CA2441028A1 - Method of making interpolymers and products made therefrom - Google Patents

Method of making interpolymers and products made therefrom Download PDF

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CA2441028A1
CA2441028A1 CA002441028A CA2441028A CA2441028A1 CA 2441028 A1 CA2441028 A1 CA 2441028A1 CA 002441028 A CA002441028 A CA 002441028A CA 2441028 A CA2441028 A CA 2441028A CA 2441028 A1 CA2441028 A1 CA 2441028A1
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molecular weight
polymer
reactor
catalyst
high molecular
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CA2441028C (en
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James C. Stevens
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
    • C08F210/16—Copolymers of ethene with alpha-alkenes, e.g. EP rubbers
    • C—CHEMISTRY; METALLURGY
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    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
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    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
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    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/08—Copolymers of ethene
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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
    • C08F4/65908—Component covered by group C08F4/64 containing a transition metal-carbon bond in combination with an ionising compound other than alumoxane, e.g. (C6F5)4B-X+
    • C—CHEMISTRY; METALLURGY
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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
    • C08F4/65912—Component covered by group C08F4/64 containing a transition metal-carbon bond in combination with an organoaluminium compound
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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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/62—Refractory metals or compounds thereof
    • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
    • C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
    • C08F4/6592—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
    • C—CHEMISTRY; METALLURGY
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    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/62—Refractory metals or compounds thereof
    • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
    • C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
    • C08F4/6592—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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
    • C—CHEMISTRY; METALLURGY
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    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2207/00—Properties characterising the ingredient of the composition
    • C08L2207/06—Properties of polyethylene
    • C08L2207/07—Long chain branching
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2314/00—Polymer mixtures characterised by way of preparation
    • C08L2314/02—Ziegler natta catalyst
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2314/00—Polymer mixtures characterised by way of preparation
    • C08L2314/06—Metallocene or single site catalysts
    • 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
    • Y02P20/00—Technologies relating to chemical industry
    • 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
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S526/00—Synthetic resins or natural rubbers -- part of the class 520 series
    • Y10S526/943—Polymerization with metallocene catalysts

Abstract

A polymerization process comprises contacting one or more olefinic comonomers in the presence of at least a high molecular weight catalyst and at least a low molecular weight catalyst in a single reactor; and effectuating the polymerization of the olefinic comonomers in the reactor to obtain an olefin polymer. Preferably, both catalysts have the ability to incorporate a substantially similar amount of comonomers in the olefin polymer. The polymers produced by the process may have a relatively higher level of long chain branching while maintaining a relatively narrow molecular weight distribution, i.e., MWD less than about 6. These interpolymers may exhibit processability similar to or better than LDPE but have physical properties similar to metallocene catalyzed polymers.

Claims (55)

1. A process of making an olefin polymer, comprising:
contacting one or more olefinic monomers in the presence of at least a high molecular weight catalyst and at least a low molecular weight catalyst in a single reactor;
and effectuating the polymerization of the olefinic monomers in the reactor under polymerization conditions to obtain an olefin polymer, wherein the high molecular weight catalyst and the low molecular weight catalyst each include a compound of the formula:
wherein: M is a metal of group 3, 4-10, or the lanthanide series of the periodic table of the elements; Cp* is a cyclopentadienyl or substituted cyclopentadienyl group Z
is a moiety comprising boron, a member of group 14 of the periodic table of the elements, or sulfur or oxygen, and having ups to 40 non-hydrogen atoms, and optionally Cp* and Z together form a fused ring system; X independently each occurrence is an anionic ligand group, said X having up to 30 non-hydrogen 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, phosphorus, oxygen or sulfur and having up to 40 non-hydrogen atoms, optionally Y and Z together form a fused ring system;

wherein the high molecular weight catalyst and the low molecular weight catalyst incorporate a similar amount of comonomers in the polymer under the polymerization conditions, and wherein the high molecular weight catalyst produces a polymer with a high molecular weight M w H from the monomers under the polymerization conditions, and the low molecular weight catalyst produces a polymer with a low molecular weight M
w I, from the same monomers under polymerization conditions, where M w H/M w I, is greater than about 4Ø

