WO2013074087A1 - Method for polymerizing polypropylene - Google Patents
Method for polymerizing polypropylene Download PDFInfo
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- WO2013074087A1 WO2013074087A1 PCT/US2011/060758 US2011060758W WO2013074087A1 WO 2013074087 A1 WO2013074087 A1 WO 2013074087A1 US 2011060758 W US2011060758 W US 2011060758W WO 2013074087 A1 WO2013074087 A1 WO 2013074087A1
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- reactor
- gas phase
- isopropyl myristate
- dicyclopentyldimethoxysilane
- phase reactor
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F10/04—Monomers containing three or four carbon atoms
- C08F10/06—Propene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F110/04—Monomers containing three or four carbon atoms
- C08F110/06—Propene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/01—Processes of polymerisation characterised by special features of the polymerisation apparatus used
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/34—Polymerisation in gaseous state
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/38—Polymerisation using regulators, e.g. chain terminating agents, e.g. telomerisation
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F210/04—Monomers containing three or four carbon atoms
- C08F210/06—Propene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F210/16—Copolymers of ethene with alpha-alkenes, e.g. EP rubbers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F4/00—Polymerisation catalysts
- C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
- C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
- C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
- C08F4/62—Refractory metals or compounds thereof
- C08F4/64—Titanium, zirconium, hafnium or compounds thereof
- C08F4/646—Catalysts comprising at least two different metals, in metallic form or as compounds thereof, in addition to the component covered by group C08F4/64
- C08F4/6465—Catalysts comprising at least two different metals, in metallic form or as compounds thereof, in addition to the component covered by group C08F4/64 containing silicium
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F4/00—Polymerisation catalysts
- C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
- C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
- C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
- C08F4/62—Refractory metals or compounds thereof
- C08F4/64—Titanium, zirconium, hafnium or compounds thereof
- C08F4/647—Catalysts containing a specific non-metal or metal-free compound
- C08F4/649—Catalysts containing a specific non-metal or metal-free compound organic
- C08F4/6494—Catalysts containing a specific non-metal or metal-free compound organic containing oxygen
Definitions
- the present disclosure relates to a method for polymerizing
- polypropylene optionally with one or more additional comonomers in a gas phase reactor in the presence of a mixed electron donor system comprising at least one selectivity control agent and at least one activity limiting agent.
- the process involves controlling the polymerization process to ensure that the difference between the reactor temperature and the dew point temperature of the incoming monomer stream is 12°C or greater.
- the "dew point temperature” is that temperature at which liquid condensate begins to form in the recirculating gas.
- operation in the "condensing mode” has become quite common in the art - see Jenkins et al.'s patents US 4,543,399 and US 4,588,790.
- a gas or liquid which will not interfere with the desired polymerization reaction may be introduced into the recycle stream to increase its dew point. The resulting ability to remove greater quantities of heat energy in same or less time has increased the production capacity of the typical exothermic fluidized bed reactor.
- Polypropylene reactors running in the condensing mode employing conventional Ziegler-Natta catalyst systems typically are operated such that the difference between the temperature of the fluidized bed and the dew point temperature of the recycle gas (also known as the "bed minus dew temperature") is small, typically about 1-2°C.
- This relatively small bed minus dew value results in an amount of liquid propylene being present in the reactor.
- the liquid propylene is considered advantageous as it serves to absorb heat of reaction (particularly during production spikes or production irregularities or production interruptions) and also serves to prevent reactor fouling. It is generally understood in the art that the bed minus dew temperature must be small in order to ensure that liquid propylene monomer is present in the reactor.
- the increase of bed minus dew can be associated with a lower reactor total pressure and/or a higher reactor temperature.
- reactor total pressure When the reactor total pressure is relatively low, the investment and operation costs of polypropylene manufacture can be reduced.
- a relatively higher reactor total pressure e.g., 450-500 psi
- a relatively lower reactor total pressure With the recently developed high activity catalysts systems, a relatively lower reactor total pressure, with a desired balance of catalyst activity and the investment/operational cost reduction, can be achieved for the purpose of minimizing manufacturing cost.
- a reactor temperature When the reactor temperature is relatively high, a few desired changes can occur accordingly, including higher catalyst activity, lower oligomer level in product (hence less volatile organic compounds (VOC) and odor), lower xylene solubles (XS), narrower molecular weight distribution, higher heat-removal driving force (hence easier to remove reaction heat), etc.
- VOC volatile organic compounds
- XS xylene solubles
- MFR melt flow rate
- the reactor should be operated at a bed minus dew temperature of less than 10°C in order to avoid static build-up or fouling (see examples in
- the present invention relates to a method for polymerizing propylene, optionally with one or more additional comonomers, comprising introducing catalyst, into a gas phase reactor wherein the gas phase reactor has a given temperature.
