WO2021126523A1 - Production d'un copolymère de polypropylène résistant aux chocs à l'aide de catalyseurs métallocène et ziegler-natta dans des réacteurs parallèles - Google Patents

Production d'un copolymère de polypropylène résistant aux chocs à l'aide de catalyseurs métallocène et ziegler-natta dans des réacteurs parallèles Download PDF

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Publication number
WO2021126523A1
WO2021126523A1 PCT/US2020/062774 US2020062774W WO2021126523A1 WO 2021126523 A1 WO2021126523 A1 WO 2021126523A1 US 2020062774 W US2020062774 W US 2020062774W WO 2021126523 A1 WO2021126523 A1 WO 2021126523A1
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reactor
fraction
catalyst
separator
product mixture
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PCT/US2020/062774
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English (en)
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Yifeng Hong
Jay L. Reimers
Xiaodan ZHANG
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Exxonmobil Chemical Patents Inc.
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Publication of WO2021126523A1 publication Critical patent/WO2021126523A1/fr

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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
    • 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
    • C08F6/00—Post-polymerisation treatments
    • C08F6/001—Removal of residual monomers by physical means
    • C08F6/003—Removal of residual monomers by physical means from polymer solutions, suspensions, dispersions or emulsions without recovery of the polymer therefrom

Definitions

  • the present disclosure generally relates to inline production of polymer blends.
  • a common method to improve the toughness and impact resistance of isotactic polypropylene (iPP) has been the addition of elastomer components as a dispersed phase within a continuous phase of iPP.
  • Two widely used elastomers for toughening iPP are ethylene- propylene rubber (EPR) and ethylene-propylene-diene rubber (EPDM).
  • EPR ethylene- propylene rubber
  • EPDM ethylene-propylene-diene rubber
  • the resulting polymer blend is referred to as impact copolymer polypropylene (ICP), which affords improved toughness and impact resistance compared to isotactic polypropylene alone.
  • ICP There are generally two methods introducing elastomers to iPP to form ICP.
  • Compounding iPP with an elastomer by melt mixing of previously synthesized polymer components may be accomplished using heat and mechanical force.
  • the other method used for producing ICP is commonly referred to as in-reactor blending, which includes first producing iPP in a first reactor and then embedding elastomers within the iPP in one or more following reactors arranged in series.
  • the in-reactor blending method has several benefits over direct compounding of previously synthesized iPP and elastomers, although there are also disadvantages to this technique, as discussed below. Namely, there are significant energy savings due to elimination of the compounding step as well as beneficial morphology and performance improvements that may be realized with in-reactor blending. As a result, most commercial scale production of ICP is conducted using in-reactor blending.
  • the molecular weight distribution of both the iPP phase and the dispersed elastomer (rubber) phase, along with the distribution ratio of the ethylene and propylene in the rubber, can influence the performance characteristics of ICP. Broadening of the molecular weight distribution of the iPP phase may afford beneficial effects of the stiffness and drawability of ICP. A narrow composition distribution of elastomer components (e.g., about a 1:1 mole ratio of ethylene and propylene) in the rubber phase may afford a balance of stiffness and toughness in ICP. If the rubber is too propylene rich (/. ⁇ ?
  • the rubber may penetrate into and soften the iPP phase, thereby lowering stiffness of the ICP. If the rubber is too ethylene rich (/. ⁇ ? ., ethylene to propylene monomer mole ratio >>1), poor compatibility of the rubber with the iPP may lead to larger dispersion domains and decrease the toughness of the ICP.
  • Ziegler-Natta catalysts and metallocene catalysts are usually incompatible with one another, which generally precludes placing these catalysts in a single reactor to promote direct production of an ICP.
  • the incompatibility of these two catalysts also creates significant difficulties in producing ICP via in-reactor blending using multiple reactors arranged in series.
  • the Ziegler-Natta catalyst used to produce the iPP may be incorporated within a matrix of the iPP, such that both the iPP and the Ziegler-Natta catalyst are transported to a downstream reactor for producing the rubber component of the ICP.
  • the Ziegler- Natta catalyst may react with the elastomeric components (monomers) to produce an undesirably wide molecular weight distribution of the rubber.
  • the transported Ziegler-Natta catalyst in fact, may preclude use of a metallocene catalyst in the downstream reactor.
  • the Ziegler-Natta catalyst leads to significant downstream process constraints for producing the rubber component. In many cases, optimized formulations cannot be realized in conventional ICP production processes.
  • the present disclosure provides methods for the production of polymer blends using multiple reactors arranged in parallel.
