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  • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
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  • B01J31/2226—Anionic ligands, i.e. the overall ligand carries at least one formal negative charge
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  • C08F2400/00—Characteristics for processes of polymerization
  • C08F2400/02—Control or adjustment of polymerization parameters

Definitions

• the present disclosure relates to processes for producing polymers and gas-phase polymerization of olefins in particular.
• Gas-phase polymerization is a known process for producing polymers. Gas-phase polymerization production efficiencies move toward the maximization of the polymer production rate. When the volume of the gas-phase reactor is fixed, an increase of the reactor inventory is one approach to toward production maximization. Reactor inventory can be increased by increasing the bulk density of the fluidized bed (i.e., increasing the fiuidized bulk density).
• the present disclosure is directed to processes and reactors for increasing the bulk density of the fluidized bed in a gas-phase polymerization reactor.
• the present processes increase polymer production by increasing the bulk density of the lluidized bed.
• the fluidized bulk density is increased with reduced risk, or no risk, of sheeting, chunking, overheating, bed collapse and/or reactor shutdown.
• a process for polymerizing one or more olefins in a gas-phase reactor has a fluidized bed and a fluidizing medium.
• the fluidizing medium has an operating gas density.
• the process includes determining a critical gas density for the fluidizing medium.
• the critical gas density is determined with the following equation,
• a is a constant having a value from about 3.5 to about 6.2
• h is a constant having a value from about 1 ,7 to about 2,7
• APS is an average particle size of the fluidized bed as measured in inches
• SBD is a settled bulk density of polymer particles of the bed measured in lb/ft 3
• SGV is a gas velocity of the fluidizing medium as measured in ft/second.
• the process also includes adjusting the operating gas density of the fluidizing medium to be less than or equal to the critical gas density. The adjustment of the operating gas density increases the bulk density of the fluidized bed.
• the process includes maintaining the fluidized bed in at a least turbulent regime during the adjustment of the operating gas density.
• the process can also include moving the fluidized bed from the fast lluidization regime to the turbulent regime. This increases the bulk density of the bed.
• adjustment can occur by way of adjustment of the partial pressure of a gas contained in the fluidizing medium, adjustment/change of the composition of the fluidizing medium, or adjustment of the reactor pressure,
• the fluidizing medium includes propylene gas and at least one other gas.
• the process includes maintaining the fluidized bed in at least a turbulent regime, and decreasing the propylene partial pressure of the fluidizing medium to increase the bulk density of the fluidized bed.
• the propylene partial pressure can be reduced alone or in combination with decreasing the velocity of the fluidizing medium.
• the process includes decreasing the operating gas density from above the critical gas density to below the critical gas density. This increases the bulk density of the fluidized bed.
• another polymerization process is provided.
• the process is for polymerizing one or more olefins in a gas-phase reactor.
• the reactor has a fluidized bed and a fluidizing medium,
• the fluidizing medium has an operating gas velocity.
• the process includes determining a critical gas velocity for the fluidizing medium.
• the critical gas velocity is determined with the following equation:
• a Is a constant having a value from about 3.5 to about 6.2
• b is a constant having a value from about 1,7 to about 2.1
• APS is an average particle size of the fluidized bed as measured in inches
• SBD is a settled bulk density of polymer particles of the bed measured in
• FMD is a density of the fluidizing medium as measured in Ib/ft J .
• the process includes adjusting the operating gas velocity to less than or equal to the critical gas velocity.
• the fluidized bed is maintained in at least the turbulent regime during the adjustraent(s).
• the adjustment of the operating velocity can include moving the fluidized bed from a fast iluidization regime to a turbulent regime,
• operating gas velocity is adjusted from a velocity greater than the critical gas velocity and is decreased to less than or equal to the critical gas velocity, This increases the bulk density of the fluidized bed,
• the process includes adjusting the operating gas velocity from a velocity greater than Uk to a velocity less than Uk. This increases the bulk density of the fluidized bed.
• the operating gas velocity is maintained at a velocity greater than Uc.
• the present disclosure provides another process.
• a process for y ⁇ ierizing one or more olefins in a gas-phase reactor is provided.
• the reactor has a fluidized bed and a fluidizing medium.
• the fluidizing medium has an operating gas density and an operating gas velocity.
• the process includes determining a critical gas velocity for the fluidizing medium with the following equation;
• a is a constant having a value from about 3.5 to about 6.2
• b is a constant having a value from about 1.7 to about 2.7
• APS is an average particle size of the fluidized bed
• SBD is a settled bulk density of the fluidized bed
• FMD is a density of the fluidizing medium.
• the process includes adjusting the operating gas density and adjusting the operating gas velocity. These adjustments are performed so that the operating gas velocity is less than or equal to the critical gas velocity.
• the iluidizing medium is composed of propylene gas and at least one other gas. The process includes decreasing the partial pressure of the propylene gas, This adjustment increases the bulk density of the iluidiz ⁇ d bed.
• the process includes decreasing the operating gas velocity from a velocity greater than the critical gas velocity to a velocity less than the critical gas velocity. This increases a bulk density of the fluidized bed.
• a gas-phase polymerization reactor includes a fluidized bed of polymer particles fluidized by a fluidizing medium.
• the polymer particles have an average particle size from about 0,014 inches to about 0.12 inches.
• the fluidized bed has a bulk density from about 7 lb/ft j to about 40 lb/ft 3 .
• the fluidizing medium has an operating gas density less than or equal to the critical gas density, the critical gas density being determined as above.
• the fluidizing medium can also have an operating velocity that is less than or equal to the critical gas velocity as discussed above.
• the fluidized bed is in at least the turbulent regime.
• the gas-phase polymerization reactor includes a catalyst composition and at least one olefin gas in an interior of the gas-phase reactor.
• the polymer particles formed from the polymerization can be propylene-based polymer, ethylene-based polymer, and ethylene/propylene rubber.
• the polymer particles have a settled bulk density from about 15 lb/ft 3 to 35 lb/ft 3 .
• the fluidizing medium has a velocity from about 0.5 ft/second to about 2.6 ft/second.
