 422 422 422 422
    Die 460 460 460 460 460 460
    Melt 419 420 420 444 471 441
    Pressure (psi)
    Zone 5 2590 2870 3790 5185 5055 4340
    Breaker 2320 2580 3250 4795 5190 4000
    Head 1730 1930 2440 3550 3700 2980
    Screw Amps 24.4 28.5 32.6 44 48.8 38.2
    Screw Speed (rpm) 38.3 56.7 36.8 38.5 44.3 39.5
    Line Speed (ft/min) 200 300 200 200 200 200
    Extruder amps 24.4 28.5 32.6 44 48.8 38.2
    Average Surface Smoothness, (micro- 11.2 10.7 22.3 53.3 57.2 20.3
    inch)
    Shrink-back on-wire after 24 hrs (%) 1.09 0.81 1.41 1.95 1.82 1.33
    Shrink-back off-wire after 24 hrs (%) 3.39 3.1 3.57 4.43 3.59 3.41
  • [0000]
    TABLE V
    Inventive
    Example 1a Comparative A Comparative B Comparative C Comparative D
    Density (g/cm3) 0.9566 0.9485 0.9444 0.9504 0.9556
    Melt Index (I2) g/10 minutes 1.746 0.790 0.162 0.076 0.306
    Melt Index (I21.6) g/10 minutes 168.405 59.756 18.541 7.714 29.478
    I21.6/I2 96 76 114 101 96
    Shore D Hardness 61.0 59.1 58.8 60.1 61.4
    Flexural Modulus (psi) 97,613 72,884 66,196 79,042 87,923
    1% Secant Modulus (psi) 2″/min. 349,119 264,620 257,942 278,073 303,872
    Tensile @ Yield (psi) 2″/min. 3,834 3,251 3,193 3,466 3,878
    Tensile @ Break 2″/min. 3,834 3,251 4,055 5,255 4,410
    Elongation (%) 2″/min. 627 642 759 711 780
    ESCR 50° C./10% Igepal Days to break 1/27 10/3 10/9 0 0
    Dielectric Constant @ 1 MHz 2.292454 2.333211 2.33668 2.328488 2.349914
    Dissipation Factor @ 1 MHz 0.000106 9.73E−05 0.000135 4.66E−05 9.32E−05
    Low Temperature Brittleness <−75° C. <−75° C. <−75° C. <−75° C. <−75° C.
  • [0000]
    TABLE VI
    Inventive Comparative Comparative Comparative Comparative Comparative Comparative
    Example 2 E1 E2 F1 F2 G1 Example G2
    Temperature (° F.)
    Zone 1 360 360 360 360 360 360 360
    Zone 2 380 380 380 380 380 380 380
    Zone 3 410 410 410 410 410 410 410
    Zone 4 420 420 420 420 420 420 420
    Zone 5 440 440 440 440 440 440 440
    Head 422 422 422 422 422 422 422
    Die 460 460 460 460 460 460 460
    Melt 420 445 426 473 441 441 424
    Pressure (psi)
    Zone 5 2620 5055 4130 5160 4630 4395 3665
    Breaker 2290 4640 3690 5240 4630 4050 3315
    Head 1730 3420 2760 3750 3280 2970 2450
    Screw Amps 24 42.6 32.9 48.7 40.5 38.7 30
    Screw Speed (rpm) 37.6 38 18.5 49.3 20.7 39.3 19.4
    Line Speed (ft/min) 200 200 100 200 100 200 100
    Extruder amps 24 42.6 32.9 48.7 40.5 38.7 30
    Average Surface 11 88.8 18.1 66.5 44.4 21.9 15.6
    Smoothness, (micro-in)
    Shrink-back on-wire 0.86 1.9 1.61 1.88 1.67 0.99 1.46
    after 24 hrs (%)
    Shrink-back off-wire 3.1 4.24 4.79 3.54 3.67 3.46 3.41
    after 24 hrs (%)
  • [0000]
    TABLE VII
    Inventive
    Example 2 Comparative H Comparative J Comparative I Comparative G1
    Density (g/cm3) 0.9702 0.9569 0.9566 0.9582 0.9677
    Melt Index (I2) g/10 minutes 1.675 0.804 0.179 0.506 0.317
    Melt Index (I21.6) g/10 minutes 155.926 62.804 23.143 40.642 30.125
    I21.6/I2 93 78 129 80 95
    Shore D Hardness 61.6 57.9 58.2 58.3 61.6
    Flexural Modulus (psi) 98,567 65,290 66,941 69,965 102,124
    1% Secant Modulus (psi) 2″/min. 239,147 150,399 202,437 173,593 274,186