  • the methods comprise: providing a first feed comprising propylene to a first reactor operated in parallel with a second reactor; catalytically converting at least a portion of the first feed in the first reactor under polymer formation conditions in the presence of a first catalyst to form a first product mixture comprising polypropylene, the first catalyst, and unreacted propylene; separating the first product mixture into a first fraction comprising the polypropylene and a second fraction comprising the unreacted propylene; returning at least a portion of the second fraction to the first reactor; providing a second feed comprising one or more elastomeric monomers to the second reactor; catalytically converting at least a portion of the second feed in the second reactor under polymer formation conditions in the presence of a second catalyst different from the first catalyst to form a second product mixture comprising an elastomeric polymer; and blending the first fraction with the second product mixture downstream from the first reactor and the
  • the Figure shows a simplified diagram of a reactor system featuring parallel reactors for producing polymer blends by downstream blending of reactor outputs according to the present disclosure.
  • the present disclosure relates to production of impact copolymer polypropylene (ICP), and, more particularly, production of ICP using multiple reactors arranged in parallel.
  • ICP impact copolymer polypropylene
  • the common commercial processes for producing ICP materials have inherent drawbacks such as the difficulty and expense of post-production melt blending or the less than desirable ICP properties resulting from in-line blending using series reactors employing Ziegler-Natta catalysts.
  • Common series reactor configurations do not easily lend themselves to utilizing different catalysts that may optimize the properties of the polymer components before a fully blended ICP is formed.
  • the present disclosure provides methods and reactor systems for producing ICP or similar polymer blends, in which a Ziegler-Natta catalyst and a metallocene catalyst may be used in parallel reactors.
  • ICP with more optimized properties may be realized by forming iPP with a preferred molecular weight distribution using a Ziegler-Natta catalyst and a rubber with preferred monomer ratios, morphologies, and molecular weights using a metallocene catalyst.
  • the disclosed reactor system may allow advantageous in-line blending of the iPP and rubber to take place downstream of the reactors arranged in parallel, as discussed in more detail hereinafter.
  • Utilizing separator recycle loops at elevated temperatures in the course of in-line blending downstream of the parallel reactors may improve the compounding of the iPP and EPR because blending may occur at the molecular level, thereby producing ICP with improved morphologies and material properties.
  • the energy requirement to maintain the blended mixture at elevated temperatures during the separation and blending process may be less than that required to compound independently produced polymers (iPP and elastomeric polymer) by melt blending, thereby resulting in lower manufacturing costs.
  • Other advantages may be further achieved by the present disclosure.
  • the new numbering scheme for groups of the Periodic Table is used.
  • the groups (columns) are numbered sequentially from left to right from 1 through 18, excluding the f-block elements (lanthanides and actinides).
  • the term “transition metal” refers to any atom from Groups 3-12 of the Periodic Table, inclusive of the lanthanides and actinide elements.
  • Ti, Zr, and Hf are Group 4 transition metals, for example.
  • polymer molecular weights are reported as the weight average molecular weight (Mw).
  • the polydispersity index (PDI) calculated is the ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn). Unless otherwise noted, all molecular weights are in units of g/mol.
  • hydrocarbon refers to a class of compounds having hydrogen bound to carbon, and encompasses (i) saturated hydrocarbon compounds, (ii) unsaturated hydrocarbon compounds, and (iii) mixtures of hydrocarbon compounds (saturated and/or unsaturated), including mixtures of hydrocarbon compounds having different numbers of carbon atoms.
  • C n refers to hydrocarbon(s) or a hydrocarbyl group having n carbon atom(s) per molecule or group, wherein n is a positive integer.
  • Such hydrocarbon compounds may be one or more of linear, branched, cyclic, acyclic, saturated, unsaturated, aliphatic, or aromatic, with optional substitution being present in some cases.
  • hydrocarbyl and “hydrocarbyl group” are used interchangeably herein.
  • hydrocarbyl group refers to any Ci-Cioo hydrocarbon group bearing at least one unfilled valence position when removed from a parent compound. Suitable “hydrocarbyl” and “hydrocarbyl groups” may be optionally substituted.
  • hydrocarbyl group having 1 to about 100 carbon atoms refers to an optionally substituted moiety selected from a linear or branched Ci-Cioo alkyl, a C3-C100 cycloalkyl, a C6-C100 aryl, a C2-C100 heteroaryl, a C1-C100 alkylaryl, a C 7 -C 100 arylalkyl, and any combination thereof.
  • substituted refers to replacement of at least one hydrogen atom or carbon atom of a hydrocarbon or hydrocarbyl group with a heteroatom or heteroatom functional group.
