Vapor phase process for producing polypropylene random copolymers

Abstract

A gas phase process for producing polypropylene random copolymers in a fluidized bed reactor is provided. The process includes feeding a fluidizing medium into a reactor vessel containing a bed of catalytically active polyolefin particles. In one embodiment, the fluidizing medium includes propylene gas, C2 and / or C4-C8 α-olefin comonomers, hydrogen, and an inert gas. The momentum flux of the fluidizing medium, defined as, is greater than or equal to 7.0 N / m. 2 and the condensation level of the reactor circulating gas upon entering the reactor is less than 25 wt.%. g is the density of the bed material and SGV is the gas superficial velocity of the bed material. TIFF2024536416000010.tif930

Description

[Background technology]

[0001] Polypropylene, a type of polyolefin polymer, generally has a linear structure based on propylene monomer. One type of polypropylene is polypropylene random copolymer, which is produced using propylene monomer and at least one other α-olefin comonomer, such as ethylene and / or 1-butene, randomly scattered within the polypropylene chain. Polypropylene random copolymer exhibits properties that are particularly useful for pipes, packaging, textiles, molding, and other applications.

[0002] One method for producing polypropylene is typically called gas-phase polymerization. During gas-phase polymerization, one or more monomers come into contact with a catalyst to form a bed of polymer particles that are kept in a fluid state by a fluid medium, and the bed contains the monomers. A typical gas-phase heavy reactor includes a vessel containing the fluid bed, a distribution plate (also called a distribution plate), and a product discharge system. The catalyst can be supplied into the polymerization reactor and brought into contact with the olefin monomers that form part of the fluid medium.

[0003] When producing polypropylene using a gas-phase process, it is crucial to maintain the reactor operating temperature through efficient heat transfer from the polymer particles to the fluidizing gas. Failure to properly remove heat can lead to softening and / or melting of the polymer particles, which can further cause particle aggregation, sheeting on the reactor walls, and in the worst case, chunking and blockage of the distribution plate and product discharge system, requiring a reactor shutdown for cleaning, which typically takes the reactor offline for several days.

[0004] Compared to other polypropylene types, random copolymers are relatively more difficult to manufacture. For example, the presence of comonomers can increase the heat of reaction and lower the melting temperature of the polymer, which means that more heat needs to be removed compared to homopolymer production, and the polymer particles tend to be relatively "sticky". Thus, efficient heat transfer from polymer particles to gas is particularly important when manufacturing polypropylene random copolymers. Even with the correct operational guidelines for selecting appropriate reactor temperature, condensation level, and propylene partial pressure, random copolymer operations can still have problems such as polymer aggregation, unstable reactor temperature, abnormal fluidity bulk density (FBD) / bed level, and hot spots in the reactor.

[0005] Previous attempts to improve heat transfer in gas-phase polypropylene processes have included the use of mechanical agitators and operation at relatively high superficial gas velocities. However, while adding mechanical agitators helps to stir and mix the polymer particle bed in the reactor, it has additional negative consequences such as extra surface area for potential fouling, reliability of moving parts in the reactor, shaft sealing under high operating pressure, and concerns about power outages. Furthermore, there are practical limitations to the superficial gas velocity as a result of the capacity of the cycle gas compressor. Therefore, further improvements are needed. [Overview of the project]

[0006] This disclosure relates, in general terms, to a gas-phase process for producing polypropylene random copolymers in a fluidized bed reactor. This process involves supplying a fluidized medium into a reaction vessel containing a bed of catalytically active polyolefin particles.

[0007] In one embodiment, the fluid medium comprises propylene gas, C2 and / or C4-C8 α-olefin comonomers, hydrogen, and at least one inert gas.

[0008]

number

[0009] Other features and aspects of this disclosure are discussed in more detail below. [Brief explanation of the drawing]

[0010] [Figure 1] This is a schematic diagram of one embodiment of the vapor polymerization process according to the present disclosure. [Modes for carrying out the invention]

[0011] Before describing some exemplary embodiments, it should be understood that the present invention is not limited to the structural or process details described below. Other embodiments of the present invention are possible and can be implemented or carried out in various ways.

[0012] In general, this disclosure relates to a gas-phase process for producing polypropylene random copolymers in a fluidized bed reactor. The inventors unexpectedly found that reactor stability is at least partially a function of the momentum flux of the fluidized medium in the fluidized bed reactor. The momentum flux used herein is

[0013]

number

[0014] While not bound by theory, increasing the gas-free velocity of the fluid medium and increasing its density is thought to increase the particle-to-gas heat transfer coefficient, making the removal of polymerization heat from polymer particles to the fluid medium more efficient. More efficient heat transfer helps prevent hot spots that can cause polymer softening or melting. Ultimately, this more efficient heat transfer enables highly stable reactor operation without particle aggregation, seating, and chunking.