- a recycle fluid comprising propylene and optionally comonomer is also introduced into the gas phase reactor, said recycle fluid having a given dew point at the inlet to the gas phase reactor.
- a mixed electron donor system is also introduced to the reactor, wherein the mixed electron donor system comprises at least one selectivity control agent and at least one activity limiting agent.
- the method is characterized by having a difference between the reactor bed temperature and the dew point temperature of the recycle fluid of 12°C, or greater.
- the reactor has a total pressure less than 375 psi (gauge).
- the reactor has a reactor bed temperature higher than 72°C.
- the recycle fluid comprises fresh and recycled propylene.
- the recycle fluid inlet temperature is lower than the dew point of the recycle stream.
- the catalyst comprises one or more Ziegler-Natta procatalyst compositions comprising one or more transition metal compounds and one or more internal electron donors comprising an ester of an aromatic dicarboxylic acid; and one or more aluminum containing cocatalysts.
- the cocatalyst can be introduced together with the catalyst or separately.
- the activity limiting agent is a carboxylic acid ester, a diether, a poly(alkene glycol), a diol ester, or a combination thereof.
- the activity limiting agent is selected from a benzoate, a C4-C30 aliphatic acid ester and combinations thereof and can advantageously be selected from a laurate, a myristate, a palmitate, a stearate, an oleate or combinations thereof.
- the selectivity control agent is selected from the group consisting of an alkoxysilane, an amine, an ether, a carboxylate, a ketone, an amide, a carbamate, a phosphine, a phosphate, a phosphite, a sulfonate, a sulfone, a sulfoxide, and combinations thereof.
- the selectivity control agent corresponds to the formula SiR m (OR')4_ m , where R is C 3-12 cycloalkyl, C 3-12 branched alkyl, or C 3-12 cyclic or acyclic amino group, R' is C 1-4 alkyl, and m is 0, l, or 2.
- the mixed external electron donor comprises three or more different electron donors.
- the catalyst system includes an aluminum containing cocatalyst and wherein the aluminum to mixed electron donor mole ratio is in the range of from 0.5 to 4.0: 1.
- the gas phase reactor has a superficial gas velocity in the range of from 0.2 to 1 m/s.
- the gas phase reactor is a fluidized bed reactor.
- the gas phase reactor includes a mechanical agitator or scraper.
- the gas phase reactor can be arranged in any configuration, with vertical or horizontal configurations being preferred.
- Figure 1 is a schematic of a typical fluidized bed reactor for making polyolefins.
- the present invention relates to a method for polymerizing propylene, optionally with one or more additional comonomers, comprising introducing catalyst, into a gas phase reactor wherein the gas phase reactor has a given temperature.
- a recycle fluid comprising propylene and optionally comonomer is also introduced into the gas phase reactor, said recycle fluid having a given dew point at the inlet to the gas phase reactor.
- a mixed electron donor system is also introduced to the reactor, wherein the mixed electron donor system comprises at least one selectivity control agent and at least one activity limiting agent.
- the method is characterized by having a difference between the reactor temperature and the dew point temperature of the recycle fluid of 12°C, or greater.
- a straight section 1 has a straight section 1 and an expanded section 5.
- a fluidized bed 2 of particulate polyolefin product made by polymerizing monomer introduced with makeup materials through line 3 from source 18, and the introduction of catalyst from source 19, all as known in the art.
- Recycle line 4 more or less continuously removes fluid from expanded section 5.
- the fluid is passed through compressor 16 and cooler 17 to remove the thermal energy originating as the heat of reaction from the exothermal polymerization process in straight section 1.
- the fluid is recycled through line 3 to deflector 6 and distribution plate 7 into the fluidized bed 2, along with makeup material from source 18.
- Particulate product is removed continuously or intermittently through line 8, controlled by valve 9, into discharge tank 10, from which it may be removed in stages to minimize monomer loss through valve 11, tank 12 and valve 13, to recover product 14, and the monomer in the discharge tank 10 can be returned to the reactor through line 21 and valve 22, all as known in the art.
- Makeup material from source 18 may include not only fresh monomer, but inert liquid or other condensable materials introduced to assist in the heat removal process as is known in the art.
- the gas in the recycle line 3 has a given dew point depending upon the gaseous content and pressure.
- the reactor system is operated to ensure that the reactor 1 has a fluidized bed 2 which is at a temperature which is at least 12°C higher than the dew point of the incoming recycle line 3. More preferably, the bed minus dew point is at least 14 °C.
- the bed minus dew point difference can be achieved by lowering the dew point of the recycle stream or increasing the temperature of the fluidized bed or a
- the present invention also requires a specific catalyst composition.
- the catalyst comprises a Ziegler-Natta procatalyst, a cocatalyst and a mixed electron donor system.
- the mixed electron donor system comprises at least one selectivity control agent (SCA) and at least one activity limiting agent (ALA).