  • Heteroatoms may include, but are not limited to, B, O, N, S, P, F, Cl, Br, I, Si, Pb, Ge, Sn, As, Sb, Se, and Te.
  • Suitable hydrocarbyl R groups may include alkyl, alkenyl, alkynyl, aryl, heteroaryl, cycloalkyl, heterocyclyl, and the like, any of which may be optionally substituted.
  • hydrocarbyl means that a hydrocarbon or hydrocarbyl group may be unsubstituted or substituted.
  • hydrocarbyl refers to replacement of at least one hydrogen atom or carbon atom in a hydrocarbyl group with a heteroatom or heteroatom functional group. Unless otherwise specified, any of the hydrocarbyl groups herein may be optionally substituted.
  • Me is methyl
  • Et is ethyl
  • Pr is propyl
  • cPr is cyclopropyl
  • nPr is n-propyl
  • iPr is isopropyl
  • Bu is butyl
  • nBu is normal butyl
  • iBu is isobutyl
  • sBu is sec -butyl
  • tBu is tert-butyl
  • Cy cyclohexyl
  • Oct is octyl
  • Ph is phenyl
  • Bn is benzyl.
  • the present disclosure provides methods for producing ICP and similar polymer blends using a system of parallel reactors, in which the methods may comprise: providing a first feed comprising propylene to a first reactor operated in parallel with a second reactor; catalytically converting at least a portion of the first feed in the first reactor under polymer formation conditions in the presence of a first catalyst to form a first product mixture comprising polypropylene, the first catalyst, and unreacted propylene; separating the first product mixture into a first fraction comprising the polypropylene and a second fraction comprising the unreacted propylene; returning at least a portion of the second fraction to the first reactor; providing a second feed comprising one or more elastomeric monomers to the second reactor; catalytically converting at least a portion of the second feed in the second reactor under polymer formation conditions in the presence of a second catalyst different from the first catalyst to form a second product mixture comprising an elastomeric polymer; and blending the first fraction with the second product
  • the first catalyst may comprise a Ziegler-Natta catalyst and the second catalyst may comprise a metallocene catalyst.
  • Suitable examples of Ziegler- Natta catalysts for producing a wide molecular weight distribution for polyolefins and metallocene catalysts for producing a narrow molecular weight distribution for polyolefins will be familiar to one having ordinary skill in the art.
  • suitable metallocenes may be represented by Formula 1
  • M is a transition metal, often a group 4 metal, such as titanium, zirconium or hafnium; n is 0 or 1; T is an optional bridging group (T is absent if n is 0 and T is present if n is 1); L 1 and L 2 are independently cyclopentadienyl, substituted cyclopentadienyl, indenyl, substituted indenyl, tetrahydroindenyl, substituted tetrahydroindenyl, fluorenyl, or substituted fluorenyl groups; and X 1 and X 2 are, independently, anionic groups selected from hydrogen, halogen, hydrocarbyl, substituted hydrocarbyl, halocarbyl, substituted halocarbyl, silyl, silylcarbyl, substituted silylcarbyl, germylcarbyl, substituted germylcarbyl, aryl, substituted aryl, heteroaryl, substituted hetero
  • X 1 and X 2 may be joined and bound to the metal atom to form a metallacycle ring containing from about 3 to about 20 carbon atoms, or both together can be an olefin, diolefin or aryne ligand.
  • Particular examples suitable for bridging group T may include, but are not limited to, CH 2 , CH2CH2, SiMe 2 , SiPh 2 , SiMePh, Si(CH 2 ) 3 , Si(CH 2 ) , O, S, NPh, PPh, NMe, PMe, NEt, NPr, NBu, PEt, PPr, Me2SiOSiMe2, and PBu.
  • bridging group T may be selected from dialkyl silyl , diarylsilyl, dialky lmethyl, diarylmethyl, methylene, hydrocarbylmethylene, ethylenyl, or hydrocarbylethylenyl, wherein one, two, three or four of the hydrogen atoms in ethylenyl may be substituted by a hydrocarbyl group
  • suitable metallocenes include, but are not limited to, the metallocenes disclosed and referenced in US Patents 7,179,876; 7,169,864; 7,157,531; 7,129,302; 6,995,109; 6,958,306; 6,884,748; 6,689,847; US Patent Application Publication 2007/0055028, and published PCT Applications WO 97/22635; WO 00/699/22; WO 01/30860; WO 01/30861; WO 02/46246; WO 02/50088;
  • non-metallocene, Ziegler-Natta catalysts suitable for use in the disclosure herein include, but are not limited to, late transition metal pyridylbisimines (e.g. , US Patent 7,087,686), group 4 pyridyldiamidos (e.g., US Patent 7,973,116), quinolinyldiamidos (e.g., US Patent Pub. No. 2018/0002352 Al), pyridylamidos (e.g., US Patent 7,087,690), phenoxyimines (e.g. , Makio, H. et al.