• the fluidizing medium has a density from about 1.0 lb/ft' to about 5.0 lb/ft 3 ,
• the fluidizing medium includes propylene and hydrogen.
• the propylene has a partial pressure from about 300 psia to about 400 psia
• Any of the processes disclosed herein can include the introduction of a catalyst composition into the reactor to form a fluidized bed having an average particle size from about 0.014 inches to about 0,12 inches,
• Any of the processes disclosed herein can include the production of polymer particles having a settled bulk density from about 15 lb/fV to about 35 lb/ff ⁇
• Any of the processes disclosed herein can include the passage of the fluidizing medium through the reactor at a velocity from about 0,8 ft/second to about 5.0 ft/second.
• any of the processes disclosed herein can Include increasing the bulk density of the fhridixed bed from about 10 wt % to about 100 wt %.
• the bulk density increase is based on the bulk density before the adjustments.
• the present disclosure provides an improved process for the gas-phase polymerization of one or more olefins.
• An advantage of the present disclosure is the ability to increase productivity by increasing the bulk density of the fluidized bed.
• An advantage of the present disclosure is the ability to increase the fluidized bulk density with little or no risk of sheeting, chunking, overheating, bed collapse and/or reactor shutdown.
• An advantage of the present disclosure is a gas-phase polymerization process with improved productivity that requires no increase in reactor residence time
• FIG. 1 is a graph of gas velocity (SGV) and propylene partial pressure in accordance with an embodiment of the present disclosure.
• FIG. 2 is a graph of fluidized bulk density and bed weight in accordance with an embodiment of the present disclosure.
• a process for polymerizing one or more olefins in a gas-phase reactor includes a fluidized bed and a fluidizing medium.
• the fluidizing medium has an operating gas density.
• the method includes determining a critical gas density for the fluidizing medium and adjusting the operating gas density to be less than or equal to the critical gas density.
• gas phase polymerization is the passage of an ascending fluidizing medium, the fluidizing medium containing one or more monomers, in the presence of a catalyst through a fluidized bed of polymer particles maintained in a fluidized state by the fluidizing medium.
• Fluidization is a gas-solid contacting process in which a bed of finely divided polymer particles is lifted and agitated by a rising stream of gas, Fluidization. occurs in a bed of particulates when an upward flow of fluid through the interstices of the bed of particles attains a pressure differential and frictional resistance increment exceeding particulate weight.
• a '"fluidized bed is a plurality of polymer particles suspended in a fluidized state by a stream of a fluidizing medium.
• a “fluidizing medium” is one or more olefin gases, optionally a carrier gas (such as H?. or N;.) and optionally a liquid (such as a hydrocarbon) which ascends through the gas-phase reactor.
• a typical gas-phas ⁇ polymerization reactor (or gas phase reactor) includes a vessel (i.e., the reactor), the fluidized bed, a distribution plate, inlet and outlet piping, a compressor, a cycle gas cooler or heat exchanger, and a product " discharge system.
• the vessel includes a reaction zone and a velocity reduction zone, each of which is located above the distribution plate.
• the bed is located in the reaction zone.
• the fluidizing medium includes propylene gas and at least one other gas such as an olefin and/or a carrier gas such as hydrogen or nitrogen.
• Many operational parameters are monitored and controlled during gas-phase polymerization.
• One parameter is fluidized bulk density.
• the "fluidized bulk density” is the weight of solid (i.e., polymer particles) per unit volume in the fluidized bed.
• FBI is a mean value which may be greater or less than the localized bulk density at any point in the fixed reactor portion.
• FBD is a direct indicator of a gas phase reactor's operating health. Unexpected changes in FBD often indicate that the reactor is experiencing problems.
• Catalyst is typically fed into a lower section of the reactor. Reaction occurs upon contact between the catalyst and the fluidizing medium yielding growing polymer particles.
• the fluidizifjg medium passes upward through the fluidized bed, providing a medium for heat transfer and fhridization.
• the reactor includes an expanded section located above the reaction section, In the expanded section, particles having a terminal velocity higher than the velocity of the fluidizing medium discntraiii from the rluidizing medium stream. After leaving the reactor, the fluidizing medium passes through a compressor and one or more heat exchangers to remove the heat of polymerization before it is re-introduced into the reaction section of the reactor.
• the fluidizing medium may or may not contain an amount of liquid after cooling and condensing.
• One or more olefin monomers can be introduced in the gas-phase reactor to react with the catalyst and to form a polymer, or a fluidized bed of polymer particles.
• suitable olefin monomers include ethylene, propylene, C 4 . 20 ⁇ -olef ⁇ ns, such as C 4 . 52 ⁇ -olefms such as 1 butene, 1- ⁇ entene, 1 h ⁇ xene, 4-methyl-l-pentene, 1 -heptene, 1- octersc, 1 -decene, 1-dodecene and the like; C.u 2 ⁇ diolefms, such as 1,3 -butadiene.
• Any olefin polymerization catalyst may be introduced into the gas-phase reactor.
• the catalyst may be added as a solid, a slurry or a solution, and may be supported on an inorganic or an organic support.
• the catalyst may be a pre-polymer.
• the catalyst may be conveyed into the reactor with a gas, liquid or gas/liquid mixture including for example gaseous ethylene, nitrogen, cycle gas and propane, or liquid propane, propylene, isopentane and liquified cycle gas condensed in the recirculation loop.
• the catalyst may be introduced into the reactor alon ⁇ or in combination with the fluidizing medium.
• a catalyst composition is a composition that forms an ol ⁇ fln- based polymer when contacted with one or more olefins under polymerization conditions.
• Polymerization conditions are temperature and pressure parameters within a polymerization reactor suitable for promoting polymerization between a catalyst and an olefin to form the desired polymer.
• the catalyst composition may optionally include a cocatalyst, an internal electron donor, an external electron donor, a selectivity control agent, and any combination thereof.
• suitable catalyst compositions include Ziegler-Natta catalyst compositions, constrained geometry catalyst compositions, and metalloccnc catalyst compositions,
• the catalyst composition is a Ziegler-Natta catalyst composition.