    Tensile @ Yield (psi) 2″/min. 4,133 3,121 3,032 3,119 3,949
    Tensile @ Break 2″/min. 4,133 3,486 4,578 4,580 3,949
    Elongation (%) 2″/min. 355 808 908 821 484
    ESCR 50° C./10% Igepal Days to break 0 10/6 1/24 0 0
    Dielectric Constant @ 1 MHz 2.608686 2.561575 2.567739 2.573513 2.604177
    Dissipation Factor @ 1 MHz 0.000236 0.000228 0.000224 0.000445 0.000261
    Low Temperature Brittleness <−75° C. <−75° C. <−75° C. <−75° C. <−75° C.
  • [0000]
    TABLE VIII
    Inventive Compara- Compara- Compara-
    Example 3 tive H tive I tive J
    Temperature (° F.)
    Zone 1 360 360 360 360
    Zone 2 380 380 380 380
    Zone 3 410 410 410 410
    Zone 4 420 420 420 420
    Zone 5 440 440 442 442
    Head 422 422 422 422
    Die 460 460 460 460
    Melt 420 435 434 435
    Pressure (psi)
    Zone 5 2620 3670 4450 3670
    Breaker 2290 3140 3840 3140
    Head 1730 2360 2820 2360
    Screw Amps 24 31 36.8 31
    Screw Speed (rpm) 37.6 35.2 36.5 35.2
    Line Speed (ft/min) 200 200 200 200
    Extruder amps 24 31 32.3 41
    Average Surface 11 17.9 22.5 33.2
    Smoothness,
    (micro-inch)
    Shrink-back on-wire 0.86 1.38 1.54 2.4
    after 24 hrs (%)
    Shrink-back off-wire 3.1 3.65 3.54 4.69
    after 24 hrs (%)
Citas de patentes
Patente citada Fecha de presentación Fecha de publicación Solicitante Título
US3888709 *10 May 197410 Jun 1975Dow Chemical CoCable filling compounds
US4302565 *16 Feb 197924 Nov 1981Union Carbide CorporationImpregnated polymerization catalyst, process for preparing, and use for ethylene copolymerization
US4438238 *25 Ene 198220 Mar 1984Sumitomo Chemical Company, LimitedLow density copolymer composition of two ethylene-α-olefin copolymers
US4508842 *29 Mar 19832 Abr 1985Union Carbide CorporationEthylene polymerization using supported vanadium catalyst
US4530914 *6 Jun 198323 Jul 1985Exxon Research & Engineering Co.Process and catalyst for producing polyethylene having a broad molecular weight distribution
US4798081 *22 Dic 198717 Ene 1989The Dow Chemical CompanyHigh temperature continuous viscometry coupled with analytic temperature rising elution fractionation for evaluating crystalline and semi-crystalline polymers
US4871705 *16 Jun 19883 Oct 1989Exxon Chemical Patents Inc.Process for production of a high molecular weight ethylene a-olefin elastomer with a metallocene alumoxane catalyst
US4937299 *1 Feb 198526 Jun 1990Exxon Research & Engineering CompanyProcess and catalyst for producing reactor blend polyolefins
US5017714 *7 Sep 198921 May 1991Exxon Chemical Patents Inc.Silicon-bridged transition metal compounds
US5026798 *13 Sep 199025 Jun 1991Exxon Chemical Patents Inc.Process for producing crystalline poly-α-olefins with a monocyclopentadienyl transition metal catalyst system
US5055438 *4 Jun 19908 Oct 1991Exxon Chemical Patents, Inc.Olefin polymerization catalysts
US5089321 *10 Ene 199118 Feb 1992The Dow Chemical CompanyMultilayer polyolefinic film structures having improved heat seal characteristics
US5096867 *13 Sep 199017 Mar 1992Exxon Chemical Patents Inc.Monocyclopentadienyl transition metal olefin polymerization catalysts
