Showing posts with label POLYOLEFINS. Show all posts
Showing posts with label POLYOLEFINS. Show all posts
Thursday, December 1, 2016
A Polyolefin Composition And Method Of Producing The Same (Dow Global Technologies)
CATEGORY: POLYOLEFINS
A Polyolefin Composition And Method Of Producing The Same (Dow Global Technologies)
United States Patent Application 20160340453
Chen; Linfeng ; et al. November 24, 2016
Assignee: Dow Global Technologies LLC
Abstract
The instant invention provides a polyolefin composition, a catalyst composition, and a method of producing the same. The method for polymerizing one or more polyolefins according to the present invention comprises the steps of: (1) selecting a first olefin monomer and optionally one or more alpha-olefin comonomers; (2) selecting one or more catalyst systems comprising one or more procatalysts comprising a first metal selected from the group consisting of Ti, V, Hf, Zr, and combinations or mixture two or more thereof, one or more cocatalysts comprising Al, and one or more self-limiting agents (SLA) selected from the group consisting of polyether, polyester, and combinations or mixtures thereof; wherein the ratio of said SLA to said first metal (SLA:first metal) is from 0.1:1 to 30:1; (3) polymerizing said first olefin monomer and optionally one or more alpha-olefin comonomers in the presence of said one or more catalyst systems via a slurry polymerization process or gas-phase polymerization process in one or more reactors; (4) thereby producing one or more olefin-based polymers; (5) wherein said catalyst system has a loss of least 85 percent of catalyst activity when the temperature is increased from 85 to 110.degree. C.
FIELD OF INVENTION
[0001] The instant invention relates to a polyolefin composition, a catalyst composition, and method of producing the same.
BACKGROUND OF THE INVENTION
[0002] Olefin (co)polymerization, for example ethylene (co)polymerization, typically operates at a temperature that is close to the softening temperature of the resultant (co)polymer. Insufficient heat removal can easily lead to temperature exceeding the softening temperature and cause (co)polymer agglomeration that may disrupt production continuity.
[0003] In a gas phase polymerization process, the polymerization reactor is cooled by the circulating monomer gasses to maintain a steady operating temperature. However, if the temperature of a growing resin particle approaches the sticking/melting point of the resin, resin sheeting on the reactor walls may occur. Growing resin particles are especially susceptible to overheating if they accumulate at the reactor walls, thereby losing heat-transfer with the circulating monomer gasses, and remaining in close contact with respect to each other. In such instances, particle-particle fusion may occur, followed by reactor sheeting, which, in turn, could cause reactor shutdown.
[0004] The currently available catalyst systems fail to address such heat removal concerns in olefin polymerization processes such as ethylene polymerization systems. Therefore, there is a need for a catalyst system having an effective mechanism that substantially reduces catalyst activity within a narrow temperature range and therefore reducing heat generation when the temperature in various parts of the reactor system approaches (co)polymer softening temperature to prevent agglomeration formation and minimizing production disruptions.
SUMMARY OF THE INVENTION
[0005] The instant invention provides a polyolefin composition, a catalyst composition, and method of producing the same.
[0006] In a first embodiment, the instant invention provides a method for polymerizing one or more olefins comprising the steps of: (1) selecting a first olefin monomer and optionally one or more alpha-olefin comonomers; (2) selecting one or more catalyst systems comprising one or more procatalysts comprising a first metal selected from the group consisting of Ti, V, Hf, Zr, and combinations or mixture of two or more thereof, one or more cocatalysts comprising Al, and one or more self-limiting agents (SLA) selected from the group consisting of polyether, polyester, and combinations or mixtures thereof; wherein the ratio of said SLA to said first metal (SLA:first metal) is from 0.1:1 to 30:1; (3) polymerizing said first olefin monomer and optionally one or more alpha-olefin comonomers in the presence of said one or more catalyst systems via a slurry polymerization process or gas-phase polymerization process in one or more reactors; (4) thereby producing one or more olefin-based polymers; (5) wherein said catalyst system has a loss of least 85 percent of catalyst activity when the temperature is increased from 85 to 110.degree. C.
[0007] In an alternative embodiment, the instant invention further provides a catalyst composition comprising one or more catalyst systems comprising one or more procatalysts comprising a first metal selected from the group consisting of Ti, V, Hf, Zr, and combinations or mixture of two or more thereof, one or more cocatalysts comprising Al, and one or more self-limiting agents (SLA) selected from the group consisting of polyether, polyester, and combinations or mixtures thereof; wherein the ratio of said SLA to said first metal (SLA:first metal) is from 0.1:1 to 30:1.
[0008] In an alternative embodiment, the instant invention further provides a polyolefin composition comprising the polymerization reaction product of the first embodiment described above.
[0009] In an alternative embodiment, the instant invention provides a polyolefin composition, a catalyst composition, a method of producing the same, in accordance with any of the preceding embodiments, except that the SLA is a polyether selected from group consisting of poly(ethylene glycol) diester, poly(ethylene glycol) mono-ester, poly(ethylene glycol) diether, poly(ethylene glycol) mono-ether, poly(ethylene glycol), poly(propylene glycol) diester, poly(propylene glycol) mono-ester, poly(propylene glycol) diether, poly(propylene glycol) mono-ether, poly(propylene glycol), and poly(vinyl ether).
[0010] In an alternative embodiment, the instant invention provides a polyolefin composition, a catalyst composition, a method of producing the same, in accordance with any of the preceding embodiments, except that the SLA is a polyether selected from group consisting of poly(ethylene glycol) diester, and poly(vinyl ether).
[0011] In an alternative embodiment, the instant invention provides a polyolefin composition, a catalyst composition, a method of producing the same, in accordance with any of the preceding embodiments, except that the SLA is a polyether selected from group consisting of poly(ethylene glycol) dilaurate, and poly(ethyl vinyl ether).
[0012] In an alternative embodiment, the instant invention provides a polyolefin composition, a catalyst composition, a method of producing the same, in accordance with any of the preceding embodiments, except that the SLA is polyester.
[0013] In an alternative embodiment, the instant invention provides a polyolefin composition, a catalyst composition, a method of producing the same, in accordance with any of the preceding embodiments, except that the polyester is poly(vinyl ester).
[0014] In an alternative embodiment, the instant invention provides a polyolefin composition, a catalyst composition, a method of producing the same, in accordance with any of the preceding embodiments, except that the poly(vinyl ester) is selected from the group consisting of poly(vinyl laurate), poly(vinyl myristate), poly(vinyl palmitate), and poly(vinyl stearate).
[0015] In an alternative embodiment, the instant invention provides a polyolefin composition, a catalyst composition, a method of producing the same, in accordance with any of the preceding embodiments, except that the poly(vinyl ester) is poly(vinyl stearate).
[0016] In an alternative embodiment, the instant invention provides a composition, a catalyst composition, a method of producing the same, in accordance with any of the preceding embodiments, except that the first olefin monomer is selected from the group consisting of ethylene, propylene, and 1-butene.
[0017] In an alternative embodiment, the instant invention provides a polyolefin composition, a catalyst composition, method of producing the same, in accordance with any of the preceding embodiments, except that the polyolefin is a polyethylene, polypropylene, or polybutene.
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Thursday, January 14, 2016
Heat Transfer in a Polymerization Reactor (United States Patent Application 20150367319 Chevron Phillips)
CATEGORY: POLYOLEFINS
Heat Transfer in a Polymerization Reactor (United States Patent Application 20150367319 Chevron Phillips)
Applicant: Chevron Phillips Chemical Company LP
United States Patent Application 20150367319
December 24, 2015
Abstract
A process comprises polymerizing an olefin monomer in a loop reactor in the presence of a catalyst and a diluent, and producing a slurry comprising solid particulate olefin polymer and diluent. The Biot number is maintained at or below about 3.0 within the loop reactor during the polymerizing process. The slurry in the loop reactor forms a slurry film having a film coefficient along an inner surface of the reactor wall, and the film coefficient is less than about 500 BTUhr.sup.-1ft.sup.-2.degree. F..sup.-1.
Abstract
A process comprises polymerizing an olefin monomer in a loop reactor in the presence of a catalyst and a diluent, and producing a slurry comprising solid particulate olefin polymer and diluent. The Biot number is maintained at or below about 3.0 within the loop reactor during the polymerizing process. The slurry in the loop reactor forms a slurry film having a film coefficient along an inner surface of the reactor wall, and the film coefficient is less than about 500 BTUhr.sup.-1ft.sup.-2.degree. F..sup.-1.
FIELD
[0004] This disclosure relates to the heat transfer in a polymerization reactor system.
BACKGROUND
[0005] Polyolefins such as polyethylene and polypropylene may be prepared by slurry polymerization. In this technique, feed materials such as diluent, monomer and catalyst are introduced to a loop reaction zone, forming a slurry in the reaction zone. In continuous loop reactors, the slurry circulates through the loop reaction zone, and the monomer reacts with the catalyst in a polymerization reaction. The polymerization reaction yields solid polyolefins in the slurry. A polymerization product having solid polyolefins is then transferred from the reactor and separated to recover the solid polyolefins.
[0006] In general, the polymerization process is exothermic, and the heat generated must be removed from the reactor to prevent the polyolefins from melting within the reactor. Such overheating may result in fouling, plugging, or other adverse effects within the reactor. In addition to limiting the adverse effects, maintaining a controlled temperature within the reactor may be important to producing a product having the desired properties.