  • late transition metal pyridylbisimines e.g. , US Patent 7,087,686
  • group 4 pyridyldiamidos e.g., US Patent 7,973,116
  • quinolinyldiamidos e.g., US Patent Pub. No. 2018/0002352 Al
  • pyridylamidos
  • the one or more elastomeric monomers may comprise ethylene and propylene, as a non-limiting example.
  • the one or more elastomeric monomers may further comprise a diene monomer in some cases, such as dicyclopentadiene or ethylidene norbornene.
  • a diene monomer in some cases, such as dicyclopentadiene or ethylidene norbornene.
  • Other olefinic elastomers formed using metallocene catalysis may also be suitably produced through application of the disclosure herein.
  • the polypropylene produced in the disclosure herein may comprise isotactic polypropylene (iPP).
  • iPP isotactic polypropylene
  • Other olefinic polymers formed using Ziegler-Natta catalysis may also be produced using the disclosure herein.
  • the blending may comprise transporting the polymer blend through at least one mixer and at least one separator.
  • the polymer blend may be maintained in a molten state while passing through the at least one mixer and the at least one separator.
  • Suitable mixers and separators will be familiar to one having ordinary skill in the art and are described in more detail below.
  • the first product mixture comprising the polypropylene may be exposed to a first (lead) separator before the polypropylene is further blended with the elastomeric polymer.
  • the resulting polymer blend may pass through at least one additional separator, more typically multiple separators operated at progressively decreasing pressures.
  • a mixer such as a static mixer, and a recycle loop may be associated with each separator used in compounding the polymer blend.
  • Methods of the present disclosure may further comprise: removing an overhead fraction from the at least one separator, specifically the at least one separator containing the polypropylene and elastomeric polymer in combination with one another, in which the overhead fraction comprises at least the one or more unreacted elastomeric monomers; and returning at least a portion of the overhead fraction to the second reactor.
  • the overhead fraction returned to the second reactor may be combined with the feed entering the second reactor, or the overhead fraction may be introduced to the second reactor separately.
  • the composition of the feed entering the second reactor may be adjusted in response to the composition of the overhead fraction being returned to the second reactor.
  • the methods of the present disclosure may also include the first product mixture being separated into the first fraction and the second fraction with a cyclone separator.
  • the propylene in the second fraction may be returned to the first reactor, and the polypropylene in the first fraction may be further compounded with an elastomeric polymer produced in the second reactor according to the disclosure herein.
  • the second reactor may be a continuously stirred tank reactor, and polymerization may take place in a solution phase or in bulk.
  • the second product mixture may initially comprise up to about fifty percent solvent by weight before being further compounded with polypropylene according to the disclosure herein.
  • the solvent may be at least partially removed before being blended with the first product mixture.
  • Operating parameters of the first reactor may be optimized to produce an isotactic polypropylene having a weight average molecular weight of about 5,000 to about 500,000 or about 500,000 to about 10,000,000.
  • Operating parameters of the second reactor may be optimized to produce an ethylene-propylene rubber or similar elastomeric polymer having a weight average molecular weight of about 100,000 to about 500,000.
  • Operating parameters of the second reactor may be optimized to produce an ethylene-propylene rubber having an ethylene weight portion between about 20% to about 80%.
  • Operating parameters of the first and second reactors may be optimized to produce an impact copolymer polypropylene having a weight portion of ethylene-propylene rubber between about 0% to about 80%.
  • Operating parameters of the first reactor may be optimized to produce an isotactic polypropylene having a PDI of at least about 2.6.
  • Operating parameters of the second reactor may be optimized to produce ethylene-propylene rubber or similar elastomeric polymer having a PDI no greater than about 2.0.
  • FIG. shows a simplified diagram of a reactor system featuring parallel reactors for producing polymer blends by downstream blending of reactor outputs according to the present disclosure.
  • Reactor system 100 includes first reactor 110 and second reactor 112 operating in parallel and configured to catalytically convert olefin monomers into different polyolefin polymers. Different catalysts are employed in first reactor 110 and second reactor 112.
  • first reactor 110 may be a loop reactor utilizing slurry polymerization of propylene to produce iPP using a Ziegler-Natta catalyst.