• a "Ziegler-Natta catalyst composition” is a combination of (1) a transition metal compound of an element for Periodic table groups IV to VIII (procatalyst) and (2) an organometaliic compound of a metal from Periodic Table groups I to III (cocatalyst).
• suitable Ziegler-Natta procatalysts include halides or oxyhalides of titanium, vanadium, chromium, molybdenum, and zirconium.
• Nonlimiting examples of Ziegler-Natta cocatalysts include hydrides, alkyls, or aryls of aluminum, lithium, zinc, tin, cadmium, beryllium, and magnesium.
• a procatalyst precursor which includes magnesium moieties, may be employed to form the procatalyst composition.
• Sources for such magnesium moieties include anhydrous magnesium chloride, magnesium alkoxides or aryloxides, mixed magnesium alkoxy halides, or carbonated magnesium dialkoxidcs or aryloxides, Nonlimiting examples of sources of magnesium moieties are magnesium di-(C 1 .4)alkoxid ⁇ s, especially diethoxymagnesium.
• the precursors may include titanium moieties. Suitable sources include titanium alkoxides, titanium aryloxides, titanium alkoxy halides, and titanium halides.
• Precursors may include one or more magnesium di ⁇ (Cj- 4 ) ⁇ alkoxides and one or more titanium tetra ⁇ (C
• Various methods of making procatalyst precursor are known in the art, In particular, the preparation involves halogenation of the foregoing mixed magnesium and titanium alkoxides, and may involve the use of one or more compounds, referred to as "clipping agents", that aid in forming specific, low molecular weight, compositions of the desired morphology, Examples of suitable clipping agents include trialkylborates, especially triethylborate, phenolic compounds, especially cresol, and silanes.
• the procatalyst precursor is a mixed magnesium/titanium compound (MagTi) of the formula Mg d Ti(OR ° ) s X f wherein R e is an aliphatic or aromatic hydrocarbon radical having 1 to 14 carbon atoms or COR' wherein R' is an aliphatic or aromatic hydrocarbon radical having 1 to 14 carbon atoms; each ORe group is the same or different; X is independently chlorine, bromine or iodine, preferably chlorine; d is 0,5 to 56, or 2 to 4; e is 2 to 1 16 or 5-15; and f is 3 to 116, or 1 to 3.
• MagTi mixed magnesium/titanium compound
• a reaction medium comprises a mixture of an aromatic liquid, especially a chlorinated aromatic compound, most especially chlorobcnzene, with an alkanol, especially ethanol.
• Suitable halogenating agents include titanium tetrabromide, titanium tetrachloride or titanium trichloride, especially titanium tetrachloride. Removal of the alkanol from the solution used in the halogenation, results in precipitation of the solid precursor, having especially desirable morphology and surface area. Moreover, the resulting precursors are particularly uniform in particle size.
• halogenation is converted to a solid procatalyst by further reaction (halogenation) with a halogenating agent (step C) and incorporation of an internal electron donor.
• Suitable halogenating agents are titanium halides having the formula Ti(OR c ) e Xi, wherein R e , X 3 and e are as defined above; h is an integer from 1 to 4; and e + h is 3 or 4.
• the halogenation agent is TiCl 4
• the halogenation is conducted in the presence of a chlorinated aromatic liquid, such as diehlorob ⁇ nz ⁇ ne, o-chiorotoluene, or chlorobenzene.
• the halogenation is conducted by use of a mixture of halogenating agent and chlorinated aromatic liquid comprising from 40 to 60 volume percent halogenating agent, such as TiCl 4 , [0049] During (step C) the reaction mixture may be heated, if desired.
• the precursor and halogenating agent are contacted initially at a temperature from 0 °C to 60 0C, or from 20 0 C to 30 0 C, and heating is commenced at a rate of 0,1 to 10.0 °C/n ⁇ nute, or at a rate of 1.0 to 5.0 °C/mirmte,
• the internal electron donor may be added later, after an initial contact period between the halogenating agent and precursor in order Io reduce fines generation, Temperatures for the halogenation are from 60 0 C to 150 0 C (or any value or subrange therebetween), or from 90 0 C to 120 0 C, Ilalog ⁇ nation may be continued in the substantial absence of the electron donor for a period from 5 to 60 minutes, or from 10 to 50 minutes.
• the internal electron donor may be a carboxylic acid ester, a di ⁇ ther, a succinate, a dialkoxybcnzene, or a diol ester.
• the internal electron donor is a carboxylic acid ester such as C MO alkyl di esters of aromatic dicarboxylic adds, particularly C j .4 alkyl di ⁇ sters of phthalic acid or ter ⁇ phthalic acid,
• suitable carboxylic acid esters include diethylphthaiate, diisopropylphthalatc, diisobutylphthalate, diisopropyltercphthalat ⁇ , and diisobutylt ⁇ r ⁇ phthalate.
• the internal electron donor is di(isobutyl)phthalate.
• Sufficient internal electron donor usually is provided so that the molar ratio of internal electron donor to the magnesium present in the solid procatalyst precursor at this stage of the preparation is from about 0.01 :1 to about 1 :1, or from about 0.05:1 to about 0.5 : 1 , or from about 0,03 : 1 to about 0.1 :1 .
• the manner in which the procatalyst precursor, halogenating agent and internal electron donor are contacted may be varied.
• the procatalyst precursor is first contacted with a mixture containing the halogenating agent and a chlorinated aromatic compound. The resulting mixture is stirred and may be heated if desired, Next, the internal electron donor is added to the same reaction mixture without isolating or recovering of the precursor.
• the foregoing process may be conducted in a single reactor with addition of the various ingredients controlled by automated process control.