- the Ziegler-Natta procatalyst composition contains a transition metal compound and a Group 2 metal compound.
- the transition metal compound may be a solid complex derived from a transition metal compound, for example, titanium-, zirconium-, chromium- or vanadium-hydrocarbyloxides, hydrocarbyls, halides, or mixtures thereof.
- the transition metal compound has the general formula TrX x where Tr is the transition metal, X is a halogen or a Cno hydrocarboxyl or hydrocarbyl group, and x is the number of such X groups in the compound in combination with a Group 2 metal compound.
- Tr may be a Group 4, 5 or 6 metal.
- Tr is a Group 4 metal, such as titanium.
- X may be chloride, bromide, Ci_ 4 alkoxide or phenoxide, or a mixture thereof. In an embodiment, X is chloride.
- Nonlimiting examples of suitable transition metal compounds that may be used to form the Ziegler-Natta procatalyst composition are TiCl 4 , ZrCl 4 , TiBr 4 , TiCl 3 , Ti(OC 2 H 5 ) 3 Cl, Zr(OC 2 H 5 ) 3 Cl, Ti(OC 2 H 5 ) 3 Br,
- transition metal compound is a titanium compound.
- Nonlimiting examples of suitable Group 2 metal compounds include magnesium halides, dialkoxymagnesiums, alkoxymagnesium halides, magnesium oxyhalides, dialkylmagnesiums, magnesium oxide, magnesium hydroxide, and carboxylates of magnesium.
- the Group 2 metal compound is magnesium dichloride.
- the Ziegler-Natta procatalyst composition is a mixture of titanium moieties supported on or otherwise derived from magnesium compounds.
- Suitable magnesium compounds include anhydrous magnesium chloride, magnesium chloride adducts, magnesium dialkoxides or aryloxides, or carboxylated magnesium dialkoxides or aryloxides.
- the magnesium compound is a magnesium di(Ci_ 4 )alkoxide, such as
- Nonlimiting examples of suitable titanium moieties include titanium alkoxides, titanium aryloxides, and/or titanium halides.
- Compounds used to prepare the Ziegler-Natta procatalyst composition include one or more magnesium-di(Ci_4)alkoxides, magnesium dihalides, magnesium alkoxyhalides, or mixtures thereof and one or more titanium tetra(Ci_4) alkoxides, titanium tetrahalides, titanium(Ci_4)alkoxyhalides, or mixtures thereof.
- a precursor composition may be used to prepare the Ziegler-Natta procatalyst composition as is commonly known in art.
- the precursor composition may be prepared by the chlorination of the foregoing mixed magnesium compounds, titanium compounds, or mixtures thereof, and may involve the use of one or more compounds, referred to as "clipping agents", that aid in forming or solubilizing specific compositions via a solid/solid metathesis.
- clipping agents include trialkylborates, especially triethylborate, phenolic compounds, especially cresol, and silanes.
- the precursor composition is a mixed
- magnesium/titanium compound of the formula MgdTi(OR e ) f X g
- 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 3 group is the same or different
- X is independently chlorine, bromine or iodine
- d is 0.5 to 56, or 2-4; or 3
- f is 2-116, or 5-15
- g is 0.5- 116, or 1-3, or 2.
- the precursor may be prepared by controlled precipitation through removal of an alcohol from the reaction mixture used in its preparation.
- the reaction medium comprises a mixture of an aromatic liquid, especially a chlorinated aromatic compound, such as chlorobenzene, with an alkanol, especially ethanol, and an inorganic chlorinating agent.
- Suitable inorganic chlorinating agents include chlorine derivatives of silicon, aluminum and titanium, such as titanium tetrachloride or titanium trichloride, and titanium tetrachloride in particular.
- the chlorinating agents lead to partial chlorination which results in a precursor containing relatively high level of alkoxy component(s). Removal of the alkanol from the solution used in the chlorination, results in precipitation of the solid precursor, having a desirable morphology and surface area.
- the precursor was separated from the reaction media.
- the resulting precursor is particularly uniform particle sized and resistant to particle crumbling as well as degradation of the resulting procatalyst.
- the precursor composition is Mg 3 Ti(OEt)sCl 2 .
- the precursor is next converted to a solid procatalyst by further reaction (halogenation) with an inorganic halide compound, preferably a titanium halide compound, and incorporation of an internal electron donor. If not already incorporated into the precursor in sufficient quantity, the electron donor may be added separately before, during or after halogenation. This procedure may be repeated one or more times, optionally in the presence of additional additives or adjuvants, and the final solid product washed with an aliphatic solvent. Any method of making, recovering and storing the solid procatalyst is suitable for use in the present disclosure.
- One suitable method for halogenation of the precursor is to react the precursor at an elevated temperature with a tetravalent titanium halide, optionally in the presence of a hydrocarbon or halohydrocarbon diluent.
