CA2441262A1 - High melt strength polymers and method of making same - Google Patents

High melt strength polymers and method of making same Download PDF

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CA2441262A1
CA2441262A1 CA002441262A CA2441262A CA2441262A1 CA 2441262 A1 CA2441262 A1 CA 2441262A1 CA 002441262 A CA002441262 A CA 002441262A CA 2441262 A CA2441262 A CA 2441262A CA 2441262 A1 CA2441262 A1 CA 2441262A1
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equal
molecular weight
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hmw
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CA2441262C (en
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Alexander W. Degroot
James C. Stevens
Sylvie Y. Desjardins
Jeffrey Weinhold
Edmund Carnahan
David Gillespie
Daniel D. Vanderlende
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Dow Global Technologies LLC
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    • C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
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    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
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    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
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    • C08F4/65908—Component covered by group C08F4/64 containing a transition metal-carbon bond in combination with an ionising compound other than alumoxane, e.g. (C6F5)4B-X+
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    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
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    • C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
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    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
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    • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
    • C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
    • C08F4/6592—Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring
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    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/62—Refractory metals or compounds thereof
    • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
    • C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
    • C08F4/6592—Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring
    • C08F4/65922—Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring containing at least two cyclopentadienyl rings, fused or not
    • C08F4/65925—Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring containing at least two cyclopentadienyl rings, fused or not two cyclopentadienyl rings being mutually non-bridged
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    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/62—Refractory metals or compounds thereof
    • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
    • C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
    • C08F4/6592—Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring
    • C08F4/65922—Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring containing at least two cyclopentadienyl rings, fused or not
    • C08F4/65927—Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring containing at least two cyclopentadienyl rings, fused or not two cyclopentadienyl rings being mutually bridged
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    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
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    • C08L2207/07—Long chain branching
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    • C08L2314/06—Metallocene or single site catalysts
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
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    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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    • Y10S526/00—Synthetic resins or natural rubbers -- part of the class 520 series
    • Y10S526/943—Polymerization with metallocene catalysts

Abstract

A polymer composition comprises: (a) a high molecular weight, branched component; and (b) a low molecular weight, branched component. Some polymer compositions are characterized by a substantial absent of amyl or methyl branches and a melt strength (MS) that satisfies the following relationship, formula (I), where x is greater than or equal to about 12.5 and y is greater than or equal to about 3. Some polymers are characterized by a melt strength (MS) that satisfies the following relationship, formula (II), where x is greater than or equal to about 3 and y is greater than or equal to about 4.5 and a molecular weight distribution of greater than 3. A process for making polymers is also disclosed.

Claims (59)

1. A process of making a polymer, comprising:

a) contacting one or mare olefinic monotrrers in the presence of at least a high molecular weight (HMW) catalyst and at least a low molecular weight (LMW) catalyst in a polymerization reactor system under polymerization conditions; and b) effectuating the polymerization of the one or more olefic monomers in the polymerization reactor system to obtain an olefin polymer, wberein the LMW catalyst has an R L w, defined as wherein [vinyl is the concentration of vinyl groups in the olefin polymer produced by the low molecular weigh catalyst expressed in vinyls/1,000 carbon atoms;
[vinylidene], [cis] and [trans] are the concentration of vinylidene, cis and traps groups in the olefin polymer expressed.

in the number of the respective groups per 1,000 carbon aroms, of greater than 0.12, and wherein the HMW catalyst has a reactivity ratio, r1 of about 5 or less; and wherein the 1.MW catalyst comprises a complex corresponding to the formula:
wherein: M is a metal of group 3, 4-10, or the lanthanide series of the periodic cable of the elements; Cp* is a eyelopentadieuyl or substituted cyclopeutadieuyl group bound in an ris bonding mode to M; Z is a moiety comprising baron, or a member of group 14 of the periodic table of the elements, and optionally sulfiu or oxygen, the moiety having up to 40 non-hydrogen atoms, and optianaily Cp* and Z together form a fused ring system; X
tndeper:dently in each occurrence is an anionic ligand group, said X having up to 30 non-hydrogene atoms; n is 2 less than the valence of M when Y is anionic, or 1 less than the valence of M when Y is neutral; L