SUMMARY
[0007] In an embodiment, a process comprises polymerizing an olefin monomer in a loop reactor in the presence of a catalyst and a diluent, and producing a slurry comprising solid particulate olefin polymer and diluent. The Biot number is maintained at or below about 3.0 within the loop reactor during the polymerizing. The slurry in the loop reactor forms a slurry film having a film coefficient along an inner surface of the shell, and the film coefficient is less than about 500 BTUhr.sup.-1ft.sup.-2.degree. F..sup.-1. The Biot number may be maintained at or below about 2.0 within the loop reactor during the polymerizing, the Biot number may be maintained at or below about 1.5 within the loop reactor during the polymerizing, and/or the Biot number may be maintained at or below about 1.1 within the loop reactor during the polymerizing. The slurry may comprise a solids concentration in the range of about 25 wt % to about 70 wt %, the slurry may comprise a solids concentration in the range of about 40 wt % to about 60 wt %, and/or the slurry may comprise a solids concentration greater than about 50 wt %. The loop reactor comprises a shell having a thickness and a thermal conductivity. A ratio of the film coefficient to the thermal conductivity may be in a range of from about 8.0 ft.sup.-1 to about 50 ft.sup.-1, and/or a ratio of the film coefficient to the thermal conductivity may be in a range of from about 14 ft.sup.-1 to about 35 ft.sup.-1. A ratio of the film coefficient to the thickness may be in a range of from about 1,400 BTUhr.sup.-1ft.sup.-3.degree. F..sup.-1 to about 240,000 BTUhr.sup.-1ft.sup.-3.degree. F..sup.-1, and/or a ratio of the film coefficient to the thickness may be in a range of from about 2,400 BTUhr.sup.-1ft.sup.-3.degree. F..sup.-1 to about 100,000 BTUhr.sup.-1ft.sup.-3.degree. F..sup.-1. A ratio of the thermal conductivity to the thickness may be in a range of from about 100 BTUhr.sup.-1ft.sup.-2.degree. F..sup.-1 to about 10,000 BTUhr.sup.-1ft.sup.-2.degree. F..sup.-1, and/or a ratio of the thermal conductivity to the thickness is in a range of from about 120 BTUhr.sup.-1ft.sup.-2.degree. F..sup.-1 to about 4,000 BTUhr.sup.-1ft.sup.-2.degree. F..sup.-1. The shell may comprise a steel selected from the group consisting of: A106 Gr 8 (60), A516 Gr 70, A537 Cl 2, A106 Gr C (40), A202 Gr 8, A285 Gr C, A514 Gr 8, A515 Gr 70, A517 Gr A, A517 Gr 8, A533 Ty A C13, A542 Ty A C12, A678 Gr C, AISI 1010, AISI 1015, MIL-S 24645, and any combination thereof. The shell has a diameter in the range of about 20 inches to about 36 inches. The inner surface of the shell has a surface smoothness of less than 100 RMS, the inner surface of the shell has a surface smoothness of less than 30 RMS, and/or the inner surface of the shell has a surface smoothness of between about 10 RMS and about 30 RMS. The process may also include circulating the slurry within the loop reactor. The slurry may be circulated at a velocity in the range of about 25 ft/s to about 60 ft/s, the slurry may be circulated at a velocity in the range of about 35 ft/s to about 50 ft/s, and/or the slurry may be circulated at a velocity greater than about 40 ft/s.
[0008] In another embodiment, a reactor comprises a continuous tubular shell comprising a thickness and a thermal conductivity, and a slurry disposed within the continuous tubular shell. The continuous tubular shell defines a continuous loop and a ratio of the thermal conductivity to the thickness is greater than or equal to about 120 BTUhr.sup.-1ft.sup.-2.degree. F..sup.-1. The slurry comprises solid particulate olefin polymer and a diluent, and the volume fraction of the solids in the slurry is greater than about 0.65. The ratio of the thermal conductivity to the thickness may be greater than or equal to about 160 BTUhr.sup.-1ft.sup.-2.degree. F..sup.-1, the ratio of the thermal conductivity to the thickness may be greater than or equal to about 250 BTUhr.sup.-1ft.sup.-2.degree. F..sup.-1, and/or the ratio of the thermal conductivity to the thickness may be greater than or equal to about 300 BTUhr.sup.-1ft.sup.-2.degree. F..sup.-1. The thermal conductivity of the shell may be between about 20 and about 40 BTUhr.sup.-1ft.sup.-2.degree. F..sup.-1. The shell may comprise a steel selected from the group consisting of: A106 Gr 8 (60), A516 Gr 70, A537 Cl 2, A106 Gr C (40), A202 Gr 8, A285 Gr C, A514 Gr 8, A515 Gr 70, A517 Gr A, A517 Gr 8, A533 Ty A C13, A542 Ty A C12, A678 Gr C, AISI 1010, AISI 1015, MIL-S 24645, and any combination thereof. The shell may comprise a steel comprising iron and one or more of components selected from the group consisting of: carbon in an amount of from about 0.05 wt % to about 0.25 wt %, silicon in an amount of from about 0.5 wt % to about 0.75 wt %, manganese in an amount of from about 0.8 wt % to about 2.0 wt %, phosphorous in an amount of from about 0.01 wt % to about 0.1 wt %, sulfur in an amount of from about 0.01 wt % to about 0.1 wt %, aluminum in an amount of from about 0.01 wt % to about 0.04 wt %, chromium in an amount of from about 0.1 wt % to about 0.5 wt %, copper in an amount of from about 0.1 wt % to about 0.5 wt %, nickel in an amount of from about 0.1 wt % to about 0.5 wt %, molybdenum in an amount of from about 0.05 wt % to about 0.1 wt %, niobium in an amount of from about 0.005 wt % to about 0.02 wt %, titanium in an amount of from about 0.01 wt % to about 0.05 wt %, vanadium in an amount of from about 0.01 wt % to about 0.04 wt %, and any combination thereof.
[0009] In another embodiment, a process comprises polymerizing an olefin monomer in a loop reactor in the presence of a catalyst and a diluent, where the loop reactor comprises a continuous tubular shell, producing a slurry comprising solid particulate olefin polymer and diluent, and circulating the slurry in the loop reactor. The slurry in the loop reactor forms a slurry film along an inner surface of the shell, and a ratio of a heat transfer resistance through the slurry film to a heat transfer resistance through the tubular shell is maintained at or below about 3.0 within the loop reactor during the polymerizing. The slurry has a velocity of greater than about 30 ft/s during the circulating. The ratio of the heat transfer resistance through the slurry film to the heat transfer resistance through the tubular shell may be maintained at or below about 2.0 within the loop reactor during the polymerizing, and/or the ratio of the heat transfer resistance through the slurry film to the heat transfer resistance through the tubular shell may be maintained at or below about 1.5 within the loop reactor during the polymerizing. The slurry may comprise a solids concentration in the range of about 25 wt % to about 70 wt %. The slurry may comprise a solids volume fraction above about 0.65. The slurry may be circulated at a velocity greater than about 40 ft/s, and/or the slurry is circulated at a velocity greater than about 50 ft/s.
[0010] In another embodiment, a polymerization process comprises polymerizing an olefin monomer in a loop reactor in the presence of a catalyst and a diluent, producing a slurry comprising solid particulate olefin polymer and diluent within the loop reactor, and contacting at least a portion of an exterior surface of the loop reactor with a coolant fluid. The slurry in the loop reactor forms a slurry film having a film coefficient along an inner surface of the loop reactor, and the coolant fluid forms a coolant film having a coolant film coefficient along an exterior surface of the loop reactor. A ratio of the film coefficient to the coolant film coefficient is greater than about 2.0. An external Biot number may be greater than about 2.0 during the polymerizing, and/or an internal Biot number may be less than about 3.0 during the polymerizing. The slurry comprises a solids volume fraction above about 0.65. The polymerization process may also include circulating the slurry in the loop reactor, and the slurry may have a velocity of greater than about 30 ft/s during the circulating.
[0011] In another embodiment, a method of designing a loop slurry polymerization reactor comprises simulating, on a processor, a loop slurry polymerization reactor, determining a Biot number of a shell region of the at least one loop slurry polymerization reactor based on the simulating, adjusting a value of at least one design parameter for the loop slurry polymerization reactor based on the simulating, repeating the simulating, by the processor, based on the adjusted value of the at least one design parameter, determining that one or more predetermined design parameters are obtained based on the repeating, and outputting a loop slurry polymerization reactor design based on the simulating, adjusting, repeating, and determining. The loop slurry polymerization reactor comprises at least one loop reactor and at least one cooling jacket, and an annulus exists between a wall of the at least one loop reactor and the cooling jacket. The method may also include graphically displaying at least a portion of the simulating, and adjusting the value of the at least one design parameter in response to the graphically displaying. The method may also include determining a position of the at least one cooling jacket adjacent and substantially parallel to at least a portion of a leg of the at least one loop reactor. The at least one design parameter for the loop slurry polymerization reactor may comprise a thermal conductivity of the wall of the at least one loop reactor, a diameter of a wall, a thickness of the wall, a velocity of a slurry within the at least one loop reactor, a slurry density of the slurry, a viscosity of the slurry, a specific heat capacity of the slurry, a thermal conductivity of the slurry, a location of the at least one cooling jacket relative to the wall, or any combination thereof. The one or more predetermined design parameters may comprise a wall thickness. The one or more predetermined design parameters may comprise an internal Biot number equal to or less than about 3.0. A slurry in the at least one loop reactor may form a slurry film having a film coefficient along an inner surface of a wall of the at least one loop reactor, and the one or more predetermined design parameters may comprise the film coefficient of less than about 500 BTUhr.sup.-1ft.sup.-2.degree. F..sup.-1. A wall of the at least one loop reactor may comprise a thickness and a thermal conductivity, and the one or more predetermined design parameters may comprise a ratio of the thermal conductivity to the thickness that is greater than or equal to about 120 BTUhr.sup.-1ft.sup.-2.degree. F..sup.-1. The at least one loop reactor may comprise a slurry disposed within a wall of the at least one loop reactor, the slurry may comprise solid particulate olefin polymer and a diluent, and the one or more predetermined design parameters may comprise a volume fraction of the solid particulate olefin polymer in the slurry that is greater than about 0.65.
[0012] These and other features will be more clearly understood from the following detailed description taken in conjunction with the accompanying drawings and claims.
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Heat Transfer in a Polymerization Reactor (United States Patent Application 20150367319 Chevron Phillips)
Applicant: Chevron Phillips Chemical Company LP
United States Patent Application 20150367319
December 24, 2015
Abstract
A process comprises polymerizing an olefin monomer in a loop reactor in the presence of a catalyst and a diluent, and producing a slurry comprising solid particulate olefin polymer and diluent. The Biot number is maintained at or below about 3.0 within the loop reactor during the polymerizing process. The slurry in the loop reactor forms a slurry film having a film coefficient along an inner surface of the reactor wall, and the film coefficient is less than about 500 BTUhr.sup.-1ft.sup.-2.degree. F..sup.-1.
Abstract
A process comprises polymerizing an olefin monomer in a loop reactor in the presence of a catalyst and a diluent, and producing a slurry comprising solid particulate olefin polymer and diluent. The Biot number is maintained at or below about 3.0 within the loop reactor during the polymerizing process. The slurry in the loop reactor forms a slurry film having a film coefficient along an inner surface of the reactor wall, and the film coefficient is less than about 500 BTUhr.sup.-1ft.sup.-2.degree. F..sup.-1.