- the preferred tetravalent titanium halide is titanium tetrachloride.
- the optional hydrocarbon or halohydrocarbon solvent employed in the production of olefin polymerization procatalyst preferably contains up to 12 carbon atoms inclusive, or up to 9 carbon atoms inclusive.
- Exemplary hydrocarbons include pentane, octane, benzene, toluene, xylene, alkylbenzenes, and decahydronaphthalene.
- Exemplary aliphatic halohydrocarbons include methylene chloride, methylene bromide, chloroform, carbon tetrachloride, 1 ,2-dibromoethane, 1,1,2-trichloroethane,
- exemplary aromatic halohydrocarbons include chlorobenzene, bromobenzene,
- the aliphatic halohydrocarbon may be a compound containing at least two chloride substituents such as carbon tetrachloride or 1,1,2-trichloroethane.
- the aromatic halohydrocarbon may be chlorobenzene or o-chlorotoluene.
- the halogenation may be repeated one or more times, optionally accompanied by washing with an inert liquid such as an aliphatic or aromatic hydrocarbon or halohydrocarbon between halogenations and following halogenation. Further optionally one or more extractions involving contacting with an inert liquid diluent, especially an aliphatic or aromatic hydrocarbon, or aliphatic or aromatic halohydrocarbon, especially at an elevated temperature greater than 100°C, or greater than 110°C, may be employed to remove labile species, especially TiCl 4 .
- an inert liquid diluent especially an aliphatic or aromatic hydrocarbon, or aliphatic or aromatic halohydrocarbon, especially at an elevated temperature greater than 100°C, or greater than 110°C
- the Ziegler-Natta procatalyst composition includes a solid catalyst component obtained by (i) suspending a dialkoxy magnesium in an aromatic hydrocarbon or halohydrocarbon that is liquid at normal temperatures, (ii) contacting the dialkoxy magnesium with a titanium halide and further (iii) contacting the resulting composition a second time with the titanium halide, and contacting the dialkoxy magnesium with a diester of an aromatic dicarboxylic acid at some point during the treatment with the titanium halide in (ii).
- the Ziegler-Natta procatalyst composition includes a solid catalyst component obtained by (i) suspending a precursor material of the formula MgdTi(OR e ) f X g (as described previously) in an aromatic hydrocarbon or halohydrocarbon that is liquid at normal temperatures, (ii) contacting the precursor with a titanium halide and further (iii) contacting the resulting composition a second time with the titanium halide, and contacting the precursor with a diester of an aromatic dicarboxylic acid at some point during the treatment with the titanium halide in (ii).
- the Ziegler-Natta procatalyst composition includes an internal electron donor.
- the internal electron donor provides tacticity control and catalyst crystallite sizing.
- suitable internal electron donors include aromatic dicarboxylic acid esters, halides or anhydrides or (poly)alkyl ether derivatives thereof, especially C 1-4 dialkyl esters of phthalic or terephthalic acid, phthaloyl dichloride, phthalic anhydride, and Ci_ 4 (poly)alkyl ether derivatives thereof.
- the internal electron donor is diisobutyl phthalate or di-n-butyl phthalate.
- the Ziegler-Natta procatalyst composition may also include an inert support material.
- the support may be an inert solid which does not adversely alter the catalytic performance of the transition metal compound.
- Examples include metal oxides, such as alumina, and metalloid oxides, such as silica.
- the cocatalyst for use with the foregoing Ziegler-Natta procatalyst composition is an aluminum containing composition.
- suitable aluminum containing compositions include organoaluminum
- the cocatalyst is a C 1-4 trialkylaluminum compound, such as triethylaluminum (TEAL).
- TEAL triethylaluminum
- the molar ratio of aluminum to titanium of from 35:1 to 50:1. In an embodiment, the molar ratio of aluminum to titanium to 45:1.
- the method of the present invention also involves introducing a mixed electron donor system to the reactor.
- the mixed electron donor system is a mixture of (i) one or more activity limiting agents (ALA) and/or (ii) one or more silane compositions as a selectivity control agent (SCA).
- the ALA is an aliphatic ester.
- the aliphatic ester may be a C4-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 C 4 - C 30 aliphatic acid ester may also be substituted with one or more Group 14, 15 or 16 heteroatom containing substituents.
- Nonlimiting examples of suitable C4-C 30 aliphatic acid esters include C 1-20 alkyl esters of aliphatic C4-30 monocarboxylic acids, Ci-2 0 alkyl esters of aliphatic Cs-2o monocarboxylic acids, C 1-4 allyl mono- and diesters of aliphatic C4-2 0 monocarboxylic acids and dicarboxylic acids, C 1-4 alkyl esters of aliphatic Cs-2o monocarboxylic acids and dicarboxylic acids, and C 4 _2o alkyl mono- or polycarboxylate derivatives of C2-1 00 (poly)glycols or C2-1 00 (poly) glycol ethers.