  • second reactor 112 may be a continuously stirred tank reactor (CSTR) utilizing solution polymerization of propylene and ethylene to produce EPR or a similar elastomeric polymer using a metallocene catalyst.
  • CSTR continuously stirred tank reactor
  • Other polyolefin elastomeric polymers may be produced similarly in second reactor 112.
  • first feed 114 comprising an olefin monomer is directed into first reactor 110. At least a portion of first feed 114 is catalytically converted within first reactor 110 under polymer formation conditions in the presence of a first catalyst, typically a Ziegler-Natta catalyst, to form a first product mixture.
  • the first product mixture comprises at least the unreacted olefin monomer, the first catalyst, and a polyolefin polymer, such as polypropylene.
  • First effluent 116 comprising the first product mixture passes from first reactor 110 to first separator 118, such as a hydrocyclone or similar cyclone separator.
  • first effluent 116 comprising the first product mixture may include at least iPP and unreacted propylene from first reactor 110, each of which is received at first separator 118.
  • first separator 118 may comprise a cyclone separator in various aspects of the present disclosure.
  • first separator 118 the first product mixture is separated into first fraction 120 comprising the polyolefin polymer and a second fraction comprising the unreacted olefin monomer.
  • First fraction 120 of the first product mixture is the output of first separator 118, which is further compounded downstream according to the disclosure provided hereinbelow.
  • First recycle loop 122 provides a pathway for at least a portion of the overhead fraction or unreacted olefin monomer in the second portion separated in first separator 118 to return to first reactor 110 via first feed 114.
  • the cyclone separator permits the first effluent 116 to be separated into a first fraction comprising iPP powder and a second fraction comprising the unreacted propylene and other volatiles in the vapor phase, which is recycled back into first reactor 110 via first recycle loop 122.
  • the residual weight balance of first effluent 116 may range from 0% to 50%, depending on the production rate, cyclone capacity, and recycle mass balance, for example.
  • the employment of the cyclone separator on first effluent 116 is a significant factor to increase propylene conversion rates and satisfy the materials balance between makeup monomers and recycled volatiles.
  • second feed 124 comprising one or more elastomeric monomers, typically multiple olefin monomers, is directed into second reactor 112. At least a portion of second feed 124 is catalytically converted within second reactor 112 under polymer formation conditions in the presence of a second catalyst that is different from the first catalyst to form a second product mixture comprising an elastomeric polymer, typically an elastomeric polyolefin polymer such as ethylene-propylene rubber (EPR) or ethylene-propylene-diene monomer rubber (EPDM).
  • EPR ethylene-propylene rubber
  • EPDM ethylene-propylene-diene monomer rubber
  • second reactor 112 may be a continuously stirred tank reactor (CSTR) utilizing solution polymerization of propylene and ethylene to produce EPR or a similar elastomeric polymer using a metallocene catalyst.
  • CSTR continuously stirred tank reactor
  • the elastomeric polymer may be obtained in a solution, which may comprise up to about 50% solvent by weight in some instances.
  • Second effluent 126 comprising the second product mixture passes from second reactor 112 and is combined with first fraction 120.
  • the second product mixture may comprise at least EPR or a similar elastomeric polymer, unreacted propylene, unreacted ethylene, and the metallocene catalyst when the reactor system is used for ICP production.
  • the first fraction may comprise at least iPP powder.
  • Second effluent 126 comprising the second product mixture and first fraction 120 of the first product mixture are blended together in vessel 128, which may comprise a first static mixer configured to induce turbulent flow in the polymer blend. Other means of mixing may be used as well, such as stirred tank mixing. The resulting polymer blend is transported/pumped from vessel 128 to second separator 132.
  • the resulting polymer blend of iPP powder and EPR or a similar elastomeric polymer forms ICP comprising iPP in a continuous phase and EPR or a similar elastomeric polymer as an elastomeric discontinuous phase.
  • a first overhead fraction comprising at least one unreacted olefinic monomer received from either first reactor 110 or second reactor 112 may be removed via exhaust line 134, which may include a condenser (not shown) for feeding unreacted olefinic monomers back into second feed 124 for subsequent recycling into second reactor 112.
  • Non-condensable materials in the first overhead fraction may be sent to a second stage condenser (not shown), or to another process in the refinery (not shown), or flaring may be conducted (not shown).