US5106926 *11 Dic 199021 Abr 1992Union Carbide Chemicals & Plastics Technology CorporationPreparation of ethylene/1-octene copolymers of very low density in a fluidized bed reactor
US5120867 *26 Feb 19919 Jun 1992Welborn Jr Howard CSilicon-bridged transition metal compounds
US5124418 *2 Dic 198823 Jun 1992Exxon Chemical Patents Inc.Supported polymerization catalyst
US5145819 *8 Nov 19918 Sep 1992Hoechst Aktiengesellschaft2-substituted disindenylmetallocenes, process for their preparation, and their use as catalysts in the polymerization of olefins
US5198401 *30 Jul 199130 Mar 1993Exxon Chemical Patents Inc.Ionic metallocene catalyst compositions
US5210352 *28 May 199111 May 1993Phillips Petroleum CompanyFluorene compounds
US5229478 *9 Oct 199020 Jul 1993Exxon Chemical Patents Inc.Process for production of high molecular weight EPDM elastomers using a metallocene-alumoxane catalyst system
US5243001 *13 Oct 19927 Sep 1993Hoechst AktiengesellschaftProcess for the preparation of a high molecular weight olefin polymer
US5264405 *13 Mar 199223 Nov 1993Exxon Chemical Patents Inc.Monocyclopentadienyl titanium metal compounds for ethylene-α-olefin-copolymer production catalysts
US5272236 *15 Oct 199121 Dic 1993The Dow Chemical CompanyElastic substantially linear olefin polymers
US5278119 *28 Abr 199211 Ene 1994Exxon Chemical Patents Inc.Catalysts, method of preparing these catalysts, and polymerization processes wherein these catalysts are used
US5278264 *24 Ago 199211 Ene 1994Hoechst AgProcess for the preparation of an olefin polymer
US5278272 *2 Sep 199211 Ene 1994The Dow Chemical CompanyElastic substantialy linear olefin polymers
US5290745 *10 Ago 19921 Mar 1994Union Carbide Chemicals & Plastics Technology CorporationProcess for producing ethylene polymers having reduced hexane extractable content
US5292845 *21 Ene 19938 Mar 1994Mitsui Petrochemical Industries, Ltd.Ethylene/alpha-olefin/7-methyl-1,6-octadiene copolymer rubber and composition of the same
US5304614 *14 Oct 199219 Abr 1994Hoechst AktiengesellschaftProcess for the preparation of an olefin polymer using metallocenes having specifically substituted indenyl ligands
US5317036 *16 Oct 199231 May 1994Union Carbide Chemicals & Plastics Technology CorporationGas phase polymerization reactions utilizing soluble unsupported catalysts
US5324800 *30 Ago 199128 Jun 1994Exxon Chemical Patents Inc.Process and catalyst for polyolefin density and molecular weight control
US5332793 *28 Jun 199326 Jul 1994Union Carbide Chemicals & Plastics Technology CorporationEthylene/propylene copolymer rubbers
US5342907 *28 Jun 199330 Ago 1994Union Carbide Chemicals & Plastics Technology CorporationEthylene/propylene copolymer rubbers
US5347025 *7 Sep 199313 Sep 1994Tosoh CorporationCatalyst for polymerization of vinyl compound
US5350723 *15 May 199227 Sep 1994The Dow Chemical CompanyProcess for preparation of monocyclopentadienyl metal complex compounds and method of use
US5384299 *19 Feb 199324 Ene 1995Exxon Chemical Patents Inc.Ionic metallocene catalyst compositions
US5391789 *5 Ago 199221 Feb 1995Hoechst AktiengesellschaftBridged, chiral metallocenes, processes for their preparation and their use as catalysts