- the C4-C 30 aliphatic acid ester may be isopropyl myristate, di-n-butyl sebacate, (poly)(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 C2-40 aliphatic carboxylic acids, and mixtures thereof.
- the C4-C30 aliphatic ester is isopropyl myristate or di-n-butyl sebacate.
- 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 dialkyl diether compound or an amine compound.
- the dialkyl diether compound is represented by the following formula,
- R 1 to R 4 are independently of one another an alkyl, aryl or aralkyl group having up to 20 carbon atoms, which may optionally contain a group 14, 15, 16, or 17 heteroatom, provided that R 1 and R 2 may be a hydrogen atom.
- Nonlimiting examples of suitable dialkyl ether compounds include dimethyl ether, diethyl ether, dibutyl ether, methyl ethyl ether, methyl butyl ether, methyl cyclohexyl ether, 2,2-dimethyl-l,3-dimethoxypropane, 2,2-diethyl-l,3- dimethoxypropane, 2,2-di-n-butyl- 1,3-dimethoxypropane, 2,2-diisobutyl- 1 ,3- dimethoxypropane, 2-ethyl-2-n-butyl- 1 ,3-dimethoxypropane, 2-n-propyl-2- cyclopentyl- 1 ,3-dimethoxypropane, 2,2-dimethyl- 1 ,3-diethoxypropane, 2- isopropyl-2-isobutyl- 1 ,3-dimethoxypropane, 2,2-dicyclopentyl-l
- the non-ester composition is an amine compound.
- suitable amine compounds include 2,6-substituted piperidines such as 2,6-dimethylpiperidine and 2,2,6,6-tetramethylpiperidine and 2,5-substituted piperidines.
- the piperidine compound is 2,2,6,6-tetramethylpiperidine.
- ALA that contains more than one carboxylate groups
- all the carboxylate groups are considered effective components.
- a sebacate molecule contains two carboxylate functional groups is considered to have two effective functional molecules.
- the SCA includes a silane composition.
- the silane composition 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 hydrocarbyl 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 Ci-20 alkyl group, and m is 0, 1, 2 or 3.
- R is C 6 -i2 aryl, alkyl or aralkyl, C3-12 cycloallyl, C3-12 branched alkyl, or C3-12 cyclic amino group
- R' is C1-4 allyl
- m is 1 or 2.
- suitable silane compositions include dicyclopentyldimethoxysilane, di-tert-butyldimethoxysilane, methylcyclohexyldimethoxysilane,
- diisobutyldimethoxysilane diisobutyldiethoxysilane, di-n-butyldimethoxysilane, cyclopentyltrimethoxysilane, isopropyltrimethoxysilane, n- propyltrimethoxysilane, n-propyltriethoxysilane, ethyltriethoxysilane, tetramethoxysilane, tetraethoxysilane, cyclopentylpyrrolidinodimethoxysilane, bis(pyrrolidino)dimethoxysilane, bis(perhydroisoquinolino)dimethoxysilane, and dimethyldimethoxysilane.
- the silane composition may be dicyclopentyldimethoxysilane, methylcyclohexyldimethoxysilane, or n- propyltrimethoxysilane, and any combination of thereof. In a further embodiment, the silane composition is dicyclopentyldimethoxysilane.
- the mixed external electron donor may comprise three or more external electron donors.
- MWD molecular weight distribution
- a catalyst composition that leads to broad MWD while greatly reducing the tendency of reactor fouling can be obtained.
- Such composition include mixtures of at least 2 alkoxysilanes wherein one of the alkoxysilane yield polymer with a melt flow rate at least twice as high as the another polymer formed under the same polymerization condition and an ALA selected from a carboxylic acid ester or a non-ester composition as described previously.
- the carboxylic acid ester ALA may be an ester of an aromatic carboxylic acid or a derivative thereof, an aliphatic ester, or a non-ester composition.
- suitable aromatic carboxylic acids include Ci_io alkyl or cycloalkyl esters of aromatic monocarboxylic acids.
- Suitable substituted derivatives thereof include compounds substituted both on the aromatic ring(s) or the ester group with one or more substituents containing one or more Group 14, 15 or 16 heteroatoms, especially oxygen. Examples of such substituents include (poly)alkylether, cycloalkylether, arylether, aralkylether, alkylthioether, arylthioether,
- the aromatic carboxylic acid ester may be a Ci_ 2 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 1-20 (poly)hydrocarbyl ether derivatives thereof, or C 1-4 alkyl benzoates and C 1-4 ring alkylated derivatives thereof, or methyl benzoate, ethyl benzoate, propyl benzoate, methyl p-methoxybenzoate, methyl p-ethoxybenzoate, ethyl p- methoxybenzoate, and ethyl p-ethoxybenzoate.