  • recycle loop 136 While the polymer blend is being processed within second separator 132, it may be recirculated through recycle loop 136, which may include at least static mixer 138. Alternative means of mixing, such as stirred tank mixing, may also take place during recirculation. Continued compounding of the polymer blend in static mixer 138 and recycle loop 136 may enhance intermingling of the polymer chains and promote removal of the volatile components as the overhead fraction removed through exhaust line 134.
  • output 140 of second separator 132 may then be transferred to third separator 142. Similar to the operation of separator 132, the polymer blend may be further processed in third separator 142 and recirculated through recycle loop 146, which may also include at least static mixer 148. Alternately, stirred tank mixing may take place within recycle loop 146. Likewise, exhaust line 144 may separate and return an overhead fraction comprising one or more unreacted olefinic monomers to second feed 124.
  • the polymer blend as output 150 of third separator 142, may be received in fourth separator 152 for further processing.
  • a third overhead fraction may be vented from fourth separator 152 via an exhaust line 154 to be further processed or flared.
  • Output 156 transports/pumps the polymer blend from fourth separator 152 for further and/or final processing.
  • first separator 128 Although three separators downstream of first separator 128 are described herein (/. ⁇ ? ., second separator 132, third separator 142, and fourth separator 152), it is contemplated that fewer or more separators may be present instead of those expressly depicted. Similarly, depending on particular process configurations, it is to be understood that not all separators are necessarily configured to return their overhead fraction to second feed 124.
  • the temperature of the polymer blend may be elevated to maintain a molten state downstream from first reactor 110 and second reactor 112 when reactor system 100 is utilized for ICP production. It is also contemplated that the polymer blend may comprise the polymers dissolved and/or suspended in solvents after the initial blending downstream from first reactor 110 and second reactor 112. Thus, the polymer blend may only need to be maintained at an elevated temperature after one or more separation process steps in some instances.
  • the operating temperatures of the separators may be about 160°C to about 200°C in many instances.
  • First separator 118 which may be a cyclone separator, may be operated at the process pressure within first reactor 110 or may be higher or lower.
  • first separator 118 may be operated at a pressure of about 375 psi to about 500 psi. It is also further contemplated that first separator 118 may be operated at even higher pressures depending on the operating pressures of the downstream separators (/. ⁇ ? ., separator 132 and optional separators 142 and 152). Downstream from first separator 118, subsequent separators may be operated at progressively decreasing pressures (/. ⁇ ? ., separator 132 and optional separators 142 and 152). Second separator 132 may be a high-pressure separator operated at a pressure of about 150 psi to about 350 psi.
  • Optional third separator 142 may be a low-pressure separator operated at a pressure of about 90 psi to about 100 psi.
  • optional fourth separator 152 may be a vacuum separator operated at a working pressure of about 40 torr. After the separation process is complete and the polymer blend has been obtained, the finishing process of the ICP may be by any standardized methods or techniques. Other aspects of reactor system 100 may be developed in light of the present disclosure. [0049] It is contemplated that reactor system 100 may produce EPR having a weight average molecular weight of about 100,000 to about 1,000,000 and iPP having a weight average molecular weight of about 5,000 to about 500,000.
  • reactor system 100 may produce EPR or a similar elastomeric polymer having an ethylene content by weight of about 20% to about 80%. It is further contemplated that reactor system 100 as described above may produce ICP having an EPR content by weight of about 0.1% to about 80%.
  • reactor system 100 has been simplified for purposes of this disclosure.
  • Conventional equipment such as, but not limited to, pumps, heat exchangers, condensers, sensors, and any other required or standard production equipment have been excluded from the FIG. in the interest of clarity and simplicity.
  • the number of reactors, separators, and static mixers is not fixed as disclosed in the FIG. There may be multiple parallel reactors beyond the two shown in the FIG. Also, there may be pre polymerization reactors feeding first reactor 110, second reactor 112, or any number of other parallel reactors. The number of separators and associated recycle loops may also be dependent on the production rate and separator capacities and thus may be more or less than the number depicted.
  • reactor system 100 may be utilized for production of various types of polymer blends beyond ICP produced according to the disclosure herein. As such, production of ICP according to the disclosure herein should be considered a non-limiting example.
  • Embodiments disclosed herein include:
  • A. Methods comprising: providing a first feed comprising propylene to a first reactor operated in parallel with a second reactor; catalytically converting at least a portion of the first feed in the first reactor under polymer formation conditions in the presence of a first catalyst to form a first product mixture comprising polypropylene, the first catalyst, and unreacted propylene; separating the first product mixture into a first fraction comprising the polypropylene and a second fraction comprising the unreacted propylene; returning at least a portion of the second fraction to the first reactor; providing a second feed comprising one or more elastomeric monomers to the second reactor; catalytically converting at least a portion of the second feed in the second reactor under polymer formation conditions in the presence of a second catalyst different from the first catalyst to form a second product mixture comprising an elastomeric polymer; and blending the first fraction with the second product mixture downstream from the first reactor and the second reactor to form a polymer blend comprising polypropylene as a continuous
  • Element 1 wherein the first catalyst comprises a Ziegler-Natta catalyst and the second catalyst comprises a metallocene catalyst.