• Contact times of the precursor with the internal electron donor are at least 10 minutes, or at least 15 minutes, or at least 20 minutes, or at least 1 hour at a temperature from at least 25 0 C, or at least 50 0 C, or at least 60 0 C up to a temperature of 150 °C, or up to 120 0C, or up to 115 0 C,
• step D The resulting precursor is then recovered and contacted one or more times (step D) in the absence of the internal electron donor with a mixture of the halogenating agent in the chlorinated aromatic compound for at least 10 minutes, or at least 15 minutes, or at least 20 minutes, and up to 1 hour, or up to 45 minutes, or up to 30 minutes, at a temperature from at least 25 °C, or at least 50 0 C. or at least 60 0 C, to a temperature up to 150 0 C 5 or up to 120 °C, or up to 1 15 °C.
• the resulting solid procatalysi composition is separated from the reaction medium employed in the final process, by filtering for example, to produce a moist filter cake.
• the moist filter cake may then be rinsed or washed with a liquid diluent to remove unreacted TiCU and may be dried to remove residual liquid, if desired.
• the solid, exchanged procatalyst composition is washed one or more times with a "wash liquid," which is a liquid hydrocarbon such as an aliphatic hydrocarbon such as isopenlane, isooctane, isohexane, hexane, pentane, or octane.
• the solid, exchanged procatalyst composition then can be separated and dried or slurried in a hydrocarbon, especially a relatively heavy hydrocarbon such as mineral oil for further storage or use.
• the resulting solid procatalyst composition is in the form of porous particles having a titanium content of from about 0,1 percent by weight to about 6.0 percent by weight, based on the total solids weight, or from about 1.0 percent by weight to about 4.5 percent by weight, or from about 1,5 percent by weight to about 3.5 percent by weight.
• the weight ratio of titanium to magnesium in the solid, exchanged, procatalyst composition is suitably between about 1 :3 and about 1 :160, or between about 1 :4 and about 1 :20, or between about 1 :6 and 1 :13.
• the internal electron donor may be present in the procatalyst composition in a molar ratio of internal electron donor to magnesium of from about 0,005:1 to about 1 :1, or from about 0.04: 1 to about 0.4:1.
• the procatalysts herein are mixed magnesium/titanium compounds of the formula, Mg ⁇ sTi(Oll e ) ⁇ X f (ED) g , wherein R e is an aliphatic or aromatic hydrocarbon radical having 1 to 14 carbon atoms or COR' wherein R' is an aliphatic or aromatic hydrocarbon radical having 1 to 14 carbon atoms; each OR e group is the same or different; X is independently chlorine, bromine or iodine; ED is an internal electron donor, such as diisobulylphthalate; d is 0.5 to 56; e is 0, 1, or 2; f is 3 to 116; and g is O.OOSd to Id.
• the procatalyst composition may be further treated by one or more of the following procedures prior to or after isolation of the solid procatalyst.
• the solid procatalyst composition may be contacted (halogenated) with a further quantity of titanium haiide compound, if desired; it may be exchanged under metathesis conditions with an acid chloride, such as phthaloyl dichloride or benzoylchloride, and it may be rinsed or washed, heat treated; or aged.
• an acid chloride such as phthaloyl dichloride or benzoylchloride
• the procatalyst is contacted with a halogenaung agent, such as a mixture of a titanium haiide and a haiohydrocarbon diluent, such as TiCU and chlorobenzene, one or more times prior to isolation or recovery.
• a halogenaung agent such as a mixture of a titanium haiide and a haiohydrocarbon diluent, such as TiCU and chlorobenzene
• the co-catalyst may be chosen from any of the known activators of olefin polymerization catalyst systems employing a titanium haiide, or an organoaluminum compound.
• suitable cocatalysts include trialkylaluminum compounds, alkylaluminum alkoxide compounds, including oligomcric or polymeric alumoxane or modified alumoxane modified by incorporation of one or more different trialkyl aluminum compounds, and alkylaluminum haiide compounds,
• the compounds of the foregoing list contain an alkyl group in which each alkyi group independently has from 1 to 6 carbon atoms.
• the cocatalyst is trialkylaluminum or a dialkylaluminumhalide compound, wherein each of the alkyl groups independently contain from 1 to 4 carbon atoms,
• the cocatalyst is triethylaluminum, triisopropylaluminum, triisobutylaluminum, di ⁇ thylaluminum chloride, or mixtures thereof.
• the cocatalyst may be employed in a molar ratio of aluminum to titanium from about 1 :1 to about 500:1, or from about 10:1 to about 200: 1, or from about 35:1 to about 50:1.
• the catalyst composition includes an externa] donor that is a mixture of an activity limiting agent (ALA) and a selectivity control agent (SCA).
• ALA activity limiting agent
• SCA selectivity control agent
• the ALA is an ester of an aromatic carboxylic acid or a derivative thereof, an aliphatic ester, or a non- ester composition
• Nordimiting examples of suitable aromatic carboxylic acids include Cwo alkyl or cycloalkyl esters of aromatic monoearboxylic acids.
• Suitable substituted derivatives thereof include compounds substituted both on the aromatic rirsg(s) or the ester group with one or more substitu ⁇ nts containing one or more Group 14, 15 or 16 heteroatoms, especially oxygen,
• substitu ⁇ nts containing one or more Group 14, 15 or 16 heteroatoms, especially oxygen Examples of such substiluenls include (poly)alkylether, eyeloaikylether, aryleth ⁇ r, aralkylether, aikylthioeth ⁇ r, arylthioether, dialkylamine, diarylamine, diaraikylamine, and trialkylsilane groups.
• the aromatic carboxyjic acid ester may b ⁇ a C 1 ⁇ o hydrocarbyl ester of benzoic acid wherein the hydrocarbyl group is unsubstituted or substituted with one or more Group 14, 15 or 16 heteroatom containing substituents and C 1-2O (poly)hydrocarbyl ether derivatives thereof, or C 1 ⁇ alkyl benzoates and Cj-J, ring alkylated derivatives thereof, or methyl benzoate, ethyl henzoate, propyl benzoate, methyl p-methoxybenzoate, methyl p- ethoxyb ⁇ nzoate, ethyl p-methoxyb ⁇ nzoatc, and ethyl p-ethoxybenzoate.
• the aromatic monoearboxylic acid is ethyl p-ethoxybenzoate.