FIELD
[0004] This disclosure relates to the heat transfer in a polymerization reactor system.
BACKGROUND
[0005] Polyolefins such as polyethylene and polypropylene may be prepared by slurry polymerization. In this technique, feed materials such as diluent, monomer and catalyst are introduced to a loop reaction zone, forming a slurry in the reaction zone. In continuous loop reactors, the slurry circulates through the loop reaction zone, and the monomer reacts with the catalyst in a polymerization reaction. The polymerization reaction yields solid polyolefins in the slurry. A polymerization product having solid polyolefins is then transferred from the reactor and separated to recover the solid polyolefins.
[0006] In general, the polymerization process is exothermic, and the heat generated must be removed from the reactor to prevent the polyolefins from melting within the reactor. Such overheating may result in fouling, plugging, or other adverse effects within the reactor. In addition to limiting the adverse effects, maintaining a controlled temperature within the reactor may be important to producing a product having the desired properties.
SUMMARY
[0007] In an embodiment, a process comprises polymerizing an olefin monomer in a loop reactor in the presence of a catalyst and a diluent, and producing a slurry comprising solid particulate olefin polymer and diluent. The Biot number is maintained at or below about 3.0 within the loop reactor during the polymerizing. The slurry in the loop reactor forms a slurry film having a film coefficient along an inner surface of the shell, and the film coefficient is less than about 500 BTUhr.sup.-1ft.sup.-2.degree. F..sup.-1. The Biot number may be maintained at or below about 2.0 within the loop reactor during the polymerizing, the Biot number may be maintained at or below about 1.5 within the loop reactor during the polymerizing, and/or the Biot number may be maintained at or below about 1.1 within the loop reactor during the polymerizing. The slurry may comprise a solids concentration in the range of about 25 wt % to about 70 wt %, the slurry may comprise a solids concentration in the range of about 40 wt % to about 60 wt %, and/or the slurry may comprise a solids concentration greater than about 50 wt %. The loop reactor comprises a shell having a thickness and a thermal conductivity. A ratio of the film coefficient to the thermal conductivity may be in a range of from about 8.0 ft.sup.-1 to about 50 ft.sup.-1, and/or a ratio of the film coefficient to the thermal conductivity may be in a range of from about 14 ft.sup.-1 to about 35 ft.sup.-1. A ratio of the film coefficient to the thickness may be in a range of from about 1,400 BTUhr.sup.-1ft.sup.-3.degree. F..sup.-1 to about 240,000 BTUhr.sup.-1ft.sup.-3.degree. F..sup.-1, and/or a ratio of the film coefficient to the thickness may be in a range of from about 2,400 BTUhr.sup.-1ft.sup.-3.degree. F..sup.-1 to about 100,000 BTUhr.sup.-1ft.sup.-3.degree. F..sup.-1. A ratio of the thermal conductivity to the thickness may be in a range of from about 100 BTUhr.sup.-1ft.sup.-2.degree. F..sup.-1 to about 10,000 BTUhr.sup.-1ft.sup.-2.degree. F..sup.-1, and/or a ratio of the thermal conductivity to the thickness is in a range of from about 120 BTUhr.sup.-1ft.sup.-2.degree. F..sup.-1 to about 4,000 BTUhr.sup.-1ft.sup.-2.degree. F..sup.-1. The shell may comprise a steel selected from the group consisting of: A106 Gr 8 (60), A516 Gr 70, A537 Cl 2, A106 Gr C (40), A202 Gr 8, A285 Gr C, A514 Gr 8, A515 Gr 70, A517 Gr A, A517 Gr 8, A533 Ty A C13, A542 Ty A C12, A678 Gr C, AISI 1010, AISI 1015, MIL-S 24645, and any combination thereof. The shell has a diameter in the range of about 20 inches to about 36 inches. The inner surface of the shell has a surface smoothness of less than 100 RMS, the inner surface of the shell has a surface smoothness of less than 30 RMS, and/or the inner surface of the shell has a surface smoothness of between about 10 RMS and about 30 RMS. The process may also include circulating the slurry within the loop reactor. The slurry may be circulated at a velocity in the range of about 25 ft/s to about 60 ft/s, the slurry may be circulated at a velocity in the range of about 35 ft/s to about 50 ft/s, and/or the slurry may be circulated at a velocity greater than about 40 ft/s.
[0008] In another embodiment, a reactor comprises a continuous tubular shell comprising a thickness and a thermal conductivity, and a slurry disposed within the continuous tubular shell. The continuous tubular shell defines a continuous loop and a ratio of the thermal conductivity to the thickness is greater than or equal to about 120 BTUhr.sup.-1ft.sup.-2.degree. F..sup.-1. The slurry comprises solid particulate olefin polymer and a diluent, and the volume fraction of the solids in the slurry is greater than about 0.65. The ratio of the thermal conductivity to the thickness may be greater than or equal to about 160 BTUhr.sup.-1ft.sup.-2.degree. F..sup.-1, the ratio of the thermal conductivity to the thickness may be greater than or equal to about 250 BTUhr.sup.-1ft.sup.-2.degree. F..sup.-1, and/or the ratio of the thermal conductivity to the thickness may be greater than or equal to about 300 BTUhr.sup.-1ft.sup.-2.degree. F..sup.-1. The thermal conductivity of the shell may be between about 20 and about 40 BTUhr.sup.-1ft.sup.-2.degree. F..sup.-1. The shell may comprise a steel selected from the group consisting of: A106 Gr 8 (60), A516 Gr 70, A537 Cl 2, A106 Gr C (40), A202 Gr 8, A285 Gr C, A514 Gr 8, A515 Gr 70, A517 Gr A, A517 Gr 8, A533 Ty A C13, A542 Ty A C12, A678 Gr C, AISI 1010, AISI 1015, MIL-S 24645, and any combination thereof. The shell may comprise a steel comprising iron and one or more of components selected from the group consisting of: carbon in an amount of from about 0.05 wt % to about 0.25 wt %, silicon in an amount of from about 0.5 wt % to about 0.75 wt %, manganese in an amount of from about 0.8 wt % to about 2.0 wt %, phosphorous in an amount of from about 0.01 wt % to about 0.1 wt %, sulfur in an amount of from about 0.01 wt % to about 0.1 wt %, aluminum in an amount of from about 0.01 wt % to about 0.04 wt %, chromium in an amount of from about 0.1 wt % to about 0.5 wt %, copper in an amount of from about 0.1 wt % to about 0.5 wt %, nickel in an amount of from about 0.1 wt % to about 0.5 wt %, molybdenum in an amount of from about 0.05 wt % to about 0.1 wt %, niobium in an amount of from about 0.005 wt % to about 0.02 wt %, titanium in an amount of from about 0.01 wt % to about 0.05 wt %, vanadium in an amount of from about 0.01 wt % to about 0.04 wt %, and any combination thereof.
[0009] In another embodiment, a process comprises polymerizing an olefin monomer in a loop reactor in the presence of a catalyst and a diluent, where the loop reactor comprises a continuous tubular shell, producing a slurry comprising solid particulate olefin polymer and diluent, and circulating the slurry in the loop reactor. The slurry in the loop reactor forms a slurry film along an inner surface of the shell, and a ratio of a heat transfer resistance through the slurry film to a heat transfer resistance through the tubular shell is maintained at or below about 3.0 within the loop reactor during the polymerizing. The slurry has a velocity of greater than about 30 ft/s during the circulating. The ratio of the heat transfer resistance through the slurry film to the heat transfer resistance through the tubular shell may be maintained at or below about 2.0 within the loop reactor during the polymerizing, and/or the ratio of the heat transfer resistance through the slurry film to the heat transfer resistance through the tubular shell may be maintained at or below about 1.5 within the loop reactor during the polymerizing. The slurry may comprise a solids concentration in the range of about 25 wt % to about 70 wt %. The slurry may comprise a solids volume fraction above about 0.65. The slurry may be circulated at a velocity greater than about 40 ft/s, and/or the slurry is circulated at a velocity greater than about 50 ft/s.
[0010] In another embodiment, a polymerization process comprises polymerizing an olefin monomer in a loop reactor in the presence of a catalyst and a diluent, producing a slurry comprising solid particulate olefin polymer and diluent within the loop reactor, and contacting at least a portion of an exterior surface of the loop reactor with a coolant fluid. The slurry in the loop reactor forms a slurry film having a film coefficient along an inner surface of the loop reactor, and the coolant fluid forms a coolant film having a coolant film coefficient along an exterior surface of the loop reactor. A ratio of the film coefficient to the coolant film coefficient is greater than about 2.0. An external Biot number may be greater than about 2.0 during the polymerizing, and/or an internal Biot number may be less than about 3.0 during the polymerizing. The slurry comprises a solids volume fraction above about 0.65. The polymerization process may also include circulating the slurry in the loop reactor, and the slurry may have a velocity of greater than about 30 ft/s during the circulating.
[0011] In another embodiment, a method of designing a loop slurry polymerization reactor comprises simulating, on a processor, a loop slurry polymerization reactor, determining a Biot number of a shell region of the at least one loop slurry polymerization reactor based on the simulating, adjusting a value of at least one design parameter for the loop slurry polymerization reactor based on the simulating, repeating the simulating, by the processor, based on the adjusted value of the at least one design parameter, determining that one or more predetermined design parameters are obtained based on the repeating, and outputting a loop slurry polymerization reactor design based on the simulating, adjusting, repeating, and determining. The loop slurry polymerization reactor comprises at least one loop reactor and at least one cooling jacket, and an annulus exists between a wall of the at least one loop reactor and the cooling jacket. The method may also include graphically displaying at least a portion of the simulating, and adjusting the value of the at least one design parameter in response to the graphically displaying. The method may also include determining a position of the at least one cooling jacket adjacent and substantially parallel to at least a portion of a leg of the at least one loop reactor. The at least one design parameter for the loop slurry polymerization reactor may comprise a thermal conductivity of the wall of the at least one loop reactor, a diameter of a wall, a thickness of the wall, a velocity of a slurry within the at least one loop reactor, a slurry density of the slurry, a viscosity of the slurry, a specific heat capacity of the slurry, a thermal conductivity of the slurry, a location of the at least one cooling jacket relative to the wall, or any combination thereof. The one or more predetermined design parameters may comprise a wall thickness. The one or more predetermined design parameters may comprise an internal Biot number equal to or less than about 3.0. A slurry in the at least one loop reactor may form a slurry film having a film coefficient along an inner surface of a wall of the at least one loop reactor, and the one or more predetermined design parameters may comprise the film coefficient of less than about 500 BTUhr.sup.-1ft.sup.-2.degree. F..sup.-1. A wall of the at least one loop reactor may comprise a thickness and a thermal conductivity, and the one or more predetermined design parameters may comprise a ratio of the thermal conductivity to the thickness that is greater than or equal to about 120 BTUhr.sup.-1ft.sup.-2.degree. F..sup.-1. The at least one loop reactor may comprise a slurry disposed within a wall of the at least one loop reactor, the slurry may comprise solid particulate olefin polymer and a diluent, and the one or more predetermined design parameters may comprise a volume fraction of the solid particulate olefin polymer in the slurry that is greater than about 0.65.