  • Element 2 wherein the one or more elastomeric monomers comprise at least ethylene and propylene.
  • Element 3 wherein the polypropylene comprises isotactic polypropylene.
  • Element 4 wherein blending comprises transporting the polymer blend through at least one mixer and at least one separator.
  • Element 5 wherein the polymer blend is maintained in a molten state while passing through the at least one mixer and the at least one separator.
  • Element 6 wherein the method further comprises: removing an overhead fraction from the at least one separator, the overhead fraction comprising at least one or more unreacted elastomeric monomers; and returning at least a portion of the overhead fraction to the second reactor.
  • Element 7 wherein at least two separators are operated at progressively decreasing pressures.
  • Element 8 wherein the first product mixture is separated into the first fraction and the second fraction with a cyclone separator.
  • Element 9 wherein the second product mixture initially comprises up to about fifty percent solvent by weight.
  • Element 10 wherein the second reactor is a continuous stirred tank reactor.
  • Element 11 wherein operating parameters of the first reactor are optimized to produce an isotactic polypropylene having a PDI of at least about 2.61 and operating parameters of the second reactor are optimized to produce ethylene-propylene rubber having a PDI no greater than about 2.0.
  • Element 12 wherein operating parameters of the first reactor are optimized to produce an isotactic polypropylene having a weight average molecular weight between about 5,000 to about 500,000.
  • Element 13 wherein operating parameters of the second reactor are optimized to produce an ethylene-propylene rubber having a weight average molecular weight between about 100,000 to about 500,000.
  • Element 14 wherein operating parameters of the second reactor are optimized to produce an ethylene-propylene rubber having an ethylene content by weight of about 20% to about 80%.
  • Element 15 wherein operating parameters of the first and second reactors are optimized to produce an impact copolymer polypropylene having an ethylene-propylene rubber content by weight of about 0.1% to about 80%.
  • exemplary combinations applicable to A include, but are not limited to: 1 and 2; 1 or 2 and 3; 1 or 2 and 4; 1 or 2 and 5; 1 or 2 and 6; 1 or 2 and 10; 1 or 2 and 11; 1 or 2 and 12; 1 or 2 and 13; 1 or 2 and 14; 1 or 2 and 15; 3 and 4; 3 or 4 and 5; 3 or 4 and 6; 3 or 4 and 6 and 7; 3 or 4 and 6 and 8; 3 or 4 and 6 and 7 and 9; 3 or 4 and 10; 3 or 4 and 11; 3 or 4 and 12; 3 or 4 and 13; 3 or 4 and 14; 3 or 4 and 15; 5 and 6; 5 and 6 and 7; 5 and 6 and 8; 5 and 7 and 9; 5 or 6 and 10; 5 or 6 and 11; 5 or 6 and 12; 5 or 6 and 13; 5 or 6 and 14; 5 or 6 and 15; 6 and 7 and 8; 6 and 7 and 9; 10 and 11; 10 or 11 and 12; 10 or 11 and 13; 10 or 11 and 13; 10; 10 or 11 and
  • thermodynamic method is based on Perturbed- Chain Statistical Association Fluid Theory (PC-SAFT).
  • PC-SAFT Perturbed- Chain Statistical Association Fluid Theory
  • the required material properties are directly obtained from the property data banks implemented in Aspen Plus.
  • the range of temperature, pressure, monomer and comonomer concentrations, etc., are designed based on an industrial scale ICP manufacturing process.
  • the reaction simulated in this example involves the copolymerization of ethylene and propylene to form EPR and homopolymerization of propylene to form iPP.
  • Copolymerization and homopolymerization kinetics are obtained from the literature and implemented in the simulation software.
  • Ethylene is treated as the comonomer when making EPR. Both heat and mass balance and polymer properties, including chemical composition and molecular weight distribution can be accurately modeled.
  • the target values of these four variables are all designed according to commercial ICP products and processes.
  • Table 1 summarizes the reactor conditions for both reactors in the simulation.
  • the iPP polymer concentration produced by the loop slurry reactor ranged between 67.3 % and 71.3% with propylene conversion rates ranging between 67.4% and 71.3%.