• the ALA is an aliphatic ester.
• the aliphatic ester may be a C 4 - C 30 aliphatic acid ester, may be a mono- or a poly- (two or more) ester, may be straight chain or branched, may be saturated or unsaturated, and any combination thereof.
• the C4-C30 aliphatic acid ester may also be substituted with one or more Group 14, 15 or 16 heteroatom containing substituents
• suitable C 4 -C 30 aliphatic acid esters include CV2 0 alkyl esters of aliphatic C4- 30 monoearboxylic acids, C 1 .20 alkyl esters of aliphatic GY20 monoearboxylic acids, Cs- 4 ally! mono- and diesters of aliphatic C4-20 monocarboxylic acids and dicarboxylic acids, C 1 .
• the C4-C 30 aliphatic acid ester may be isopropyl myristate, di-n ⁇ butyl sebacaie, ( ⁇ oly)(alkylene glycol) mono- or diacetates, (poly)(alkylene glycol) mono- or di-myristates, (poly)(alkylene glycol) mono- or di-laurates, (poly)(alkylene glycol) mono- or di ⁇ oleates, glyceryl tri(acetate), glyceryl tri-ester of C 2 - 40 aliphatic carboxylic acids, and mixtures thereof.
• the C4-C30 aliphatic ester is isopropyl myristate or di-n-butyl sebacaie.
• the ALA is a non-ester composition.
• a “non- ester composition” is an atom, molecule, or compound that is free of an ester functional group. In other words, the "non-ester composition” does not contain the following functional group.
• the non-ester composition may be a diaikyl diether compound or an amine compound.
• the dialkyi diether compound is represented by the following formula,
• Nonliniiting examples of suitable dialkyl ether compounds include dimethyl ether, diethyl ether, dibutyl ether, methyl ethyl ether, methyl butyl ether, methyl cycloh ⁇ xyl ether, 2,2-dim ⁇ thyl-l ,3- dim ⁇ thoxypropan ⁇ , 2 s 2-dieihyl-l,3-dimethoxypropane, 2,2-di ⁇ n ⁇ butyl-l,3 ⁇ dlmethoxypropane, 2,2-di-iso-butyl- 1 ,3-dimethoxypropanc, 2-eihyI-2-butyl- 1,3- diniethoxypropane, 2-n ⁇ propyl-2-cyolopentyl-l,3-dim ⁇ thoxypropane, 2,2-dim ⁇ thyl-l ,3- diethoxypropane, 2-iso-propyl-2-iso ⁇ butyl- 1 ,3-d
• the non- ⁇ stcr composition is an amine compound.
• suitable amine compounds include 2,6-substituted piperidines such as 2,6-dimethylpip ⁇ ridin ⁇ and 2,2,6,6-tetramethylpip ⁇ ridine and 2,5-substituted piperidines, ⁇ n a further embodiment, the piperidine compound is 2,2,6,6-tetramethylpiperidine.
• the SCA includes a silane
• the silane may include one or more alkoxysilanes having the general formula: SiR m (OR') 4 . m (I) where R independently each occurrence is hydrogen or a hydroearbyl or an amino group optionally substituted with one or more substituents containing one or more Group 14, 15, 16, or 17 heteroatoms R contains up to 20 atoms not counting hydrogen and halogen R' is a C MO alkyl group, and m is 0, 1, 2 or 3.
• R is CVn aryl, alkyl or araikyl, Cs -O cycloallyl, C 3 - 12 branched alkyl, or C3.J2 cyclic amino group, R' is C 3 .
• Nonlimiting examples of suitable silane compositions include dicyclopentyldimcthoxysilane, di-tert-butyldim ⁇ thoxysilane, methylcyclohexyldimethoxysilane, ethylcyclohexyldiraethoxysilan ⁇ , diphenyldimethoxysilane, diisopropyldimethoxysilane, di-n-propyldimcthoxysilane, diisobutyldimethoxysIJane, di-n-butyldimethoxysilane, cyclopeniyltrim ⁇ thoxysilane, isopropyltrimethoxysilane, n-propyltrimethoxysilane, n-propykriethoxysilan ⁇ , ⁇ thy Itriethoxysilane, t ⁇ tram ⁇ thoxysi lane, tetraethoxysil
• the silane composition is dicyclopentyldimethoxysilan ⁇ , methylcyclohexyldimethoxysilane, or n- propyltrimethoxysilane, and any combination of thereof.
• the silane is dicyclopentyldim ⁇ thoxysilane.
• Gas-phase polymerization requires that the velocity of the fluidizing medium be sufficient to maintain the bed of formed polymer particles in a fluidiz ⁇ d state.
• the velocity of the fluidizing medium is also referred to as the superficial gas velocity.
• “superficial gas velocity” (or “SGV) is a measure of the flow of the fluidizing medium through the reactor, SGV is calculated by dividing cycle gas volumetric flow by reactor cross-sectional area, ⁇ minimum SGV is needed for proper fluidization of the particle bed. In cond ⁇ nsed-modc operation of the gas-phase polymerization reactor, a minimum SGV is required to carry condensed liquid from the heat exchanger to the reactor.
• fluidizing medium velocity and “superficial gas velocity” are used interchangeably.
• the product produced in the gas-phase polymerization reactor is a propylene-based polymer (propylene homopolymer, propylene/olefin copolymer), an ethylene-based polymer (ethylene homopolymer, ethylene/olefin copolymer) or an ethylene/propylene rubber.
• the fluidiz ⁇ d bed allows rapid transfer of heat from the growing polymer particles to the fluidizing medium.
• the fluidizing medium can be cycled/recycled from the reactor to remove heat from the system.
• the fluidized bed also enables rapid transfer of r ⁇ actants to active catalyst sites, enhancing effective catalyst productivity.
• the reactor can be a gas- phas ⁇ condensing-mode polymerization reactor.
• Fluidization regimes are distinguishable by bubble behavior.
• the bubbling Iluidization regime exhibits discernible bubbles. Bubble interaction is dominated by bubble coalescence in the bubbling fluidization regime.