[0012] These and other features will be more clearly understood from the following detailed description taken in conjunction with the accompanying drawings and claims.
Free Full Text Source: http://appft.uspto.gov/netacgi/nph-Parser?Sect1=PTO2&Sect2=HITOFF&p=1&u=%2Fnetahtml%2FPTO%2Fsearch-bool.html&r=2&f=G&l=50&co1=AND&d=PG01&s1=catalyst&s2=chevron&OS=catalyst+AND+chevron&RS=catalyst+AND+chevron
Friday, November 15, 2013
Method For Preparation Of Polyolefins Containing Exo-Olefin Chain Ends (The University Of Southern Mississippi; and Chevron Oronite Company Llc)
PATENT
Method For Preparation Of Polyolefins Containing Exo-Olefin Chain Ends (The University Of Southern Mississippi; and Chevron Oronite Company Llc)
United States Patent Application 20130150539
Inventors:
Stokes, Casey D. (Belle Chasse, LA, US)
Storey, Robson F. (Hattiesburg, MS, US)
Harrison, James J. (Novato, CA, US)
Application Number:
13/765563
Publication Date:
06/13/2013
Assignee:
The University Of Southern Mississippi (Hattiesburg, Ms, Us)
Chevron Oronite Company Llc (San Ramon, Ca, Us)
Abstract:
The present invention is directed to a method for preparation of polyolefins containing exo-olefin chain ends. The method involves quenching a cationic quasi-living polyolefin polymer system with a nitrogen-containing five-membered aromatic ring having at least two hydrocarbyl substituent compounds attached to the ring.
FIELD OF THE INVENTION
The present invention is directed to a method for preparation of polyolefins containing exo-olefin chain ends. The method involves quenching a cationic quasi-living polyolefin polymer system with one or more nitrogen-containing five-membered aromatic ring compounds having at least two hydrocarbyl substituents attached to the ring.
BACKGROUND OF THE INVENTION
Linear polyolefins made using a mono-functional initiator containing a single “exo-olefin”, “1,1-di-substituted” olefin, or “methylvinylidene,” end group are useful precursors for the preparation of polymers containing specific functional end groups. Polymers made using multi-functional initiators would have multiple exo-olefinic end groups. Polymers containing specific end groups are useful as lubricating oil additives. One example of a functionalized polymer containing hetero atoms is polyisobutenylsuccinic anhydride. Functional end groups may also be desirable for making polymers with potential for further reactions.
Conventional ionic polymerizations can be anionic or cationic. Anionic polymerizations proceed, in the presence of a base, through carbanions and favor monomers having electron withdrawing groups. Cationic polymerizations proceed, in the presence of an acid, through a carbocation, also called a carbenium ion, and favor monomers that have electron releasing groups.
Similarly to the conventional polymerization systems, living polymerization systems may be either anionic or cationic. The difference between conventional polymerizations and living polymerizations is that an ideal living polymerization proceeds in the absence of chain transfer and chain termination. Living polymerization systems are of great commercial importance because the degree of polymerization may be controlled by controlling the feed ratio of monomer to initiator and sequential addition of two or more different monomers affords the ability to produce block copolymers. Polymerization continues until the monomer is exhausted, but the polymers retain their ability to add additional monomers any time in the future. A number of such systems are well known in the art.
A further development is the cationic quasi-living polymerization systems using conventional monomers. Quasi-living polymerization requires certain restrictive conditions, for example anhydrous reagents. Cationic quasi-living polymerizations differ from truly living polymerizations in that, although the rate of chain transfer approaches zero, chain termination is present but reversible. One important example of a cationic quasi-living polymerization is the cationic quasi-living polymerization of isobutylene.
Typically, cationic quasi-living polymerizations of isobutylene yield narrow molecular weight distribution and one major polymer product containing the 2-chloro-2-methylpropyl end group, also referred to as the “tert-chloride” end group. Under certain conditions minor amounts of olefinic isomers may also be produced.
On the other hand, there are two major olefinic isomers produced during conventional polymerization of isobutylene with BF3, for example, the highly reactive exo-olefin isomer and the relatively unreactive 2-methyl-1-propenyl isomer, also referred to as the “tri-substituted” isomer or “endo olefin” isomer. Furthermore, conventional polymerizations of isobutylene yield polymers with broad molecular weight distributions or polydispersity indices.
Exclusive production of the exo-olefin isomer has not been previously achieved under conventional polymerization conditions.
There are two established methods for producing polyisobutylene containing only the exo-olefin end group. One method involves chemical dehydrohalogenation of tert-chloride terminated polyisobutylene using potassium tert-butoxide in a post polymerization reaction (U.S. Pat. No. 4,342,849). The other method involves in situ quenching of quasi-living isobutylene with methallyltrimethylsilane, which converts an active, living carbenium ion to the exo-olefin end group. (M. Roth and H. Mayr, Macromolecules, 29, 6104, 1996)
Polyisobutylene polymers containing more than one exo-olefin end group may be prepared using the above methods by the use of a multi-functional initiator.
The preparation of polyolefins, including polyisobutylene polymers, is well known in the art. A number of patents have discussed processes for making polyisobutylene polymers containing exo-olefin end groups, but none using quenching a cationic quasi-living polymerization system with one or more nitrogen-containing five-membered aromatic ring compounds.
European Patent No. 341012 discloses a method for producing polymers with narrow molecular weight distribution, where the ratio of the weight average molecular weight, M(w), to the number average molecular weight, M(n), approaches 1.
U.S. Pat. No. 4,152,499 discloses isobutylene polymers having a mean degree of polymerization from 10 to 100 and where the proportion of theoretically possible terminal double bonds is greater than in products prepared using aluminum trichloride. The patent also discloses the method of making the isobutylene polymers using boron trifluoride as the initiator.
U.S. Pat. No. 4,342,849 discloses the synthesis of polyisobutylene carrying either unsaturation or hydroxyl groups at both ends, in the case of a linear polymer, or at all ends in the case of a star polymer. The method involves the steps of refluxing a solution of telechelic di-halogen polyisobutylene, adding a solution strong base such as potassium t-butoxide and stirring to form the telechelic di-olefin polyisobutylene.
U.S. Pat. No. 4,393,199 discloses a method for carrying out cationic polymerization with molecular weight control in which a pre-initiator and a catalyst effective for cationic polymerization are mixed with a monomer. The resulting living polymer is then treated as desired.
U.S. Pat. No. 4,758,631 discloses a method of preparing allyl-terminated polyisobutylene by allylation with allyltrimethylsilane of tertiary chloro-capped polyisobutylene by electrophilic substitution. The synthesis begins with the boron trichloride catalyzed mono- or oligo-tertiary chloride “inifer” initiated polymerization of isobutylene, followed in the same reaction vessel by the addition of hexane, allyltrimethylsilane and titanium tetrachloride.
U.S. Pat. Nos. 4,910,321 and 5,122,572 disclose a catalyst composed of a complex of an organic acid or its ester and a Lewis acid, preferably boron trichloride that can add olefin monomers to increase the molecular weight of the complex from as low as 200 to in excess of a million. The patents also disclose polymers of different molecular weights having useful end groups such as halogens and specifically chloride, allyl, acryl or methacryl, acetate or formate.
U.S. Pat. Nos. 4,929,683 and 5,066,730 disclose a catalyst composed of a complex of an organic ether and a Lewis acid, preferably boron trichloride that can add olefin monomers to increase the molecular weight of the complex from as low as 200 to in excess of a million. The patents also disclose polymers of different molecular weights having useful end groups such as halogens and specifically chloride, allyl, acryl or methacryl, acetate or formate.
U.S. Pat. No. 5,219,948 discloses a method for preparing elastomeric polymers comprising alpha-olefins or conjugated alkadienes by cationic polymerization in the presence of titanium tetrachloride and an electron pair donor selected from pyridine or a non-hindered alkylpyridine. The polymers have very narrow, mono-modal molecular weight distribution.
U.S. Pat. No. 5,336,745 discloses a method for the direct synthesis of polymeric materials functionalized with desirable nitrogen-containing functional groups such as terminal azido, cyano, carbonylamino or thiocarbonylamino groups. Polymerization and functionalization occur in a substantially simultaneous manner.
U.S. Pat. No. 5,428,111 discloses a process for the living polymerization of aromatic, preferably styrenic monomers initiated from a living polyolefin, particularly polyisobutylene, chain end for making block copolymers having polyolefin mid-blocks and styrenic end-blocks.
U.S. Pat. No. 5,448,000 discloses a one-pot method of preparing sulfonic acid-terminated polyisobutylene by sulfonation with acetyl sulfate of a living polyisobutylene in a single step. The method involves “inifer” initiated carbocationic polymerization with Lewis acid to form the polymer followed by the sulfonation.
U.S. Pat. Nos. 5,637,647 and 5,677,386 disclose the capping of a living polymer with one or more capping compounds comprising non-polymerizable monomer selected from a group consisting of substituted or unsubstituted diphenyl alkylene, methoxystyrene, trans-stilbene, 1-isopropenylnaphthalene and 2,4-dimethyl styrene.
U.S. patent application Ser. No. 10/433,439, Publication No. 2004/0015029 A1, discloses a process for the preparation of polyisobutylenes in which, at least 60 percent of the polymer chains have at least one olefinically unsaturated terminal group, by cationic polymerization of isobutylene or isobutylene-containing monomer mixtures in the condensed phase and in the presence of an initiator system.