- the aromatic monocarboxylic acid is ethyl p- ethoxybenzoate.
- the ALA is an aliphatic ester.
- the aliphatic ester may be a C4-C30 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.
- Nonlimiting examples of suitable C4-C30 aliphatic acid esters include C 1-20 alkyl esters of aliphatic C4-30 monocarboxylic acids, C 1-20 alkyl esters of aliphatic Cs-2o monocarboxylic acids, C 1-4 allyl mono- and diesters of aliphatic C4-20 monocarboxylic acids and dicarboxylic acids, C 1-4 alkyl esters of aliphatic Cs-2o monocarboxylic acids and dicarboxylic acids, and C4-20 mono- or polycarboxylate derivatives of C2-100 (poly)glycols or C2-100 (poly)glycol ethers.
- the C4-C30 aliphatic acid ester may be isopropyl myristate, di-n-butyl sebacate, (poly)(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 C2-40 aliphatic carboxylic acids, and mixtures thereof.
- the C4-C30 aliphatic ester is isopropyl myristate or di-n-butyl sebacate.
- one of the alkoxysilanes in the mixtures is
- the molar ratio of aluminum to total SCA is from 0.5:1 to 4:1 (or any value therebetween), or from 1:1 to 3:1, or from 2:1 to 3:1 or less than or equal to 2.5:1.
- the "total SCA” is meant to include all external electron donors and thus is the combined amount of the ALA (if present) and the silane composition and the non-ester composition (if present) present in the catalyst composition.
- the molar ratio of aluminum to total SCA is 2.5:1.
- the ALA is an alkyl ester of C4-C30 aliphatic acid or a non-ester composition.
- the molar ratio of aluminum to total SCA is from 0.5:1 to 50:1, or from 0.75:1 to 30:1, or 1:1 to 20:1 when (poly)(alkylene glycol) ester of C4-C 30 aliphatic acid is the ALA.
- the catalyst, cocatalyst, and mixed electron donor can be introduced to the reactor together or separately, as is generally known in the art.
- the reactor process there are several ways of controlling the reactor process to ensure a bed minus dew temperature of 12°C or more.
- the dew point of the recycle fluid is a function of pressure
- one way to increase the bed minus dew point difference is to operate the reactor at a lower pressure.
- the reactor is operated at a total pressure of less than 375 psi (gauge), more preferably less than 350 psi (gauge).
- the reactor has a reactor temperature higher than 70°C, more preferably higher than 72°C.
- Another way to increase the difference between the bed temperature and the dew point of the recycle stream is to add condensing agents to the recycle fluid in order to lower its dew point.
- Propylene monomer may be used as a condensing agent as well as a raw material when polypropylene is being manufactured.
- Polypropylene homopolymers can be so prepared as well as copolymers with other comonomers, such as for example, random copolymers of ethylene-propylene and/or butene -propylene.
- Alternative condensing agents may be added to the polypropylene process, non-limiting examples of which include propane, butane, pentane, isopentane and hexane.
- the condensing agents can be added at levels to facilitate condensing, preferably in the range of 5 to 90 wt. percent condensing.
- Propane on the other hand, although added in great quantity, does not greatly dissolve and soften the propylene-butene copolymer resin and is therefore an excellent tool for lowering the dew point of the recycle fluid.
- two or more condensing agents may be used together.
- isopentane may be added at a level that does not cause undue resin stickiness
- propane may be added to further increase the amount of condensing as well as to increase the heat capacity of the cycle gas.
- Propane may prevent resin agglomeration in the fluid bed in regions not penetrated by liquid. Propane may also aid in the removal of heavier hydrocarbons during the resin degassing process after product removal.
- the method of introducing the condensing agent may vary. For example, it may be introduced as a gas or a liquid, together with the monomer or a comonomer, through line 3 or a separate line to distribution plate 7, alone or together with other additives for the process such as inert solids, hydrogen, catalyst and/or cocatalyst.
- the recycle stream may include both fresh and recycled propylene.
- the recycled fluid may also be introduced directly into the fluidized bed 2 through the wall of straight section 1 or by means of a conduit passing directly through distributor plate 7 (see US Patent 5,804,677). It may be divided or split into two or more streams having the same or differing ratios of liquid to gas.
- the method of cooling, condensing and reintroducing the recycle stream to the fluid bed may vary. Multiple or single heat exchange coolers in the recirculation line may be used in series or parallel. Water may be used as the cooling medium, and refrigeration can be employed to increase the amount of cooling.
- the blower that recirculates the recycle stream around the loop may be located before, after or in between the coolers.
- the partially condensed recycle stream may be split into two parts, one containing mainly liquid and one containing mainly gas, and the two streams introduced separately into the fluid bed. The separate gas or liquid streams may be further heated, cooled, compressed, pumped or condensed prior to reintroduction to the fluid bed as is known in the art.