US5391790 *15 Jun 199321 Feb 1995Hoechst AktiengesellschaftProcess for the preparation of bridged, chiral metallocene catalysts of the bisindenyl type
US5399636 *11 Jun 199321 Mar 1995Phillips Petroleum CompanyMetallocenes and processes therefor and therewith
US5408017 *14 Jun 199318 Abr 1995Exxon Chemical Patents Inc.High temperature polymerization process using ionic catalysts to produce polyolefins
US5410003 *31 Mar 199425 Abr 1995Union Carbide Chemicals & Plastics Technology CorporationProcess for production of homogeneous polyethylenes
US5455366 *17 Ene 19953 Oct 1995Hoechst AgMetallocenes having benzo-fused indenyl derivatives as ligands, processes for their preparation and their use as catalysts
US5491207 *14 Dic 199313 Feb 1996Exxon Chemical Patents Inc.Process of producing high molecular weight ethylene-α-olefin elastomers with an indenyl metallocene catalyst system
US5527752 *29 Mar 199518 Jun 1996Union Carbide Chemicals & Plastics Technology CorporationCatalysts for the production of polyolefins
US5534473 *5 Jun 19959 Jul 1996Phillips Petroleum CompanyCatalyst systems for producing broad molecular weight polyolefin
US5539124 *19 Dic 199423 Jul 1996Occidental Chemical CorporationPolymerization catalysts based on transition metal complexes with ligands containing pyrrolyl ring
US5554775 *17 Ene 199510 Sep 1996Occidental Chemical CorporationBorabenzene based olefin polymerization catalysts
US5621126 *15 Oct 199315 Abr 1997Exxon Chemical Patents Inc.Monocyclopentadienyl metal compounds for ethylene-α-olefin-copolymer production catalysts
US5684098 *15 Feb 19964 Nov 1997Industrial Technology Research InstituteProcess for the polymerization or copolymerization of ethylene using mao- or borate-free single site catalysts
US5693730 *7 Jun 19952 Dic 1997Hoechst AktiengesellschaftMetallocenes, process for their preparation and their use as catalysts
US5698634 *18 Jul 199616 Dic 1997Mitsui Toatsu Chemicals, Inc.Process for preparing block copolymer of monoolefin
US5710297 *13 Sep 199620 Ene 1998Hoechst AktiengesellschaftMetallocenes, and their use as catalysts
US5712354 *10 Jul 199627 Ene 1998Mobil Oil CorporationBridged metallocene compounds
US5714427 *23 Sep 19943 Feb 1998Hoechst AktiengesellschaftCatalyst system comprising two zirconocenes and aluminoxane
US5718974 *24 Jun 199617 Feb 1998Union Carbide Chemicals & Plastics Technology CorporationCable jacket
US5770664 *13 May 199723 Jun 1998Japan Polyolefins Co., Ltd.Catalyst component for producing polyolefin, catalyst for producing polyolefin comprising the catalyst component, and process for producing polyolefin in the presence of the catalyst
US5770753 *7 Jun 199523 Jun 1998Targor GmbhMetallocenes containing aryl-substituted indenyl derivatives as ligands, process for their preparation, and their use as catalysts
US6147167 *21 Jun 199914 Nov 2000Equistar Chemicals, LpProcess for producing polyethylene film composition having broad molecular weight distribution and improved bubble stability
US6152543 *4 Jun 199228 Nov 2000Basf AktiengesellschaftIsolatable catalyst system suitable for the polymerization of C2 -C10 -alk-1-enes
US6180721 *3 Mar 199930 Ene 2001Borealis Polymers OyInsulating composition for communication cables