U.S. patent application Ser. No. 10/600,898, Publication No. 2004/0260033 A1, discloses the method for manufacturing and producing monodisperse telechelic polymers through cationic polymerization of suitable monomer under living polymerization conditions and quenching the polymerization with an N-substituted-pyrrole. The functionalized polymers containing N-substituted-pyrroles may be employed as fuel additives and/or lubricating oil additives.
PCT International Application No. PCT/EP/05472, International Publication No. WO99/09074, discloses a process for functionalizing polymers prepared by cationic polymerization wherein a living carbocationic polymerization system is reacted with one or more aromatic ring systems, and the use of substituted or unsubstituted reaction products of said process in lubricating oil or fuel compositions and additive concentrates, for example as dispersants, detergents or antioxidant additives or VI improvers.
β-Proton elimination by Free Bases in the Living cationic Polymerization of Isobutylene, by Young Cheol Bae and Rudolf Faust, Macromolecules, Volume 30, 7341-7344 (1997). The authors investigated β-proton elimination from quasi-living polyisobutylene, after observing exo-olefin formation in the presence of 2,6-di-tert-butylpyridine (DTBP) of low purity. They ascribed elimination to the presence of a sterically hindered cyclic imine base present in the DTBP in a concentration of 6×10−6 moles per liter. They simulated this impurity using 2-tert-butylpyridine (TBP) and discovered that the latter, when added to the reactor at the start of the polymerization (i.e., in the presence of monomer) resulted in about 65 percent elimination after 3 hours of reaction time to produce exclusively exo-olefin. When the extent of elimination had reached 20 percent or higher, significant coupling was observed from both 1H NMR and GPC analyses. Bae and Faust clearly considered that elimination by sterically hindered bases such as TBP was undesirable and should be avoided. The first paragraph of the paper was summarized as follows: “Finally, strong bases may also eliminate β-protons, which should be avoided.” Later, they refer to the cyclic imine base impurity in DTBP as “the culprit”. Finally, they summarized the entire paper by saying that the elimination process should be avoided for polymer preparation purposes, although it might facilitate the measurement of kinetic rate constants: “While β-proton elimination should be avoided for the synthesis of well-defined macromolecules, if diffusion control of this process can be shown, it may provide a novel method of establishing the concentration of active centers, from which absolute propagation rate constants could be calculated.”
SUMMARY OF THE INVENTION
The present invention is directed to a method for the preparation of polyolefins containing exo-olefin chain ends. The method involves quenching a cationic quasi-living polyolefin polymer system with one or more nitrogen-containing five-membered aromatic ring compounds having at least two hydrocarbyl substituents attached to the ring. The method also involves use of Lewis acid and an electron donor, or a common ion salt or its precursor to form the cationic quasi-living polyolefin polymer to which is added the quenching agent to form the polymer product.
More specifically, the present invention is directed to a method for preparing a polyolefin containing one or more exo-olefinic end groups on the polymer chain, comprising quenching a cationic quasi-living polyolefin polymer system with one or more nitrogen-containing five-membered aromatic ring compounds selected from pyrroles and imidazoles having at least two hydrocarbyl substituents attached to the aromatic ring, provided the nitrogen containing five-membered aromatic ring is not:
•(a) 2,4-dimethylpyrrote;
•(b) 1,2,5-trimethylpyrrole;
•(c) 2-phenylindole;
•(d) 2-methylbenzimidazole;
•(e) 1,2-dimethylimidazole;
•(f) 2-phenylimidazole; and
•(g) 2,4,5-triphenylimidazole.
Preferably the quenching is carried out at a temperature in the range of from about −130° C. to about 10° C. More preferably the quenching is carried out at a temperature from about −80° C. to about 0° C., and even more preferably from about −72° C. to about −10° C. Most preferably the quenching is carried out at a temperature in the range of from about −60° C. to about −20° C.
Preferably the polyolefin is polyisobutylene.
In a preferred embodiment of the present invention the polyolefin is prepared in situ.
The nitrogen-containing five-membered aromatic ring employed in an embodiment of the present invention is a substituted pyrrole.
Free Full Text Source: http://www.freepatentsonline.com/y2013/0150539.html
Method For Preparation Of Polyolefins Containing Exo-Olefin Chain Ends (The University Of Southern Mississippi; and Chevron Oronite Company Llc)
United States Patent Application 20130150539
Inventors:
Stokes, Casey D. (Belle Chasse, LA, US)
Storey, Robson F. (Hattiesburg, MS, US)
Harrison, James J. (Novato, CA, US)
Application Number:
13/765563
Publication Date:
06/13/2013
Assignee:
The University Of Southern Mississippi (Hattiesburg, Ms, Us)
Chevron Oronite Company Llc (San Ramon, Ca, Us)
Abstract:
The present invention is directed to a method for preparation of polyolefins containing exo-olefin chain ends. The method involves quenching a cationic quasi-living polyolefin polymer system with a nitrogen-containing five-membered aromatic ring having at least two hydrocarbyl substituent compounds attached to the ring.
FIELD OF THE INVENTION
The present invention is directed to a method for preparation of polyolefins containing exo-olefin chain ends. The method involves quenching a cationic quasi-living polyolefin polymer system with one or more nitrogen-containing five-membered aromatic ring compounds having at least two hydrocarbyl substituents attached to the ring.
BACKGROUND OF THE INVENTION
Linear polyolefins made using a mono-functional initiator containing a single “exo-olefin”, “1,1-di-substituted” olefin, or “methylvinylidene,” end group are useful precursors for the preparation of polymers containing specific functional end groups. Polymers made using multi-functional initiators would have multiple exo-olefinic end groups. Polymers containing specific end groups are useful as lubricating oil additives. One example of a functionalized polymer containing hetero atoms is polyisobutenylsuccinic anhydride. Functional end groups may also be desirable for making polymers with potential for further reactions.
Conventional ionic polymerizations can be anionic or cationic. Anionic polymerizations proceed, in the presence of a base, through carbanions and favor monomers having electron withdrawing groups. Cationic polymerizations proceed, in the presence of an acid, through a carbocation, also called a carbenium ion, and favor monomers that have electron releasing groups.
Similarly to the conventional polymerization systems, living polymerization systems may be either anionic or cationic. The difference between conventional polymerizations and living polymerizations is that an ideal living polymerization proceeds in the absence of chain transfer and chain termination. Living polymerization systems are of great commercial importance because the degree of polymerization may be controlled by controlling the feed ratio of monomer to initiator and sequential addition of two or more different monomers affords the ability to produce block copolymers. Polymerization continues until the monomer is exhausted, but the polymers retain their ability to add additional monomers any time in the future. A number of such systems are well known in the art.
A further development is the cationic quasi-living polymerization systems using conventional monomers. Quasi-living polymerization requires certain restrictive conditions, for example anhydrous reagents. Cationic quasi-living polymerizations differ from truly living polymerizations in that, although the rate of chain transfer approaches zero, chain termination is present but reversible. One important example of a cationic quasi-living polymerization is the cationic quasi-living polymerization of isobutylene.
Typically, cationic quasi-living polymerizations of isobutylene yield narrow molecular weight distribution and one major polymer product containing the 2-chloro-2-methylpropyl end group, also referred to as the “tert-chloride” end group. Under certain conditions minor amounts of olefinic isomers may also be produced.
On the other hand, there are two major olefinic isomers produced during conventional polymerization of isobutylene with BF3, for example, the highly reactive exo-olefin isomer and the relatively unreactive 2-methyl-1-propenyl isomer, also referred to as the “tri-substituted” isomer or “endo olefin” isomer. Furthermore, conventional polymerizations of isobutylene yield polymers with broad molecular weight distributions or polydispersity indices.
Exclusive production of the exo-olefin isomer has not been previously achieved under conventional polymerization conditions.
There are two established methods for producing polyisobutylene containing only the exo-olefin end group. One method involves chemical dehydrohalogenation of tert-chloride terminated polyisobutylene using potassium tert-butoxide in a post polymerization reaction (U.S. Pat. No. 4,342,849). The other method involves in situ quenching of quasi-living isobutylene with methallyltrimethylsilane, which converts an active, living carbenium ion to the exo-olefin end group. (M. Roth and H. Mayr, Macromolecules, 29, 6104, 1996)
Polyisobutylene polymers containing more than one exo-olefin end group may be prepared using the above methods by the use of a multi-functional initiator.
The preparation of polyolefins, including polyisobutylene polymers, is well known in the art. A number of patents have discussed processes for making polyisobutylene polymers containing exo-olefin end groups, but none using quenching a cationic quasi-living polymerization system with one or more nitrogen-containing five-membered aromatic ring compounds.
European Patent No. 341012 discloses a method for producing polymers with narrow molecular weight distribution, where the ratio of the weight average molecular weight, M(w), to the number average molecular weight, M(n), approaches 1.
U.S. Pat. No. 4,152,499 discloses isobutylene polymers having a mean degree of polymerization from 10 to 100 and where the proportion of theoretically possible terminal double bonds is greater than in products prepared using aluminum trichloride. The patent also discloses the method of making the isobutylene polymers using boron trifluoride as the initiator.
U.S. Pat. No. 4,342,849 discloses the synthesis of polyisobutylene carrying either unsaturation or hydroxyl groups at both ends, in the case of a linear polymer, or at all ends in the case of a star polymer. The method involves the steps of refluxing a solution of telechelic di-halogen polyisobutylene, adding a solution strong base such as potassium t-butoxide and stirring to form the telechelic di-olefin polyisobutylene.
U.S. Pat. No. 4,393,199 discloses a method for carrying out cationic polymerization with molecular weight control in which a pre-initiator and a catalyst effective for cationic polymerization are mixed with a monomer. The resulting living polymer is then treated as desired.
U.S. Pat. No. 4,758,631 discloses a method of preparing allyl-terminated polyisobutylene by allylation with allyltrimethylsilane of tertiary chloro-capped polyisobutylene by electrophilic substitution. The synthesis begins with the boron trichloride catalyzed mono- or oligo-tertiary chloride “inifer” initiated polymerization of isobutylene, followed in the same reaction vessel by the addition of hexane, allyltrimethylsilane and titanium tetrachloride.