[0015] When such problems occur, there are methods to manipulate the reactor conditions to prevent chunking and complete shutdown of the reactor, but it is preferable to be able to maintain stable operation without aggressive or delicate manipulation. Surprisingly, the inventors have found that reactors operating with low momentum flux tend to chunk, reactors with medium momentum flux can be operated continuously with some special manipulation, and reactors operating with high momentum flux tend to operate stably and reliably without requiring delicate manipulation, while also providing good particle morphology for granular polymer products. Thus, momentum flux is a strong indicator of reactor stability.

[0016] The inventors also found that, because there are practical limits to the SGV of the fluid medium due to the compressor capacity in the recirculating flow, the momentum flux can be increased by increasing the density of the fluid medium through an increase in the total reactor pressure. Increasing the partial pressure of propylene gas can help increase the total pressure and gas density, but it can also cause several operational problems that are intended to be prevented, such as overheating of the polymerization reaction leading to hot spots and polymer particle aggregation. In fact, the partial pressure of propylene and comonomers needs to be maintained within an appropriate range to provide good catalytic productivity without causing overheating. Therefore, it has been found that intentionally increasing the partial pressure of the inert gas instead of the partial pressure of propylene or comonomers is an effective and safe way to increase the total reactor pressure and gas density and thus increase the momentum flux without causing "over" polymerization. For example, one inert gas that is usually present as an impurity in the propylene gas feed is propane. Therefore, it is desirable to operate the reactor for random copolymerization at a relatively high propane partial pressure. This can be achieved by maintaining a relatively high level of propane accumulated in the reactor through the operation of the vent recovery system and / or by adding additional propane to the feed to the reactor.

[0017] The propylene feed contains very little propane, and supplying additional propane can incur extra costs, such as the cost of purchasing propane plus the cost of a propane purification system, thus limiting the amount of available propane that can be stored in the system. In addition, very high propane levels in the reactor can have several negative consequences. For example, high levels of propane can condense excessively high levels of circulating gas upon entering the reactor, which increases the pressure in the product discharge system (PDS) and lowers the temperature of the resin in the PDS and product degassing column. This can result in difficulty in achieving good resin degassing, a higher load on the vent recovery system which can lead to lower operational efficiency (i.e., an increased ratio of consumed monomers to comonomers to the final polymer product), and possible resin particle stickiness. Excessive levels of condensation can also raise concerns about insufficient mixing near the bottom of the reactor, as the effective gas rate before condensation evaporates is relatively low. In this regard, typically, the level of condensation is about 25% or less, about 20% or less in some embodiments, and about 17% or less in some embodiments. Therefore, additionally or alternatively, the inert gas used to increase the momentum flux may include non-condensable gases such as nitrogen. Nitrogen is typically present as an inert gas in fluidized media. For example, nitrogen is derived from the gas flow used to purge nozzles and pressure taps in gas-phase polymerization reactors. During reactor startup, nitrogen is also frequently used as a fluidized media before monomers and comonomers are introduced into the reactor. Thus, another convenient and advantageous way to increase the momentum flux of a fluidized media is to increase the partial pressure of nitrogen in the reactor. Preferably, the fluidized media has relatively high concentrations of both propane and nitrogen, as long as the concentration of condensable inert gases is kept low enough to prevent excessive condensing of the circulating gas. However, although these inert gases may be the most readily available, any inert gas can be used to increase the total pressure and therefore increase the density of the fluidized media, as long as it does not polymerize the monomers / comonomers or inhibit the reaction.

[0018] 7.0 N / m 2 Operating the reactor with the above momentum flux has been found to provide the desirable result of a stable and robust copolymerization. Preferably, the momentum flux is 8.3 N / m 2 or more, for example 8.5 N / m 2 or more, for example 9 N / m 2 or more, for example 9.5 N / m 2 or more. Typically, the momentum flux is less than 20 N / m 2 for example less than 18 N / m 2 for example less than 15 N / m 2 and less.

[0019] The superficial gas velocity (SGV) is limited from below by the minimum fluidization velocity which is the minimum velocity at which the bed of polymer particles becomes fluidized. Preferably, the SGV is 0.3 and above, for example 0.36 m / s or more, for example 0.38 m / s or more, for example 0.39 m / s or more, for example 0.4 m / s or more. The SGV is typically less than 0.6 m / s, but is limited by compressor capacity or speed such that reactor operation becomes undesirable, such as with excessive carry-over of fines from the reactor.

[0020] The gas density ρg of the fluidizing medium is preferably about 55 kg / m 3 or more, for example about 57 kg / m 3 or more, for example about 58 kg / m 3 or more, for example about 59 kg / m 3 or more, for example about 60 kg / m 3 or more. The gas density of the fluidizing medium is typically less than about 80 kg / m 3 for example less than about 70 kg / m 3 and less.