US6187866 *4 Jun 199913 Feb 2001Union Carbide Chemicals & Plastics Technology CorporationStaged reactor process
US6248831 *6 Dic 199919 Jun 2001Union Carbide Chemicals & Plastics Technology CorporationHigh strength polyethylene film
US6329054 *3 Jul 199611 Dic 2001Borealis Polymers OyCable and method for using a cable-sheathing composition including an ethylene polymer mixture
US6485662 *3 Dic 199626 Nov 2002Union Carbide Chemicals & Plastics Technology CorporationProcess for preparing a simulated in situ polyethylene blend
US6511935 *8 Jun 200128 Ene 2003Union Carbide Chemicals & Plastics Technology CorporationMethods of making magnesium/transition metal alkoxide complexes and polymerization catalysts made therefrom
US6596392 *29 Ene 199922 Jul 2003Mitsui Chemicals, Inc.Sheathed wires and cables
US6924031 *23 Mar 20012 Ago 2005Pirelli Cavi E Sistemi S.P.A.Low-smoke self-extinguishing electrical cable and flame-retardant composition used therein
US20060287445 *7 Abr 200421 Dic 2006Whited Stephanie MProcess for control of polymer fines in a gas-phase polymerization
Citada por
Patente citante Fecha de presentación Fecha de publicación Solicitante Título
US8445594 *2 May 200721 May 2013Dow Global Technologies LlcHigh-density polyethylene compositions, method of making the same, articles made therefrom, and method of making such articles
US8697806 *22 Abr 201315 Abr 2014Dow Global TechnologiesHigh-density polyethylene compositions and method of making the same
US918142112 Mar 201410 Nov 2015Dow Global Technologies LlcHigh-density polyethylene compositions, method of making the same
US9458310 *13 Ago 20124 Oct 2016Exxonmobil Chemical Patents Inc.Modified polyethylene film compositions
US9477261 *14 Feb 201325 Oct 2016Google Inc.Portable computer with cylinders providing friction in hinge
US974024021 Mar 201622 Ago 2017Google Inc.Base with rotating mount that increases friction of rotation when portable computing device is placed onto mount
US20080221273 *2 May 200711 Sep 2008Michie Jr William JHigh-Density Polyethylene Compositions, Method of Making the Same, Articles Made Therefrom, and Method of Making Such Articles
US20130211008 *13 Ago 201215 Ago 2013Pradeep P. ShirodkarModified Polyethylene Film Compositions
US20150307679 *2 Dic 201329 Oct 2015Dow Global Technologies LlcPolyolefin-Based Cable Compound Formulation for Improved Foamability and Enhanced Processability
WO2014099335A22 Dic 201326 Jun 2014Dow Global Technologies LlcPolyolefin-based cable compound formulation for improved foamability and enhanced processability
WO2014099360A14 Dic 201326 Jun 2014Dow Global Technologies LlcPolyolefin-based compound for cable jacket with reduced shrinkage and enhanced processability
WO2015094516A112 Nov 201425 Jun 2015Dow Global Technologies LlcOptical fiber cable components
WO2016137695A13 Feb 20161 Sep 2016Union Carbide Chemicals & Plastics Technology LlcPolyolefin compounds for cable coatings
Clasificaciones
Clasificación de EE.UU.428/218, 428/341
Clasificación internacionalB32B27/08, B32B7/02
Clasificación cooperativaC08L23/0815, C08L23/08, C08L2203/10, C08L23/04, Y10T428/24992, Y10T428/273, C08L23/06
Clasificación europeaC08L23/08A1, C08L23/06, C08L23/04