U.S. Pat. Nos. 4,910,321 and 5,122,572 disclose a catalyst composed of a complex of an organic acid or its ester and a Lewis acid, preferably boron trichloride that can add olefin monomers to increase the molecular weight of the complex from as low as 200 to in excess of a million. The patents also disclose polymers of different molecular weights having useful end groups such as halogens and specifically chloride, allyl, acryl or methacryl, acetate or formate.
U.S. Pat. Nos. 4,929,683 and 5,066,730 disclose a catalyst composed of a complex of an organic ether and a Lewis acid, preferably boron trichloride that can add olefin monomers to increase the molecular weight of the complex from as low as 200 to in excess of a million. The patents also disclose polymers of different molecular weights having useful end groups such as halogens and specifically chloride, allyl, acryl or methacryl, acetate or formate.
U.S. Pat. No. 5,219,948 discloses a method for preparing elastomeric polymers comprising alpha-olefins or conjugated alkadienes by cationic polymerization in the presence of titanium tetrachloride and an electron pair donor selected from pyridine or a non-hindered alkylpyridine. The polymers have very narrow, mono-modal molecular weight distribution.
U.S. Pat. No. 5,336,745 discloses a method for the direct synthesis of polymeric materials functionalized with desirable nitrogen-containing functional groups such as terminal azido, cyano, carbonylamino or thiocarbonylamino groups. Polymerization and functionalization occur in a substantially simultaneous manner.
U.S. Pat. No. 5,428,111 discloses a process for the living polymerization of aromatic, preferably styrenic monomers initiated from a living polyolefin, particularly polyisobutylene, chain end for making block copolymers having polyolefin mid-blocks and styrenic end-blocks.
U.S. Pat. No. 5,448,000 discloses a one-pot method of preparing sulfonic acid-terminated polyisobutylene by sulfonation with acetyl sulfate of a living polyisobutylene in a single step. The method involves “inifer” initiated carbocationic polymerization with Lewis acid to form the polymer followed by the sulfonation.
U.S. Pat. Nos. 5,637,647 and 5,677,386 disclose the capping of a living polymer with one or more capping compounds comprising non-polymerizable monomer selected from a group consisting of substituted or unsubstituted diphenyl alkylene, methoxystyrene, trans-stilbene, 1-isopropenylnaphthalene and 2,4-dimethyl styrene.
U.S. patent application Ser. No. 10/433,439, Publication No. 2004/0015029 A1, discloses a process for the preparation of polyisobutylenes in which, at least 60 percent of the polymer chains have at least one olefinically unsaturated terminal group, by cationic polymerization of isobutylene or isobutylene-containing monomer mixtures in the condensed phase and in the presence of an initiator system.
U.S. patent application Ser. No. 10/600,898, Publication No. 2004/0260033 A1, discloses the method for manufacturing and producing monodisperse telechelic polymers through cationic polymerization of suitable monomer under living polymerization conditions and quenching the polymerization with an N-substituted-pyrrole. The functionalized polymers containing N-substituted-pyrroles may be employed as fuel additives and/or lubricating oil additives.
PCT International Application No. PCT/EP/05472, International Publication No. WO99/09074, discloses a process for functionalizing polymers prepared by cationic polymerization wherein a living carbocationic polymerization system is reacted with one or more aromatic ring systems, and the use of substituted or unsubstituted reaction products of said process in lubricating oil or fuel compositions and additive concentrates, for example as dispersants, detergents or antioxidant additives or VI improvers.
β-Proton elimination by Free Bases in the Living cationic Polymerization of Isobutylene, by Young Cheol Bae and Rudolf Faust, Macromolecules, Volume 30, 7341-7344 (1997). The authors investigated β-proton elimination from quasi-living polyisobutylene, after observing exo-olefin formation in the presence of 2,6-di-tert-butylpyridine (DTBP) of low purity. They ascribed elimination to the presence of a sterically hindered cyclic imine base present in the DTBP in a concentration of 6×10−6 moles per liter. They simulated this impurity using 2-tert-butylpyridine (TBP) and discovered that the latter, when added to the reactor at the start of the polymerization (i.e., in the presence of monomer) resulted in about 65 percent elimination after 3 hours of reaction time to produce exclusively exo-olefin. When the extent of elimination had reached 20 percent or higher, significant coupling was observed from both 1H NMR and GPC analyses. Bae and Faust clearly considered that elimination by sterically hindered bases such as TBP was undesirable and should be avoided. The first paragraph of the paper was summarized as follows: “Finally, strong bases may also eliminate β-protons, which should be avoided.” Later, they refer to the cyclic imine base impurity in DTBP as “the culprit”. Finally, they summarized the entire paper by saying that the elimination process should be avoided for polymer preparation purposes, although it might facilitate the measurement of kinetic rate constants: “While β-proton elimination should be avoided for the synthesis of well-defined macromolecules, if diffusion control of this process can be shown, it may provide a novel method of establishing the concentration of active centers, from which absolute propagation rate constants could be calculated.”
SUMMARY OF THE INVENTION
The present invention is directed to a method for the preparation of polyolefins containing exo-olefin chain ends. The method involves quenching a cationic quasi-living polyolefin polymer system with one or more nitrogen-containing five-membered aromatic ring compounds having at least two hydrocarbyl substituents attached to the ring. The method also involves use of Lewis acid and an electron donor, or a common ion salt or its precursor to form the cationic quasi-living polyolefin polymer to which is added the quenching agent to form the polymer product.
More specifically, the present invention is directed to a method for preparing a polyolefin containing one or more exo-olefinic end groups on the polymer chain, comprising quenching a cationic quasi-living polyolefin polymer system with one or more nitrogen-containing five-membered aromatic ring compounds selected from pyrroles and imidazoles having at least two hydrocarbyl substituents attached to the aromatic ring, provided the nitrogen containing five-membered aromatic ring is not:
•(a) 2,4-dimethylpyrrote;
•(b) 1,2,5-trimethylpyrrole;
•(c) 2-phenylindole;
•(d) 2-methylbenzimidazole;
•(e) 1,2-dimethylimidazole;
•(f) 2-phenylimidazole; and
•(g) 2,4,5-triphenylimidazole.
Preferably the quenching is carried out at a temperature in the range of from about −130° C. to about 10° C. More preferably the quenching is carried out at a temperature from about −80° C. to about 0° C., and even more preferably from about −72° C. to about −10° C. Most preferably the quenching is carried out at a temperature in the range of from about −60° C. to about −20° C.
Preferably the polyolefin is polyisobutylene.
In a preferred embodiment of the present invention the polyolefin is prepared in situ.
The nitrogen-containing five-membered aromatic ring employed in an embodiment of the present invention is a substituted pyrrole.
Free Full Text Source: http://www.freepatentsonline.com/y2013/0150539.html
Tuesday, August 27, 2013
Production of vinylidene-terminated and sulfide-terminated telechelic polyolefins via quenching with disulfides (Chevron Oronite Company)
CATEGORY: POLYOLEFINS
PATENT
Production of vinylidene-terminated and sulfide-terminated telechelic polyolefins via quenching with disulfides (Chevron Oronite Company)
Publication number
US20130158207 A1
Application number
US 13/765,550
Publication date
Jun 20, 2013
Inventors
Casey D. Stokes
Original Assignee
Chevron Oronite Company Llc
Abstract
Provided herein are methods for preparing vinylidene-terminated polyolefins. Further provided herein are sulfide-terminated polyolefins.
Description
FIELD
Provided herein are methods for producing vinylidene-terminated polyolefins. Further, provided herein are novel sulfide-terminated polyolefins and methods for producing the same.
3. BACKGROUND
Terminally functionalized polymers are useful precursors for the preparation of polymers containing functional end groups. Examples of terminally functionalized polymers are vinylidene-terminated polyolefins. Polymers containing functional end groups have several useful purposes. For example, polyisobutylene (PIB) containing vinylidene chain ends are utilized in the synthesis of PIB-succinic anhydrides (PIBSAs), which are key intermediates in the production of PIB-based succinimide dispersants for use as additives for engine lubricants. Vinylidene-terminated PIBs are also utilized in the production of PIB-amines, which are useful as fuel additives. An opportunity exists to create polyolefins containing sulfide end groups for use in lubricant applications. These thio-terminated polyolefins can offer oxidation inhibition and surface affinity, two important factors in the design of lubricant additive technology. Thus, there is a need for new classes of terminally functionalized polymers, as well as methods of selectively or exclusively producing terminally functionalized polymers, such as vinylidene-terminate polyolefins and sulfide-terminated polyolefins.
4. SUMMARY
In some embodiments, provided herein are methods for preparing telechelic polyolefins, comprising:
• ◦a. ionizing a polyolefin in the presence of a Lewis acid or mixture of Lewis acids to form an ionized polyolefin;
◦b. reacting the ionized polyolefin from step (a) with one or more disulfides to form an intermediate; and
◦c. reacting the intermediate of step (b) with one or more alcohols, amines, or thiols.
In some embodiments, provided herein are methods for preparing a vinylidene terminated polyolefin, comprising:
• ◦a. ionizing a polyolefin in the presence of a Lewis acid or mixture of Lewis acids to form an ionized polyolefin;
◦b. reacting the ionized polyolefin from step (a) with one or more disulfides to form an intermediate; and
◦c. reacting the intermediate of step (b) with one or more alcohols or amines.
Free Full Text Source: http://www.google.com/patents/US20130158207?dq=inassignee:chevron+%7C+inassignee:uop+%7C+inassignee:shell+%7C+inassignee:exxon+%7C+inassignee:exxonmobil&hl=en&sa=X&ei=V_gIUotFiKrIAcXUgJgB&ved=0CG8Q6AEwCA
PATENT
Production of vinylidene-terminated and sulfide-terminated telechelic polyolefins via quenching with disulfides (Chevron Oronite Company)
Publication number
US20130158207 A1
Application number
US 13/765,550
Publication date
Jun 20, 2013
Inventors
Casey D. Stokes
Original Assignee
Chevron Oronite Company Llc
Abstract
Provided herein are methods for preparing vinylidene-terminated polyolefins. Further provided herein are sulfide-terminated polyolefins.
Description
FIELD
Provided herein are methods for producing vinylidene-terminated polyolefins. Further, provided herein are novel sulfide-terminated polyolefins and methods for producing the same.