independently each occurrence is a neutral Lewis base ligand group, said L
having up to 30 non-hydrogen atoms; M is 0,1, 2, 3, or 4; and Y is an anionic or neutral ligand group bonded to Z and M comprising nitrogen, pbosphorus, oxygen or sulfur and having up to 40 non-hydrogen atoms, optionally Y and Z together form a fused ring system.
The process of claim 1, wherein an R~ for the high molecular weight catalyst is defined
3. The process of claim 1, wherein R~ is greater than 0.15.
4. The process of claim 1, wherein R~ is greater than 0.20.
5. The process of claim 1, wherein R~ is greater than 0.25.
6. The process of claim 1, wherein R~ is greater than 0.35.
7. The process of claim ~, wherein R~ is greater than 0.45.
8. The process of claim 1, wherein R~ is greater than 0.50.
9. The process of claim 1, wherein r1 is about 4 or less.
10. The process of claim 1, wherein r1 is about 3 or less.
11. The process of claim 2, wherein the R~/~R~ ratio is about 0.80 to about 1.40.
12. The process of claim 1, wherein the process is operated under continuous solution polymerization conditions.
13. The process of claim 1 wherein the process is a slurry process.
14. The process of claim 1, wherein the high molecular weight catalyst or the low molecular weight catalyst are supported on an inert support.
15. The process of claim 1, wherein the polymerization reactor system includes a first reactor connected to a second reactor in parallel so that mixing occurs in a third reactor.
16. The process of claim 15 wherein the HMW catalyst contacts the one or more olefin monomers in the first reactor to produce a first reactor product and the LMW
catalyst contacts the first reactor product in the second reactor.
17. The process of claim 1, wherein the first reactor is connected to the second reactor in series and the HMW catalyst contacts the one or more olefin monomers in the first reactor to produce a first reactor product and the LMW catalyst contacts the first reactor product in the second reactor.
18. The process of claim 15, wherein the HMW catalyst, the LMW catalyst, and the one or more olefinic monomers are sequentially introduced into the polymerization reactor system.
19. The process of claim 1, wherein the first reactor is operated under continuous solution polymerization conditions.
20. A polymer composition, comprising:
a) a high molecular weight (HMW), branched component ; and b) a low molecular weight (LMW), branched, component wherein the composition is bimodal, substantially free of short chain branches characteristic of LDPE, and characterized by a melt strength (MS) that satisfies the following relationship:

where x is greater than or equal to about 12.5 and y is greater than or equal to about 3.

21. A polymer composition, comprising:
a) a backbone chain; and b) a plurality of long chain branches connected to the backbone;

where x is greater than or equal to about 12.5 and y is greater than or equal to about 3.
21. A polymer composition, comprising:
a) a backbone chain; and b) a plurality of long chain branches connected to the backbone;
wherein the a value of 2g~-~g~ of less than 0.22, where ~g~ is the long chain branching index for a fraction of the composition having a M w of 100,000 and 2 g~ is the long chain branching index for a fraction of the composition having a M w of 500,000 and wherein the HMW component and the LMW component have a substantially equal comonomer incorporation.

20. A polymer composition, comprising:
a) a high molecular weight (HMW), branched component ; and b) a low molecular weight (LMW), homogeneous, branched, component wherein the composition is bimodal, substantially free of short chain branches characteristic of LDPE, and characterized by a melt strength (MS) that satisfies the following relationship:

22. A polymer composition, comprising:
a) a high molecular weight (HMW), branched component; and b) a low molecular weight (HMW), homogeneous, branched, component wherein the composition is bimodal, substantially free of short chain branches characteristic of LDPE, and characterized by a melt strength (MS) that satisfies the following relationship:

where x is greater than or equal to about 3 and y is greater than or equal to about 4.5 and a molecular weight distribution of greater than 3.

wherein the a value of 2 g'LCB -1g LCB of less than 0.22, where 1g LCB is the long chain branching index for a fraction of the composition having a M w of 100,000 and 2g LCB is the long chain branching index for a fraction of the composition having a M w of 500,000.
22. A polymer composition, comprising:
a) a high molecular weight (HMW), branched component ; and b) a low molecular weight (LMW), branched, component wherein the composition is bimodal, substantially free of short chain branches characteristic of LDPE, and characterized by a melt strength (MS) that satisfies the following relationship:

where x is greater than or equal to about 3 and y is greater than or equal to about 4.5 and a molecular weight distribution of greater than 3.
23. The composition of claim 20 or 22, wherein x is about 12.5 and y is about 4.5.
24. The composition of claim 20 or 22, wherein x is about 15 and y is greater than or equal to about 4.5.
25. The composition of claim 20 or 22, wherein x is about 20 and y is greater than or equal to about 7.5.
26. The composition of claim 20, wherein the composition has a value of 2 g'LCB -1 g'LCB of less than or equal to 0.22, , where 1 g LCB is the long chain branching index for a fraction of the composition having a M w of 100,000 and 2 g'LCB is the long chain branching index for a fraction of the composition having a M w of 500,000.
27. The composition of claim 21 or 26, wherein 2g'LCB -1g'LCB is less than or equal to 0.20.
28. The composition of claim 21 or 26, wherein 2g'LCB -1g'LCB is less than or equal to 0.15.
29. The composition of claim 21 or 26, wherein 2g'LCB-1g'LCB is less than or equal to 0.12.
30. The composition of claim 20 or 21, wherein the composition has a molecular weight distribution greater than 3Ø
31. The composition of claim 20 or 21, wherein the composition has a molecular weight distribution from greater than 3.0 to about 12Ø
32. The composition of claim 21 comprising a high molecular weight (HMW) component and a low molecular weight (LMW) component.
33. The composition of claim 22 comprising a high molecular weight (HMW) component and a low molecular weight (LMW) component.
34. The composition of claim 20, 21, or 32, wherein the HMW component has a M
w/M n of about 1.5 to about 4Ø
35. The composition of claim 20, 21, or 32, wherein LMW component has a M w/M
n of about 1.5 to about 4Ø
36. The composition of claim 20, 21, or 32, wherein the HMW component has a M
w greater than about 300,000 g/mol.
37. The composition of claim 20, 21, or 32, wherein the LMW component has a M
w less than about 200,000.
38. The composition of claim 20, 21, or 22, wherein the composition is characterized by a DOS of about 5 or higher.
39. The composition of claim 20 or 21, wherein the composition is characterized by a DOS
of about 20 or higher.
40. The composition of claim 20, 21, or 22, wherein the composition is characterized by a DOS of 50 or higher.
41. The composition of claim 20, 21, or 22, wherein the composition is characterized by a DOS of 100 or higher.
42. The composition of claim 20, 21, or 22, wherein the composition is characterized by a DOS of 1000 or higher.
43. The composition of claim 20, 21, or 22, wherein the composition is characterized by a DOS of 10000 or higher.
44. The composition of claim 20, 21, or 32, wherein the HMW component has a molecular weight distribution of less than about 3.0 and the LMW component has a molecular weight distribution of less than about 3Ø
45. The composition of claim 20, 21, or 32, wherein the HMW component and the LMW
component have a substantially equal comonomer incorporation.
46. The composition of claim 20, 21, or 32, wherein composition has a ratio of the molecular weight of the HMW component to the molecular weight of the LMW component, M~/~M~, that is greater than about 10.
47. The composition of claim 20, 21, or 32, wherein the HMW component comprises from greater than 0 % to about 50 % by weight of the total composition and the LMW
component comprises from about 50 % by weight to less than about 100 % by weight of the total composition.
48. The composition of claim 20, 21, or 32, wherein the HMW component comprises from greater than 1 % to about 10 % by weight of the total composition and the LMW
component comprises from about 90 % by weight to about 99 % by weight of the total composition.
49. The composition of claim 20, 21, or 32, wherein the HMW component comprises from greater than 2 % to about 5 % by weight of the total composition and the LMW
component comprises from about 95 % by weight to about 98 % by weight of the total composition.
50. The composition of claim 21 wherein the composition has a melt strength (MS) that satisfies the following relationship:

where x is greater than or equal to about 12.5, and y is greater than or equal to about 3.
51. The composition of claim 21 wherein the composition has a melt strength (MS) that satisfies the following relationship:

where x is greater than or equal to about 12.5 and y is greater than or equal to about 4.5.
52. The composition of claim 21 wherein the composition has a melt strength (MS) that satisfies the following relationship:

where x is greater than or equal to about 15.0 and y is greater than or equal to about 4.5.
53. The composition of claim 21 wherein the composition has a melt strength (MS) that satisfies the following relationship:

where x is greater than or equal to about 20 and y is greater than or equal to about 7.5.
54. The composition of claim 22, wherein x is greater than about 5 and y is greater than or equal to about 4.5.
55. The composition of claim 22, wherein x is greater than about 7.5 and y is greater than or equal to about 4.5.
56. The composition of claim 22, wherein x is greater than about 9.5 and y is greater than or equal to about 7.
57. An article of manufacture comprising the composition of any of claims 20, 21, or 22.
58. Claim 57 wherein the article of manufacture is a film, afiber, a molding, a coating, a profile, a pouch, a sealant film, a carpet backing, a liner, a shrink film, a stretch film, an extrusion coating, a laminating film, a rotomoloding, a sack, a bag, or a pipe.
59. Claim 58 wherein the bag or sack is fabricated using form-fill-seal (FFS) equipment or verticle form-fill-seal equipment.
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