• the "turbulent regime/' or “turbulent " fluidization” is characterized by many small bubbles/voids with a predominant tendency of bubble break-up as opposed to bubble coalescence. Turbulent fluidization occurs when a significant portion of the bubbles begin to lose their shape near the top of the bed, and a turbulent motion of clusters and voids of gas of various sizes and shapes appears. Bubbles in the turbulent regime split and reorganize frequently, the bubbles being irregular in shape with vague boundaries and are often referred to as "gas voids" or "voids. 5" Bubbles/voids move violently, rendering it difficult to distinguish the continuous and discrete phases in the bed.
• transition velocity is the SGV at which the mean amplitude of pressure fluctuations peak.
• the transition velocity, U 0 also demarcates the onset of the turbulent regime (from the bubbling regime). It is recognized that turbulent fluidization might not exist homogeneously across the vertical dimension of the bed.
• “Fast fluidization” or “fast fluidization regime” is characterized in that the pressure gradient along the direction of transport is a monotonic function of the quantity of injected solid, for equal flow rate and density of the fluidizing medium. Turbulent fluidization yields to fast fluidization when the bubbles and voids are diminished in size to the same order of magnitude of the solid particles.
• “transport velocity” or “U R” is the termination of turbulent fluidization and the onset of fast fluidization, as the superficial gas velocity increases.
• the Uj 1 is the SGV which demarcates the termination of turbulent fluidization and the onset of fast fluidization,
• the transport velocity is the gas velocity at which the mean amplitude of pressure fluctuations level off as the gas velocity is increased beyond U c .
• the gas-phase polymerization process includes determining a critical gas density for the fjuidizing medium and adjusting the operating gas density of the fluidizing medium to be less than or equal to the critical gas density,
• critical gas density is the density of the fluidizing medium at the transition point.
• transition point ' ' is the demarcation between turbulent fluidization and fast fluidization.
• the critical gas density is determined by the following equation ( ⁇ ) below:
• a is a constant with a value from about 3.5 to about 6.2
• b is a constant with a value from about 1.7 to about 2,7
• APS is the average particle size of the fluklized bed
• SBD is the settled bulk density of the fluidized bed
• SGV is the superficial gas velocity of the fluidizing medium.
• a is a value from about 4,3 to about 5.6 and b is a value from about 1.9 to about 2.5.
• operating gas density is the gas density of the fluidizing medium under reactor operating conditions.
• the operating gas density of the fluidizing medium is maintained less than or equal to the critical gas density as determined by the following equation (II) below: (H)
• the applicants have surprisingly and unexpectedly discovered a mode! that accurately determines the demarcation between the turbulent regime and the fast fluidization regime.
• the parameters of APS, SBD, and/or SGV influence the value of the critical gas density.
• the ⁇ PS, SBD, SBD (as well as values for a and b) influence or otherwise determine the demarcation between the turbulent regime and the fast fluidization regime.
• the present gas-phase polymerization process maintains the fhiidizing medium at a velocity greater than the transition velocity, U c , Consequently, at least a portion (or all, or substantially all) of the fmidized bed is in at least the turbulent regime during the polymerization process.
• the fluidizcd bed is maintained in at least the turbulent regime during and/or after the adjustment of the operating gas density.
• the present process operates beyond the bubbling fliridization regime before, during, and/or after adjustment of the operating gas density.
• the fluidized bed in the fast fluidization regime and adjustment of the operating gas density to or below the critical gas density increases the bulk density of the fluidized bed and moves the fluidized bed to the turbulent regime,
• Adjustment of the operating gas density can occur in a number of ways.
• the operating gas density of the fluidizing medium can be moved or otherwise placed at or below the critical gas density by (i) adjusting a partial pressure of one or more gases that compose the fluidizing medium, (ii) adjusting or otherwise changing or altering the composition of the fluidizing medium, (iii) adjusting a gas phase reactor pressure, and (Iv) any combination of (i) - (iii).
• the fluidizing medium contains propylene gas and at least one other gas.
• the other gas can be hydrogen, an olefin gas (such as ethylene, buten ⁇ , or octene), and/or nitrogen gas.
• the process Includes maintaining (some or all of) the fluidlzed bed in at least the turbulent regime and decreasing a propylene partial pressure of the fluidizing medium.
• reduction of the propylene partial pressure moves or otherwise places the operating gas density at or below the critical gas density,
• reduction of the propylene partial pressure Increases the bulk density of the fluidized bed.
• the propylene partial pressure of the fluidizing medium can be reduced alone or in combination with a reduction in the velocity of the fluidizing medium to place the operating gas density at or below the critical gas density. This also increases the bulk density of the fluidized bed.
• the composition of the fluidizing medium can be changed to adjust the gas density.
• the composition of a fluidizing medium composed of an olefin gas and nitrogen can be changed by replacing the nitrogen gas with hydrogen gas. This change from nitrogen to hydrogen can change the partial pressure of the olefin gas and/or change the density of the fluidizing medium.
• the overall reactor pressure can be changed, adjusted, and/or altered to change the operating gas density of the fluidizing medium.
• the polymerization process includes introducing a catalyst composition into the reactor to form polymer particles which compose the lluidized bed.
• the catalyst composition can be any catalyst composition as disclosed herein.
• the polymer particles have an average particle sized (APS) from about 0.014 inches to about 0,12 inches, or from about 0.01 8 inches to about 0.03 inches.
• the polymer particles have a settled bulk density (SBD) from about 15 Ib/'ft 3 to about 35 lb/ft J ,
• the fl ⁇ idizing medium flows or otherwise passes through the bed at a velocity from about 0.8 ft/second to about 5.0 ft/second.
• adjustment of the operating gas velocity increases the bulk density of the ffuidiz ⁇ d bed from about 10 wt % to about 100 wt %, or from about 20 % to about 50%.
• the FBD increase is based on the FBD of the bed prior to adjustment of the operating gas density.
• another process for polymerizing one or more olefins in a gas- phase reactor is provided.
• the gas-phase reactor has a fluidiz ⁇ d bed and a fluidizing medium.