3. BACKGROUND
Terminally functionalized polymers are useful precursors for the preparation of polymers containing functional end groups. Examples of terminally functionalized polymers are vinylidene-terminated polyolefins. Polymers containing functional end groups have several useful purposes. For example, polyisobutylene (PIB) containing vinylidene chain ends are utilized in the synthesis of PIB-succinic anhydrides (PIBSAs), which are key intermediates in the production of PIB-based succinimide dispersants for use as additives for engine lubricants. Vinylidene-terminated PIBs are also utilized in the production of PIB-amines, which are useful as fuel additives. An opportunity exists to create polyolefins containing sulfide end groups for use in lubricant applications. These thio-terminated polyolefins can offer oxidation inhibition and surface affinity, two important factors in the design of lubricant additive technology. Thus, there is a need for new classes of terminally functionalized polymers, as well as methods of selectively or exclusively producing terminally functionalized polymers, such as vinylidene-terminate polyolefins and sulfide-terminated polyolefins.
4. SUMMARY
In some embodiments, provided herein are methods for preparing telechelic polyolefins, comprising:
• ◦a. ionizing a polyolefin in the presence of a Lewis acid or mixture of Lewis acids to form an ionized polyolefin;
◦b. reacting the ionized polyolefin from step (a) with one or more disulfides to form an intermediate; and
◦c. reacting the intermediate of step (b) with one or more alcohols, amines, or thiols.
In some embodiments, provided herein are methods for preparing a vinylidene terminated polyolefin, comprising:
• ◦a. ionizing a polyolefin in the presence of a Lewis acid or mixture of Lewis acids to form an ionized polyolefin;
◦b. reacting the ionized polyolefin from step (a) with one or more disulfides to form an intermediate; and
◦c. reacting the intermediate of step (b) with one or more alcohols or amines.
Free Full Text Source: http://www.google.com/patents/US20130158207?dq=inassignee:chevron+%7C+inassignee:uop+%7C+inassignee:shell+%7C+inassignee:exxon+%7C+inassignee:exxonmobil&hl=en&sa=X&ei=V_gIUotFiKrIAcXUgJgB&ved=0CG8Q6AEwCA
Tuesday, February 19, 2013
Plasticized polyolefin compositions
CATEGORY: POLYOLEFINS
PATENT
Plasticized polyolefin compositions
Patent number: 8211968
Issue date: Jul 3, 2012
Application number: 12/693,287
Abstract
Inventors: Henry Wu-Hsiang Yang, Wen Li, Bruce R. Lundmark, Chon-Yie Lin, Chia Yung Cheng, Bryan R. Chapman, Petra Eiselt, Galina Ourieva, Manika Varma-Nair, James N. Coffey, Sandra Denise Schregenberger, David J. Lohse, Norman Yang, Jeffrey Theodore Zudock, Robert Jay Wittenbrink
Original Assignee: ExxonMobil Chemical Patents Inc.
FIELD OF THE INVENTION
The present invention relates to plasticized polyolefins comprising a polyolefin and a non-functionalized plasticizer. More particularly, the present invention relates to plasticized polyolefins such as propylene polymers and or butene polymers having improved properties such as processability, flexibility, softness, and impact resistance.
BACKGROUND OF THE INVENTION
Polyolefins are useful in any number of everyday articles. HoWever, one draWback to many polyolefins, especially propylene homopolymers and some propylene copolymers, is their relatively high glass transition temperature. This characteristic makes these polyolefins brittle, especially at loW temperatures. Many applications of polyolefins benefit from having useful properties over a broad range of temperatures; consequently, there is a need to provide polyolefins that can maintain desirable characteristics such as high or loW temperature performance, etc., While maintaining or improving upon the impact strength and toughness at loWer temperatures. In particular, it Would be advantageous to provide a propylene polymer possessing improved toughness and or high use temperature Without sacrificing its other desirable properties.
Addition of a plasticizer or other substance to a polyolefin is one Way to improve such properties as impact strength and toughness. Some patent disclosures directed to such an end are U.S. Pat. Nos. 4,960,820; 4,132,698; 3,201,364; WO 02/31044; WO 01/18109 A1; and EP 0 300 689 A2. These disclosures are directed to polyolefins and elastomers blended With functionalized plasticizers. The functionalized plasticizers are materials such as mineral oils Which contain aromatic groups, and high (greater than —20° C.) pour point compounds. Use of these compounds typically does not preserve the transparency of the polyolefin, and impact strength is often not improved.
WO 98/44041 discloses plastic based sheet like material for a structure, especially a floor covering, Which contains in a blend a plastic matrix comprising a chlorine free polyolefin or mixture of polyolefins and a plasticizer characterized in that the plasticizer is an oligomeric polyalphaolefin type substance.
Other background references include EP 0 448 259 A, EP 1 028 145 A, U.S. Pat. Nos. 4,073,782, and 3,415,925.
What is needed is a polyolefin With loWer flexural modulus, loWer glass transition temperature, and higher impact strength near and beloW 0° C., While not materially influencing the peak melting temperature of the polyolefin, the polyolefin crystallization rate, or its clarity, and With minimal migration of plasticizer to the surface of fabricated articles. A
plasticized polyolefin according to this invention can fulfill
these needs. More specifically, there is a need for a plasticized polypropylene that can be used in such applications as food containers and toys.
LikeWise, a plasticized polyolefin With improved softness, better flexibility (loWer flexural modulus), a depressed glass transition temperature, and or improved impact strength (improved Gardner impact) at loW temperatures (beloW 0° C.), Where the melting temperature of the polyolefin, the polyolefin crystallization rate, or its clarity are not influenced and With minimal migration of the plasticizer to the surface of articles made therefrom is desirable.
It Would be particularly desirable to plasticize polyolefins by using a simple, non-reactive compound such as a paraflin. HoWever, it has been taught that aliphatic or paraflinic compounds Would impair the properties of polyolefins, and Was thus not recommended. (See, e.g., CHEMICAL ADDITIVES FOR PLAsT1Cs INDUSTRY 107-116 (Radian Corp., Noyes Data Corporation, N.J. 1987); WO 01/18109 A1).
Mineral oils, Which have been used as extenders, softeners, and the like in various applications, consist of thousands of different compounds, many of Which are undesirable in a lubricating system. Under moderate to high temperatures these compounds can volatilize and oxidize, even With the addition of oxidation inhibitors.
Certain mineral oils, distinguished by their viscosity indices and the amount of saturates and sulfur they contain, have been classified as Hydrocarbon Basestock Group I, II or III by the American Petroleum Institute (API). Group I basestocks are solvent refined mineral oils. They contain the most unsaturates and sulfur and have the loWest viscosity indices. They define the bottom tier of lubricant performance. Group I basestocks are the least expensive to produce, and they currently account for abut 75 percent of all basestocks. These comprise the bulk of the “conventional” basestocks. Groups II and III are the High Viscosity Index and Very High Viscosity Index basestocks. They are hydroprocessed mineral oils. The Group III oils contain less unsaturates and sulfur than the Group I oils and have higher viscosity indices than the Group II oils do. Additional basestocks, named Groups IV andV, are also used in the basestock industry. Rudnick and Shubkin describe the five basestock Groups as typically being: Group Iimineral oils refined using solvent extraction of
aromatics, solvent deWaxing, hydrofining to reduce sulfur
content to produce mineral oils With sulfur levels greater
than 0.03 Weight %, saturates levels of 60 to 80% and a
viscosity index of about 90;
Group Ilimildly hydrocracked mineral oils With conventional solvent extraction of aromatics, solvent deWaxing, and more severe hydrofining to reduce sulfur levels to less than or equal to 0.03 Weight % as Well as removing double bonds from some of the olefinic and aromatic compounds, saturate levels are greater than 95-98% and VI is about 80-120;
Group IIIiseverely hydrotreated mineral oils With saturates levels of some oils virtually 100%, sulfur contents are less than or equal to 0.03 Weight % (preferably betWeen 0.001 and 0.01%) and VI is in excess of 120;
Group IVipoly-alpha-olefins-hydrocarbons manufactured by the catalytic oligomerization of linear olefins having 6 or more carbon atoms. In industry hoWever, the Group IV basestocks are referred to as “polyalphaolefins” are generally thought of as a class of synthetic basestock fluids produced by oligomerizing C4 and greater alphaolefins; and
Group V4esters, polyethers, polyalkylene glycols, and includes all other basestocks not included in Groups I, II, III and IV. (see Synthetic Lubricants and High-Performance Functional Fluids, Second edition, Rudnick, Shubkin, eds., Marcel Dekker, Inc. NeW York, 1999.)
Other references of interest include: U.S. Pat. Nos. 5,869,555, 4,210,570, 4,1 10,185, GB 1,329,915,U.S. Pat.Nos. 3,201, 364, 4,774,277, JP01282280, FR2094870, JP69029554, Rubber Technology Handbook, Werner Hoffman, Hanser Publishers, NeW York, 1989, pg 294-305, Additives for Plastics, J . Stepek, H. Daoust, Springer Verlag, NeW York, 1983, pg-6-69.
U.S. Pat. No. 4,536,537 discloses blends of LLDPE (UC 7047), polypropylene (5520) and Synfluid 2CS, 4CS, or 6CS having a viscosity of 4.0 to 6.5 cSt at 100° F./38° C., hoWever the Synfluid 4CS and 8CS are reported to “not Wor ” (col 3, ln 12).
SUMMARY OF THE INVENTION
This invention relates to plasticized polyolefin compositions comprising one or more polyolefins and one or more non-functionalized plasticizers (“NFP”).
This invention relates to plasticized polyolefin compositions comprising one or more polyolefins and one or more non-functionalized plasticizers (“NFP’s”) Where the nonfunctionalized plasticizer has a kinematic viscosity (“KV”) of 2 cSt or less at 100° C. For purposes of this invention if the NFP has a flash point of less than 100° C. it is defined to have a KV at 100° C. ofless than 2 cSt.
This invention also relates to plasticized polyolefin compositions comprising one or more polyolefins and one or more non-functionalized plasticizers Where the non-functionalized plasticizer is a polyalphaolefin comprising oligomers of C5 to C14 olefins having a Kinematic viscosity of 10 cSt or more at 100° C. and a viscosity index of 120 or more.
This invention also relates to plasticized polypropylene compositions comprising polypropylene and one or more non-functionalized plasticizers Where the non-functionalized plasticizer comprises oligomers of C5 to C14 olefins having viscosity index of 120 or more, provided that When the plasticized composition comprises betWeen 4 and 10 Weight % of polyalphaolefin that is a hydrogenated, highly branched dimer of an alpha olefin having 8-12 carbon atoms, the composition does not comprises betWeen 18 and 25 Weight percent of a linear loW density polyethylene having a density of 0.912 to 0.935 g/cc.