- the liquid can be sprayed into the reactor using an assist gas that may be the cycle gas.
- the polymerization catalyst can be added to the reactor with the condensed liquid recycle stream introduced separately into the fluidized bed while operation under the turbulent fluidization regime with the advantage that the catalyst is better dispersed and localized hot spotting of the catalyst is reduced relative to such operation under the bubbling fluidization regime.
- the reactor itself may be any gas phase reactor known in the art.
- the reactor is a fluidized bed reactor such as depicted in Figure 1. If a fluidized bed reactor is used, it may be advantageous to operate the reactor such that it has a superficial gas velocity in the range of from 0.2 to 1 m/s.
- the reactor can also include a mechanical agitator or scraper.
- the reactor can be arranged horizontally or vertically or in other arrangements, as is generally known in the art.
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Abstract
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Priority Applications (11)
Application Number | Priority Date | Filing Date | Title |
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KR1020207030293A KR102416240B1 (en) | 2011-11-15 | 2011-11-15 | Method for polymerizing polypropylene |
PCT/US2011/060758 WO2013074087A1 (en) | 2011-11-15 | 2011-11-15 | Method for polymerizing polypropylene |
JP2014542281A JP2015501857A (en) | 2011-11-15 | 2011-11-15 | Polymerization method of polypropylene |
MX2014005781A MX2014005781A (en) | 2011-11-15 | 2011-11-15 | Method for polymerizing polypropylene. |
KR1020187020926A KR20180086292A (en) | 2011-11-15 | 2011-11-15 | Method for polymerizing polypropylene |
SG11201402166RA SG11201402166RA (en) | 2011-11-15 | 2011-11-15 | Method for polymerizing polypropylene |
BR112014011600A BR112014011600A2 (en) | 2011-11-15 | 2011-11-15 | Polypropylene polymerization method |
KR1020147015991A KR20140089607A (en) | 2011-11-15 | 2011-11-15 | Method for polymerizing polypropylene |
CN201180076256.5A CN104066755B (en) | 2011-11-15 | 2011-11-15 | Method for polymeric polymer propene |
RU2014124115/04A RU2014124115A (en) | 2011-11-15 | 2011-11-15 | METHOD OF POLYMERIZATION OF PROPYLENE |
EP11788729.9A EP2780379B1 (en) | 2011-11-15 | 2011-11-15 | Method for polymerizing polypropylene |
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PCT/US2011/060758 WO2013074087A1 (en) | 2011-11-15 | 2011-11-15 | Method for polymerizing polypropylene |
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EP (1) | EP2780379B1 (en) |
JP (1) | JP2015501857A (en) |
KR (3) | KR102416240B1 (en) |
CN (1) | CN104066755B (en) |
BR (1) | BR112014011600A2 (en) |
MX (1) | MX2014005781A (en) |
RU (1) | RU2014124115A (en) |
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Cited By (12)
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WO2016198344A1 (en) | 2015-06-12 | 2016-12-15 | Sabic Global Technologies B.V. | Process for manufacture of low emission polypropylene |
US9534063B2 (en) | 2008-12-31 | 2017-01-03 | W. R. Grace & Co.—Conn | Procatalyst composition with substituted 1,2-phenylene aromatic diester internal donor and method |
WO2017025327A1 (en) * | 2015-08-07 | 2017-02-16 | Sabic Global Technologies B.V. | Process for the polymerization of olefins |
WO2017025330A1 (en) * | 2015-08-07 | 2017-02-16 | Sabic Global Technologies B.V. | Process for the polymerization of olefins |
WO2017025331A1 (en) * | 2015-08-07 | 2017-02-16 | Sabic Global Technologies B.V. | Process for the polymerization of olefins |
WO2018067367A1 (en) | 2016-10-06 | 2018-04-12 | W.R. Grace & Co.-Conn. | Procatalyst composition made with a combination of internal electron donors |
WO2019231916A1 (en) | 2018-05-31 | 2019-12-05 | E. I. Du Pont De Nemours And Company | Molded articles, and methods thereof |
US10696756B2 (en) | 2015-08-07 | 2020-06-30 | Sabic Global Technologies B.V. | Process for the polymerization of olefins |
WO2020190681A1 (en) * | 2019-03-15 | 2020-09-24 | W.R. Grace & Co.-Conn. | Catalyst system for producing olefin polymers with no fines |
WO2022056053A1 (en) * | 2020-09-09 | 2022-03-17 | W.R. Grace & Co.-Conn. | Polypropylene polymer having ultra-high melt flow rate |
CN116003656A (en) * | 2022-12-29 | 2023-04-25 | 湖北华邦化学有限公司 | External electron donor composition, ziegler-Natta catalyst composition and propylene polymerization process |