  • the EPR polymer concentration produced by the CSTR ranged between 5.8% and 16.4% with ethylene conversion rates ranging between 24.8% and 75.4% and with propylene conversion rates ranging between 10.6% and 50.1%.
  • [0076] 2 summarizes the operating temperature and pressures of the three vapor- liquid separators modeled in the simulation.
  • a high-pressure separator, a low-pressure separator, and a vacuum separator were modeled as described in the reactor system above.
  • the cyclone separator processing the effluent from the reactor producing iPP was modeled as operating at a temperature of about 200°C in the simulation.
  • the high pressure separator was modeled as operating at about 130°C and with pressures ranging from 185-350 pounds per square inch gage pressure.
  • the temperature of the high pressure separator is acceptable because at this process point the polymers in the blended mixture are still at least partially dissolved and/or suspended in a solvent solution.
  • the low pressure and vacuum separators may be operated at progressively higher temperatures.
  • the low pressure separator was modeled as operating at temperatures ranging between 160-180°C and with pressures ranging from 90-100 pounds per square inch gage pressure.
  • the vacuum pressure separator was modeled as operating at a temperature of about 200 °C and with a pressure of about 40 torr.
  • Table 3 summarizes the modeled properties of the polymer blends produced under the above simulation conditions.
  • the ethylene content in EPR produced in the simulations ranged from about 20% to about 42% by weight.
  • the weight average molecular weight of EPR ranged from about 150,000 to about 250,000.
  • the content of EPR in the ICP ranged from about 17% to about 42% by weight.
  • the weight average molecular weight of iPP produced in the simulations ranged from about 100,000 to about 200,000. Since the simulated EPR was produced with a metallocene catalyst having a single active site, the polydispersity index (PDI) of the EPR portion in the ICP was a narrow and desirable 2.00.
  • the simulated iPP portions had broader molecular weight distributions, corresponding to a PDI range between about 2.61 and about 2.69, as a resulting of the Ziegler-Natta catalyst having multiple active sites.
  • the simulation process shows that the present disclosure can successfully produce ICP using metallocene and Ziegler-Natta catalysts simultaneously in parallel reactors, ensuring design flexibility of the product components sufficient to achieve the optimal performance for a desired ICP product.
  • compositions described herein may be free of any component, or composition not expressly recited or disclosed herein. Any method may lack any step not recited or disclosed herein.
  • compositions, element or group of elements are preceded with the transitional phrase “comprising,” it is understood that we also contemplate the same composition or group of elements with transitional phrases “consisting essentially of,” “consisting of,” “selected from the group of consisting of,” or “is” preceding the recitation of the composition, element, or elements and vice versa.
  • compositions and methods are described in terms of “comprising,” “containing,” or “including” various components or steps, the compositions and methods can also “consist essentially of’ or “consist of’ the various components and steps. All numbers and ranges disclosed above may vary by some amount. Whenever a numerical range with a lower limit and an upper limit is disclosed, any number and any included range falling within the range is specifically disclosed. In particular, every range of values (of the form, “from about a to about b,” or, equivalently, “from approximately a to b,” or, equivalently, “from approximately a-b”) disclosed herein is to be understood to set forth every number and range encompassed within the broader range of values.

Abstract

La présente divulgation concerne des procédés pour la production de mélanges polymères à l'aide de multiples réacteurs agencés en parallèle. Les procédés consistent à : introduire une première charge comprenant du propylène dans un premier réacteur fonctionnant en parallèle avec un second réacteur ; convertir par voie catalytique la première charge présente dans le premier réacteur, dans des conditions de formation de polymères, à l'aide d'un premier catalyseur pour former un premier mélange de produits ; séparer le premier mélange de produits en une première fraction comprenant du polypropylène et en une seconde fraction comprenant du propylène n'ayant pas réagi ; introduire une seconde charge comprenant un ou plusieurs monomères élastomères dans le second réacteur ; convertir par voie catalytique la seconde charge présente dans le second réacteur, dans des conditions de formation de polymères, à l'aide d'un second catalyseur différent du premier catalyseur pour former un second mélange de produits comprenant un polymère élastomère ; et mélanger la première fraction avec le second mélange de produits en aval du premier réacteur et du second réacteur pour former un mélange polymère.
PCT/US2020/062774 2019-12-19 2020-12-02 Production d'un copolymère de polypropylène résistant aux chocs à l'aide de catalyseurs métallocène et ziegler-natta dans des réacteurs parallèles WO2021126523A1 (fr)

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