• the process includes determining a critical gas velocity for the fluidizing medium and adjusting the operating gas velocity of the fluidizing medium to be less than or equal to the critical gas velocity.
• 'critical gas velocity is the density of the fluidizing medium at the transition point.
• the '"transition point is the demarcation between turbulent fMdization and fast fluidization.
• the critical gas density is determined by the following equation (III) below:
• a is a constant with a value from about 3.5 to about 6.2
• b is a constant with a value from about 1.7 to about 2.7
• APS is the average particle size of the fluidized bed
• SBD is the settled bulk density of the fluidiz ⁇ d bed
• FMD is the fluidiz ⁇ d medium density.
• a I a value from about 4.3 to about 5.6 and b is a value from about 1.9 to about 2.5.
• '"operating gas velocity is the gas velocity of the fluidizing medium under reactor operating conditions.
• the operating gas velocity of the fluidizing medium is maintained less than or equal to the critical gas velocity as determined by the following equation (IV) below: (IV)
• the parameters of APS, SBD, and/or FMD influence the value for the critical gas velocity.
• the operating gas velocity is maintained at a velocity greater than Uc.
• the process includes maintaining the fluidized bed in at least the turbulent regime during the adjusting. This may include maintaining the operating gas velocity at a velocity greater than Uc. This increases the FBD, Not wishing to be bound by any particular theory, it is believed that reduction in operating gas velocity decreases the density of the tluidizing medium. Reducing the fluidizing medium density reduces the fluidizing medium momentum (i.e., gas density x SGV) which reduces the lifting force on the bed, thereby allowing the bed to compress.
• the fluidizing medium momentum i.e., gas density x SGV
• the process includes adjusting the operating gas velocity from a velocity greater than the critical gas velocity to less than or equal to the critical gas velocity. This increases the bulk density of the fluidized bed. For example, when the operating gas velocity is greater than the critical gas velocity, the fluidized bed can be in the fast fluidization regime. In this situation the operating gas velocity is controlled or otherwise adjusted to place some or all of the fluidized bed in a state of fast fluidization, Thus, the operating gas velocity can be greater than the transport " velocity, U k , The process includes decreasing the operating gas velocity to move the fluidized bed to the turbulent regime.
• the process includes adjusting the operating gas velocity from a velocity greater than Uk to a velocity less than Uk, This increases the FBD.
• the process includes introducing a catalyst composition into the reactor and forming a fluidized bed having an APS from about 0,014 Inches to about 0.12 inches.
• the catalyst composition can be any catalyst composition as disclosed herein,
• the polymer particles have an SBD from about 15 Ib/ft J to about 35 Ib/ft 3 .
• the fluidizing medium is composed of propylene gas and optionally a carrier gas such as hydrogen and/or nitrogen.
• the fluidizing medium has a gas density from about 2.5 Ib/ft " ' to about 5.0 ib/ft 3 .
• the propylene gas can have a partial pressure from about 300 psia to about 400 psia.
• adjustment of the operating gas density increases the bulk density of the fluidized bed from about 10 wt % to about 100 wt %, or from about 20% to about 50%. The increase is based on the FBD prior to adjustment of the operating gas velocity.
• another polymerization process is provided.
• the process is a polymerizing process for one or more olefins in a gas-phase reactor.
• the gas phase has a fluidized bed and a fluidizing medium.
• the fluidizing medium has an operating gas density and an operating gas velocity.
• the process includes determining a critical gas velocity for the fluidizing medium based on equation (III) above and adjusting the operating gas density or the operating gas velocity so that the operating gas velocity is less than or equal to the critical gas velocity. Adjustment of the operating gas density and/or the operating gas velocity increases the FBD from about 10% to about 100% (based on the FBD prior to adjustment).
• the process includes adjusting both the operating gas density and the operating gas velocity so the operating gas velocity is less than the critical gas velocity.
• the fluidizing medium is composed of propylene gas and at least one other gas.
• the process includes decreasing a partial pressure of the propylene gas to place the operating gas velocity at or below the critical gas velocity, This also increases the hulk density of the fiuidized bed.
• the density of the fluidlzing medium may be decreased by decreasing the propylene partial pressure and the operating gas velocity can also be decreased to move the operating gas velocity below the critical gas velocity. Reduction of both these parameters increases the FBD.
• the fluidized bed is maintained in at least the turbulent regime throughout the adjustments.
• the process includes decreasing the operating gas velocity from a velocity greater than the critical gas velocity to a velocity less than the critical gas velocity.
• the reduction in the operating gas velocity increases the bulk density of the fluidized bed.
• the process includes introducing a catalyst composition into the reactor and forming a fluidized bed having an APS from about 0.014 inches to about 0.12 inches,
• the catalyst composition can be any catalyst composition as disclosed herein.
• the process includes producing polymer particles having an SBD from about 15 Ib/ft 3 to about 35 Ib/ft 3 .
• any of the foregoing process can increase the bulk density of the fluidized bed from 10% to about 100%, or from about 20% to about 80%, or from about 15% to 50%. The increase is based on the fiuidized bed bulk density before the decreasing, In an embodiment.
• any of the foregoing processes can produce a fluidized bed with an FBD from about lib/ft" to about 40 Ib/ft 3 , or from about 7 Ib/ ft 3 to about 40 Ib/ft 3 ', or from about 71b/ft 3 to about 35 Ib/ ft 3 .
• any of the foregoing processes can produce polymer at a rate from about 28 tons/hour to about 40 tons/hour, or from about 30 tons/hour to about 35 tons/hr, or about 33 tons/hour.
• any of the foregoing process can produce less than 5 wt % polymer fines, or from about 0.1 wx% to about 4 wt %, or from about 1 wt % to about 3 wt %, based on the weight of the produced polymer.
• polymer fines is a polymer particle having a maximum diameter less than 180 ⁇ m as measured using a Gradex 2000 automated particle size analyzer.
• none of the foregoing processes increase the residence time of the catalyst composition, the olefin gas(es) and/or the polymer particles in the reactor.