RU2818247C2 (en) * | 2019-03-15 | 2024-04-26 | В.Р. Грейс Энд Ко.-Конн. | Catalyst system for producing olefin polymers without fine particles |
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WO2017114930A1 (en) * | 2015-12-30 | 2017-07-06 | Sabic Global Technologies B.V. | Improved gas phase olefins polymerization process operating in condensing mode |
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- 2011-11-15 CN CN201180076256.5A patent/CN104066755B/en active Active
- 2011-11-15 BR BR112014011600A patent/BR112014011600A2/en not_active IP Right Cessation
- 2011-11-15 EP EP11788729.9A patent/EP2780379B1/en active Active
- 2011-11-15 JP JP2014542281A patent/JP2015501857A/en active Pending
- 2011-11-15 RU RU2014124115/04A patent/RU2014124115A/en not_active Application Discontinuation
- 2011-11-15 SG SG11201402166RA patent/SG11201402166RA/en unknown
- 2011-11-15 KR KR1020207030293A patent/KR102416240B1/en active IP Right Grant
- 2011-11-15 KR KR1020187020926A patent/KR20180086292A/en active Application Filing
- 2011-11-15 KR KR1020147015991A patent/KR20140089607A/en active Application Filing
- 2011-11-15 WO PCT/US2011/060758 patent/WO2013074087A1/en active Application Filing
- 2011-11-15 MX MX2014005781A patent/MX2014005781A/en unknown
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US9534063B2 (en) | 2008-12-31 | 2017-01-03 | W. R. Grace & Co.—Conn | Procatalyst composition with substituted 1,2-phenylene aromatic diester internal donor and method |
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WO2016198344A1 (en) | 2015-06-12 | 2016-12-15 | Sabic Global Technologies B.V. | Process for manufacture of low emission polypropylene |
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CN107922694B (en) * | 2015-06-12 | 2023-08-15 | Sabic环球技术有限责任公司 | Process for producing low emission polypropylene |
WO2017025327A1 (en) * | 2015-08-07 | 2017-02-16 | Sabic Global Technologies B.V. | Process for the polymerization of olefins |
WO2017025330A1 (en) * | 2015-08-07 | 2017-02-16 | Sabic Global Technologies B.V. | Process for the polymerization of olefins |
WO2017025331A1 (en) * | 2015-08-07 | 2017-02-16 | Sabic Global Technologies B.V. | Process for the polymerization of olefins |
US20180230251A1 (en) * | 2015-08-07 | 2018-08-16 | Sabic Global Technologies B.V. | Process for the polymerization of olefins |
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US10759883B2 (en) | 2015-08-07 | 2020-09-01 | Sabin Global Technologies B.V. | Process for the polymerization of olefins |
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WO2018067367A1 (en) | 2016-10-06 | 2018-04-12 | W.R. Grace & Co.-Conn. | Procatalyst composition made with a combination of internal electron donors |
US11014995B2 (en) | 2016-10-06 | 2021-05-25 | W.R. Grace & Co.—Conn. | Procatalyst composition made with a combination of internal electron donors |
WO2019231916A1 (en) | 2018-05-31 | 2019-12-05 | E. I. Du Pont De Nemours And Company | Molded articles, and methods thereof |
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WO2020190681A1 (en) * | 2019-03-15 | 2020-09-24 | W.R. Grace & Co.-Conn. | Catalyst system for producing olefin polymers with no fines |
RU2818247C2 (en) * | 2019-03-15 | 2024-04-26 | В.Р. Грейс Энд Ко.-Конн. | Catalyst system for producing olefin polymers without fine particles |
WO2022056053A1 (en) * | 2020-09-09 | 2022-03-17 | W.R. Grace & Co.-Conn. | Polypropylene polymer having ultra-high melt flow rate |
CN116003656A (en) * | 2022-12-29 | 2023-04-25 | 湖北华邦化学有限公司 | External electron donor composition, ziegler-Natta catalyst composition and propylene polymerization process |
CN116003656B (en) * | 2022-12-29 | 2024-04-26 | 湖北华邦化学有限公司 | External electron donor composition, ziegler-Natta catalyst composition and propylene polymerization process |
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Publication number | Publication date |
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SG11201402166RA (en) | 2014-06-27 |
CN104066755B (en) | 2017-07-14 |
KR102416240B1 (en) | 2022-07-01 |
JP2015501857A (en) | 2015-01-19 |
CN104066755A (en) | 2014-09-24 |
EP2780379B1 (en) | 2017-01-11 |
KR20180086292A (en) | 2018-07-30 |
KR20140089607A (en) | 2014-07-15 |
EP2780379A1 (en) | 2014-09-24 |
BR112014011600A2 (en) | 2017-05-30 |
MX2014005781A (en) | 2014-05-30 |
KR20200123282A (en) | 2020-10-28 |
RU2014124115A (en) | 2015-12-27 |
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