The process of claim 1, wherein the high molecular weight catalyst has a reactivity ratio r~ and the low molecular weight catalyst has a reactivity ratio r~; r~ is 18 or less.
2. The process of claim 1, wherein the olefin polymer is characterized by a R
v as defined in the following:
~
wherein [vinyl] is the concentration of vinyl groups in the olefin polymer expressed in vinyls/1,000 carbon atoms; [vinylidene], [cis] and [trans] are the concentration of vinylidene, cis and trans groups in the olefin polymer expressed in the number of the respective groups per 1,000 carbon atoms, wherein R v is 0.12 or higher.
3. The process of claim 0, wherein r~/r,~, is between 0.2 to 5.
4. The process of claim 0, wherein r~/r~ is between 0.3 to 3.3.
5. The process of claim 0, wherein r~/r~ is between 0.4 to 2.5
6. The process of claim 0, wherein r~/r~ is between 0.5 to 2Ø
7. The process of claim 0, wherein r~/r~ is between 0.6 to 1.7.
8. The process of claim 0, wherein r~/r~ is between 0.7 to 1.4.
9. The process of claim 0, wherein r~/r~ is between 0.8 to 1.3.
10. The process of claim 0, wherein r~/r~ is between 0.9 to 1.1.
11. The process of claim 0, wherein r~/r~ is substantially equal to one.
12. The process of claim 1, wherein the high molecular weight catalyst is characterized by R~, the low molecular weight catalyst is characterized by R~, wherein R, for each catalyst is defined is defined by the following equation in terms of a polymer produced by the catalyst, when used alone:

wherein [vinyl] is the concentration of vinyl groups in the polymer expressed in vinyls/1,000 carbon atoms; [vinylidene], [cis] and [trans] are the concentration of vinylidene, cis and trans groups in the polymer expressed in the number of the respective groups per 1,000 carbon atoms.
13. The process of claim 12, wherein R~ is 0.12 or higher, and R~ is 0.08 or less.
14. The process of claim 12, wherein R~ is 0.12 or higher, and R~ is 0.08 or higher.
15. The process of claim 12, wherein R~ is 0.08 or less, and R~ is 0.12 or higher.
16. The process of claim 12, wherein R~ is 0.08 or less, and R ~ is 0.12 or less.
17. The process of claim 1, wherein the process is a continuous solution process, and the olefin polymer has a steady state concentration of 15% or more by weight of the reactor content.
18. The process of claim 17, wherein the olefin polymer comprises ethylene with a steady-state concentration 3.5% or less by weight of the reactor content.
19. The process of claim 1, wherein the M w H/M w L is between 4.0 and 40.
20. The process of claim 1, wherein the M w H/M w L is between 4.0 and 8.5.
21. The process of claim 1, wherein the M w H/M w L, is between 4.0 and 7Ø
22. The process of claim 1, wherein the M w H/M w L is between 4.0 and 6Ø
23. The process of claim 1, wherein one of the catalysts is (N-1,1-dimethylethyl)-1,1-(4-methylphenyl)-1-((1,2,3,3a,7a-n)-3-(1,3-dihydro-2H-isoindol-2-yl)-1H-inden-1-yl)silanaminato-(2-)-N-)dimethyltitanium.
24. The process of claim 1, wherein one of the catalysts (N-1,1-dimethylethyl)-1,1-(4-butylphenyl)-1-((1,2,3,3a,7a-n)-3-(l,3-dihydro-2H-isoindol-2-yl)-1H-inden-1-yl)silanaminato-(2-)-N-)dimethyltitanium.
25. The process of claim 1, wherein one of the catalysts is (C5Me4SiMe2N1Bu)Ti(.eta.4-1,3-pentadiene).
26. The process of claim 1, wherein the high molecular weight catalyst is (N-1,1-dimethylethyl)-1,1-(4-butylphenyl)-1-((1,2,3,3a,7a-n)-3-(1,3-dihydro-2H-isoindol-2-y1)-1H-inden-1-yl)silanaminato-(2-)-N-)dimethyltitanium.
27. The process of claim 1, wherein the high molecular weight catalyst is (N-1,1-dimethylethyl)-1,1-(4-methylphenyl)-1-((1,2,3,3a,7a-n)-3-(1,3-dihydro-2H-isoindol-2-yl)-1H-inden-1-yl)silanaminato-(2-)-N-)dimethyltitanium.
28. The process of claim 1, wherein the low molecular weight catalyst is (C5Me4SiMe2N1Bu)Ti(.eta.4-1,3-pentadiene).
29. The process of claim 1, wherein the olefinic monomers are selected from ethylene, propylene, 1-butene, 1-hexene, 1-octene, 1-decene, vinyl-cyclohexene, styrene, ethylidene norbornene, norbornadiene, 1.5-hexadiene, 1,7-octadiene, and 1,9-decadiene.
30. The olefin polymer of claim 1, wherein the olefin polymer has a comb-like structure.
31. The process of claim 1, wherein the olefin polymer is a homopolymer.
32. The process of claim 31, wherein the olefin monomer is propylene, 1-butene, 1-hexene, 1-octene, 1-decene, vinyl-cyclohexene, styrene, ethylidene norbornene, norbornadiene, 1.5-hexadiene, 1,7-octadiene, and 1,9-decadiene.
33. The process of claim 31, wherein the homopolymer is polypropylene, polybutene, or polystyrene.
34. The process of claim 31, wherein the homopolymer has 3 long chain branches per carbons.
35. An polyethylene polymer having a melt strength of about 5 cN at 190°C., and when the polymer is made into a film, the film has a CD shrink of at least 20%.
36. The polymer of claim 35 characterised by a comb-like structure and having at least 0.03 long chain branches per 1000 carbons.
37. The olefin polymer of claim 35 or 36, wherein the polymer includes a high molecular weight fraction and a low molecular weight fraction.
38. The olefin polymer of claim 37, wherein the high molecular weight fraction is from 0 to 100.
39. The olefin polymer of claim 37, wherein the low molecular weight fraction is from 0 to 100.
40. The olefin polymer of claim 35 or 36, wherein the polymer is an ethylene/propylene copolymer, ethylene/1-butene copolymer, ethylene/1-hexene, ethylene/styrene, ethylene/1-octene copolymers, or ethylene/propylene/diene terpolymer.
41. A process for producing a C2-20 olefin homopolymer or interpolymer, comprising:
continuously feeding one or more C2-20 olefins into the reactor;
continuously feeding the low molecular weight catalyst into the reactor at a fixed rate;
continuously feeding the high molecular weight catalyst into the reactor under polymerization conditions, wherein the low molecular weight catalyst and the high molecular weight catalyst incorporate similar amount of comonomer in the polymer and the ratio of the molecular weight of the polymer produced by the high molecular weight catalyst to the molecular weight of the polymer produced by the low molecular weight catalyst, M wH/M wL in the range from 4.0 to 40; and recovering the polymer product.
42. The process of claim 41, wherein continuously feeding the low molecular weight catalyst into the reactor comprises feeding the low molecular weight at a first rate to produce with a melt index equal to or greater than about two times a target melt index; and continuously feeding the high molecular weight catalyst into the reactor comprises feeding the high molecular weight catalyst at a second rate to adjust the melt index of the polymer to produce a polymer product with the target melt index.
43. The process of claim 41, wherein the first reactor is connected to the second reactor in parallel so that the mixing occurs in a third reactor.
44. The process of claim 41, wherein the first reactor is connected to the second reactor in series.
45. The process of claim 44, wherein the first-reactor contents are sequentially introduced into the second reactor.
46. The process of claim 41, wherein the first reactor is operated under continuous solution polymerization conditions.
47. The process of claim 41, wherein the second reactor is operated under continuous solution polymerization conditions.
48. The process of claim 41, wherein at least one of the catalysts is a single site catalysts having an R v greater than about 0.12.
49. The process of Claim 47, wherein the ethylene has a steady state concentration of about 3.5% or less by weight of the first-reactor contents.
50. The process of claim 47, wherein the first reactor has a polymer with a steady state concentration of about 15% or more by weight of the first-reactor contents.
51. The process of claim 41, wherein M wH/M wL is between 4.0 and 10.
52. The process of claim 41, wherein the ethylene concentration is 2.5% or less by weight of the reactor content.
53. The process of claim 41, wherein the ethylene concentration is 2.0% or less by weight of the reactor content.
54. The process of claim 47, wherein the ethylene polymer concentration is 18%
or more by weight of the reactor content.
55. The process of claim 47, wherein the ethylene polymer concentration is 20%
or more by weight of the reactor content.
CA2441028A 2001-03-16 2002-03-15 Method of making interpolymers and products made therefrom Expired - Lifetime CA2441028C (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
US27671901P 2001-03-16 2001-03-16
US60/276,719 2001-03-16
PCT/US2002/008121 WO2002074817A2 (en) 2001-03-16 2002-03-15 Method of making interpolymers and products made therefrom

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