This invention also relates to plasticized polypropylene compositions comprising polypropylene and one or more non-functionalized plasticizers Where the non-functionalized plasticizer comprises oligomers of C6 to C14 olefins having viscosity index of 120 or more, provided that When the composition does not comprises an impact copolymer of polypropylene and 40-50 Weight % of an ethylene propylene rubber or provided that the composition does not comprise a random copolymer of propylene and ethylene.
This invention also relates to plasticized polyolefin compositions comprising one or more polyolefins and one or more non-functionalized plasticizers Where the non-functionalized plasticizer comprises linear and or branched paraflinic hydrocarbon compositions produced by one or more gas to liquids process having a number average molecular Weight of 500 to 20,000.
Free Full Text Source: http://www.google.com/patents/US20100152346?dq=exxon+OR+exxonmobil
PATENT
Plasticized polyolefin compositions
Patent number: 8211968
Issue date: Jul 3, 2012
Application number: 12/693,287
Abstract
Inventors: Henry Wu-Hsiang Yang, Wen Li, Bruce R. Lundmark, Chon-Yie Lin, Chia Yung Cheng, Bryan R. Chapman, Petra Eiselt, Galina Ourieva, Manika Varma-Nair, James N. Coffey, Sandra Denise Schregenberger, David J. Lohse, Norman Yang, Jeffrey Theodore Zudock, Robert Jay Wittenbrink
Original Assignee: ExxonMobil Chemical Patents Inc.
FIELD OF THE INVENTION
The present invention relates to plasticized polyolefins comprising a polyolefin and a non-functionalized plasticizer. More particularly, the present invention relates to plasticized polyolefins such as propylene polymers and or butene polymers having improved properties such as processability, flexibility, softness, and impact resistance.
BACKGROUND OF THE INVENTION
Polyolefins are useful in any number of everyday articles. HoWever, one draWback to many polyolefins, especially propylene homopolymers and some propylene copolymers, is their relatively high glass transition temperature. This characteristic makes these polyolefins brittle, especially at loW temperatures. Many applications of polyolefins benefit from having useful properties over a broad range of temperatures; consequently, there is a need to provide polyolefins that can maintain desirable characteristics such as high or loW temperature performance, etc., While maintaining or improving upon the impact strength and toughness at loWer temperatures. In particular, it Would be advantageous to provide a propylene polymer possessing improved toughness and or high use temperature Without sacrificing its other desirable properties.
Addition of a plasticizer or other substance to a polyolefin is one Way to improve such properties as impact strength and toughness. Some patent disclosures directed to such an end are U.S. Pat. Nos. 4,960,820; 4,132,698; 3,201,364; WO 02/31044; WO 01/18109 A1; and EP 0 300 689 A2. These disclosures are directed to polyolefins and elastomers blended With functionalized plasticizers. The functionalized plasticizers are materials such as mineral oils Which contain aromatic groups, and high (greater than —20° C.) pour point compounds. Use of these compounds typically does not preserve the transparency of the polyolefin, and impact strength is often not improved.
WO 98/44041 discloses plastic based sheet like material for a structure, especially a floor covering, Which contains in a blend a plastic matrix comprising a chlorine free polyolefin or mixture of polyolefins and a plasticizer characterized in that the plasticizer is an oligomeric polyalphaolefin type substance.
Other background references include EP 0 448 259 A, EP 1 028 145 A, U.S. Pat. Nos. 4,073,782, and 3,415,925.
What is needed is a polyolefin With loWer flexural modulus, loWer glass transition temperature, and higher impact strength near and beloW 0° C., While not materially influencing the peak melting temperature of the polyolefin, the polyolefin crystallization rate, or its clarity, and With minimal migration of plasticizer to the surface of fabricated articles. A
plasticized polyolefin according to this invention can fulfill
these needs. More specifically, there is a need for a plasticized polypropylene that can be used in such applications as food containers and toys.
LikeWise, a plasticized polyolefin With improved softness, better flexibility (loWer flexural modulus), a depressed glass transition temperature, and or improved impact strength (improved Gardner impact) at loW temperatures (beloW 0° C.), Where the melting temperature of the polyolefin, the polyolefin crystallization rate, or its clarity are not influenced and With minimal migration of the plasticizer to the surface of articles made therefrom is desirable.
It Would be particularly desirable to plasticize polyolefins by using a simple, non-reactive compound such as a paraflin. HoWever, it has been taught that aliphatic or paraflinic compounds Would impair the properties of polyolefins, and Was thus not recommended. (See, e.g., CHEMICAL ADDITIVES FOR PLAsT1Cs INDUSTRY 107-116 (Radian Corp., Noyes Data Corporation, N.J. 1987); WO 01/18109 A1).
Mineral oils, Which have been used as extenders, softeners, and the like in various applications, consist of thousands of different compounds, many of Which are undesirable in a lubricating system. Under moderate to high temperatures these compounds can volatilize and oxidize, even With the addition of oxidation inhibitors.
Certain mineral oils, distinguished by their viscosity indices and the amount of saturates and sulfur they contain, have been classified as Hydrocarbon Basestock Group I, II or III by the American Petroleum Institute (API). Group I basestocks are solvent refined mineral oils. They contain the most unsaturates and sulfur and have the loWest viscosity indices. They define the bottom tier of lubricant performance. Group I basestocks are the least expensive to produce, and they currently account for abut 75 percent of all basestocks. These comprise the bulk of the “conventional” basestocks. Groups II and III are the High Viscosity Index and Very High Viscosity Index basestocks. They are hydroprocessed mineral oils. The Group III oils contain less unsaturates and sulfur than the Group I oils and have higher viscosity indices than the Group II oils do. Additional basestocks, named Groups IV andV, are also used in the basestock industry. Rudnick and Shubkin describe the five basestock Groups as typically being: Group Iimineral oils refined using solvent extraction of
aromatics, solvent deWaxing, hydrofining to reduce sulfur
content to produce mineral oils With sulfur levels greater
than 0.03 Weight %, saturates levels of 60 to 80% and a
viscosity index of about 90;
Group Ilimildly hydrocracked mineral oils With conventional solvent extraction of aromatics, solvent deWaxing, and more severe hydrofining to reduce sulfur levels to less than or equal to 0.03 Weight % as Well as removing double bonds from some of the olefinic and aromatic compounds, saturate levels are greater than 95-98% and VI is about 80-120;
Group IIIiseverely hydrotreated mineral oils With saturates levels of some oils virtually 100%, sulfur contents are less than or equal to 0.03 Weight % (preferably betWeen 0.001 and 0.01%) and VI is in excess of 120;
Group IVipoly-alpha-olefins-hydrocarbons manufactured by the catalytic oligomerization of linear olefins having 6 or more carbon atoms. In industry hoWever, the Group IV basestocks are referred to as “polyalphaolefins” are generally thought of as a class of synthetic basestock fluids produced by oligomerizing C4 and greater alphaolefins; and
Group V4esters, polyethers, polyalkylene glycols, and includes all other basestocks not included in Groups I, II, III and IV. (see Synthetic Lubricants and High-Performance Functional Fluids, Second edition, Rudnick, Shubkin, eds., Marcel Dekker, Inc. NeW York, 1999.)
Other references of interest include: U.S. Pat. Nos. 5,869,555, 4,210,570, 4,1 10,185, GB 1,329,915,U.S. Pat.Nos. 3,201, 364, 4,774,277, JP01282280, FR2094870, JP69029554, Rubber Technology Handbook, Werner Hoffman, Hanser Publishers, NeW York, 1989, pg 294-305, Additives for Plastics, J . Stepek, H. Daoust, Springer Verlag, NeW York, 1983, pg-6-69.
U.S. Pat. No. 4,536,537 discloses blends of LLDPE (UC 7047), polypropylene (5520) and Synfluid 2CS, 4CS, or 6CS having a viscosity of 4.0 to 6.5 cSt at 100° F./38° C., hoWever the Synfluid 4CS and 8CS are reported to “not Wor ” (col 3, ln 12).
SUMMARY OF THE INVENTION
This invention relates to plasticized polyolefin compositions comprising one or more polyolefins and one or more non-functionalized plasticizers (“NFP”).
This invention relates to plasticized polyolefin compositions comprising one or more polyolefins and one or more non-functionalized plasticizers (“NFP’s”) Where the nonfunctionalized plasticizer has a kinematic viscosity (“KV”) of 2 cSt or less at 100° C. For purposes of this invention if the NFP has a flash point of less than 100° C. it is defined to have a KV at 100° C. ofless than 2 cSt.
This invention also relates to plasticized polyolefin compositions comprising one or more polyolefins and one or more non-functionalized plasticizers Where the non-functionalized plasticizer is a polyalphaolefin comprising oligomers of C5 to C14 olefins having a Kinematic viscosity of 10 cSt or more at 100° C. and a viscosity index of 120 or more.
This invention also relates to plasticized polypropylene compositions comprising polypropylene and one or more non-functionalized plasticizers Where the non-functionalized plasticizer comprises oligomers of C5 to C14 olefins having viscosity index of 120 or more, provided that When the plasticized composition comprises betWeen 4 and 10 Weight % of polyalphaolefin that is a hydrogenated, highly branched dimer of an alpha olefin having 8-12 carbon atoms, the composition does not comprises betWeen 18 and 25 Weight percent of a linear loW density polyethylene having a density of 0.912 to 0.935 g/cc.
This invention also relates to plasticized polypropylene compositions comprising polypropylene and one or more non-functionalized plasticizers Where the non-functionalized plasticizer comprises oligomers of C6 to C14 olefins having viscosity index of 120 or more, provided that When the composition does not comprises an impact copolymer of polypropylene and 40-50 Weight % of an ethylene propylene rubber or provided that the composition does not comprise a random copolymer of propylene and ethylene.
This invention also relates to plasticized polyolefin compositions comprising one or more polyolefins and one or more non-functionalized plasticizers Where the non-functionalized plasticizer comprises linear and or branched paraflinic hydrocarbon compositions produced by one or more gas to liquids process having a number average molecular Weight of 500 to 20,000.
Free Full Text Source: http://www.google.com/patents/US20100152346?dq=exxon+OR+exxonmobil
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