• the present processes advantageously increases the FBD thereby increasing productivity by increasing the amount of polymer product produced in the same amount of time before any process adjustments. In other words, by increasing the FBD, the present processes produce more product without increasing production time.
• the residence time is from about 0.5 hour to about 2 hours, or about 1 hour.
• a gas-phase polymerization reactor includes a fluidized bed of polymer particles.
• the polymer particles have an average particle size from about 0.014 inches to about 0,012 inches.
• the fluidized bed has a bulk density from about 1 lb/ft 3 to about 40 Ib/ft 3 or from about 7 lb/fi J to about 35 lb/ft 3 .
• the gas-phase reactor also includes a fluidizing medium.
• the fluidizing medium has an operating gas density less than or equal to the critical gas density as determined by equation (I) above.
• the fluidizing medium can also have an operating gas velocity less than or equal to the critical gas velocity as determined by equation (III) above.
• the fluidized bed is in at least the turbulent regime.
• the gas ⁇ phas ⁇ polymerization reactor includes a catalyst composition and at least one olefin gas in an interior of the gas-phase reactor.
• the polymer particles formed as a result of the polymerization can be propylene-based polymer, ethylene- based polymer, and ethylene/propylene rubber.
• the polymer particles can have a settled bulk density from about 15 lb/ft 3 to 35 lb/ft 3 .
• the fluidizing medium velocity is from about 0.5 ft/second to about 2.6 ft/second.
• the fluidizing medium is composed of propylene and at least one other gas, such as hydrogen or nitrogen.
• the fluidizing medium as a density from about 1.0 Ib/ft " to about 5,0 Ib/ft* , or about 3 Ib/ft 3 .
• the propylene has a partial pressure from about 300 psia to about 400 psia.
• any numerical range recited herein includes all values from the lower value and the upper value, in increments of one unit, provided that there is a separation of at least two units between any lower value and any higher value.
• a compositional, physical or other property such as, for example, molecular weight, melt index, etc.
• a compositional, physical or other property such as, for example, molecular weight, melt index, etc.
• a compositional, physical or other property such as, for example, molecular weight, melt index, etc.
• sub ranges such as 100 to 144, 155 to 170, 197 to 200, etc.
• any numerical range recited herein includes any value or subrange within the slated range. Numerical ranges have been recited, as discussed herein, in reference to density, weight percent of component, molecular weights and other properties,
• compositions claimed herein through use of the term “comprising” may include any additional additive, adjuvant, or compound whether polymeric or otherwise, unless stated to the contrary,
• blend or "polymer blend,” as used herein, is a blend of two or more polymers. Such a blend may or may not be miscible (not phase separated at molecular level). Such a blend may or may not be phase separated. Such a blend may or may not contain, one or more domain configurations, as determined from transmission electron spectroscopy, light scattering, x-ray scattering, and other methods known in the art.
• composition includes a mixture of materials which comprise, the composition, as well as reaction products and decomposition products formed from the materials of the composition.
• polymer is a raacromol ⁇ cular compound prepared by polymerizing monomers of the same or different type.
• Polymer includes homopolymers, copolymers, terpolymers, interpolymers, and so on.
• interpolymer means a polymer prepared by the polymerization of at least two types of monomers or comonomers.
• interpolyrner refers to polymers prepared by the polymerization of at least two different types of monomers.
• the generic term interpolymer thus includes copolymers, usually employed to refer to polymers prepared from two different monomers, and polymers prepared from more than two different types of monomers,
• ⁇ thylene-containing polymer refers to a polymer that comprises at least 0.1 weight percent polymerized ethylene monomer (based on the total weight of polymerizable monomers), and optionally may comprise at least one polymerized comonomer.
• propylene-based polymer refers to a polymer that comprises a majority weight percent polymerized propylene monomer (based on the total amount of polymerizable monomers), and optionally may comprise at least one polymerized comonomer.
• Processivity is the weight of polymer produced per weight of catalyst used in the polymerization process (i.e., grams polymer/gram catalyst),
• a polypropylene fluidized bed reactor was run at two different conditions: A, and B as outlined in the table below,
• the catalyst system is a Ziegler-Natta type supported catalyst together with an aluminum alky! activator and an external donor,
• gas density was reduced from 4.53 lb/Tt.3 (A) to 4.00 Ib/ft3 (B) and SGV was reduced from 1.27 ft/s (0.39 m/s) (A) to 1 .20 ft/s (0.37 m/s) (B).
• the gas density was reduced by decreasing the propylene (C3H6) partial pressure from 393 psi (27,6 kg/cni2) to 360 psi (25.3 kg/eni2) (see Figure 1).
• the gas density is greater than the critical gas density while in case B, the gas density is less than the critical gas density indicating a change in fluidization regime from fast fluidized to turbulent (Equation Il above).
• the upper iluldized bulk density increased by 25% from 7.7 to 9,6 lb/ft 3 (124 to 154 kg/ni 3 ) and the lower fluidized bulk density increased by 21% from 8.0 to 9.7 lb/ft 3 (128 to 155 kg/ rtr) (see Figure 2)
• the polymer powder for this example had an APS of approximately 0.025 inch and a settled bulk density of 22 to 24 lb/ft 3 ,
• Figure 1 is a plot of fluidized bulk densities and bed weight [00130]
• a polypropylene fluidized bed reactor was ran at two different conditions: ⁇ , and B during which time SGV was reduced from 1.30 ft/s (A) to 0.87 ft/s (B), AU other reactor conditions were approximately held constant including the gas density at 2,82 ib/ ⁇ 3.
• the critical gas density as calculated by Equation I above increased from 2.19 Ib/ft3 to 7.00 Ib/ft3 (with a - ⁇ 4.0 and b ::: 2,3),
• the gas density is greater than the critical gas density while in case B, the gas density is less than the critical gas density indicating a change in fiuidization regime from fast fluidized to turbulent (Equation II above).
• the fluidized bulk density increased by 74% from 5.5 Ib/ft3 (A) to 9, ⁇ Ib/ft3 (B).

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• Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
• Polymerisation Methods In General (AREA)
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