[0021] As described above, the inert gas preferably contains propane. In one embodiment, propane constitutes about 4 mol% or more of the fluid medium, for example, about 6 mol% or more of the fluid medium, for example, about 8 mol% or more of the fluid medium, for example, about 10 mol% or more of the fluid medium, for example, about 12 mol% or more of the fluid medium. Typically, propane constitutes less than about 40 mol% of the fluid medium, for example, about 30 mol% or less of the fluid medium, for example, about 25% by weight or less of the fluid medium, for example, about 20% by weight or less of the fluid medium.

[0022] In another embodiment, the inert gas includes nitrogen. Preferably, nitrogen constitutes about 4 mol% or more of the fluid medium, for example, about 6 mol% or more of the fluid medium, for example, about 7 mol% or more of the fluid medium, for example, about 9 mol% or more of the fluid medium, for example, about 11 mol% or more of the fluid medium, for example, about 13 mol% or more of the fluid medium, for example, about 15 mol% or more of the fluid medium, for example, about 19 mol% or more of the fluid medium, for example, about 25 mol% or more of the fluid medium. Typically, nitrogen constitutes less than about 60 mol% of the fluid medium.

[0023] In one embodiment, the fluid medium contains both propane and nitrogen. Preferably, the total molar percentages of propane and nitrogen in the fluid medium are about 10% or more, for example, about 16% or more, for example, about 25% or more, for example, about 32% or more. Typically, the total molar percentages of propane and nitrogen are less than about 70%.

[0024] Generally, polymerization described herein is carried out in a fluidized bed gas-phase reactor. Polymerization is carried out with propylene and C2 and C2. 4~8 This is carried out by reacting at least one olefin comonomer selected from with a catalyst system, preferably in the presence of hydrogen, to produce a propylene-based polymer. The catalyst system may be a metallocene catalyst system, a Ziegler-Natta catalyst system, or a mixture of a Ziegler-Natta catalyst and a metallocene catalyst. Preferably, the catalyst system is a Ziegler-Natta catalyst system.

[0025] The propylene polymer may be a propylene copolymer (having a single comonomer) or a terpolymer (having two comonomers), or having more comonomers. As used herein, the term propylene copolymer is used broadly to refer to embodiments having a single comonomer or multiple comonomers, and therefore includes terpolymers. When the polymer is a terpolymer, preferably one of the comonomers is ethylene. When only one type of comonomer is used, the random copolymer is preferably a propylene random copolymer with ethylene or 1-butene. The polymerization temperature is preferably about 50 to about 90°C, for example about 55 to about 75°C, or alternatively about 58 to about 68°C. If hydrogen is present, the ratio of hydrogen to propylene used in polymerization is preferably about 0.003 to about 0.25, for example about 0.005 to about 0.18.

[0026] The melt flow rate (MFR) of the manufactured propylene polymer, measured according to ASTM D1238, is typically about 0.15 to about 400 g / 10 min, and the measurement of the MFR includes the addition of antioxidants to provide a stable and repeatable measurement. The antioxidants used typically include 2000 ppm Cyanox-2246, 2000 ppm Irgafos-168, or 1000 ppm ZnO, or equivalents thereof. Preferably, the melt flow rate is about 0.15 to about 250 g / 10 min. More preferably, the melt flow rate is about 0.2 to about 200 g / 10 min. This melt flow rate is measured for the material manufactured in the reactor without subsequent bis-breaking.

[0027] Referring to Figure 1, for illustrative purposes only, one embodiment of a gas-phase polymerization process in a fluidized bed reactor is shown. As shown in Figure 1, the system includes a gas-phase reactor 10, which includes a reaction zone 12 and a deceleration zone 14. In particular, the cross-sectional area of ​​the reaction zone should be used for the purpose of calculating the SGV. In one exemplary embodiment, the ratio of the height to the diameter of the reaction zone may vary in the range of about 2:1 to about 7:1.

[0028] The reaction zone 12 comprises a bed of growing and grown polymer particles, polymerizable monomers, and other gaseous components (including inert gases and optionally hydrogen) in the form of a fluid medium flowing through the reaction zone. As described above, the SGV of the fluid medium (typically in a gaseous state for most of the reactor) is sufficient to form a fluid bed. For example, the gas emptying velocity may be greater than 1.5 times the minimum fluidization velocity, for example, greater than 2.5 times, for example, greater than 4 times.

[0029] Replenishment fluid (such as fresh polyolefin monomers(s) to replenish those consumed during polymerization) is generally supplied to the process at point 18 and combined in the recirculation line 22, or supplied to the process at other points in the cycle loop, such as upstream of the compressor 30. The composition of the recycled flow is typically measured by a gas analyzer 21. The SGV in reactor 10 can be adjusted by adjusting the flow rate of the fluid passing through the compressor 30. The gas analyzer 21 can be positioned to test the recycled gas at a point between the compressor 30 and the heat exchanger 24, as shown in Figure 1.

[0030] The fluidized medium contained in the recycled flow 22 is supplied to the reactor 10 at a point 26 below the floor, towards the bottom. The reactor 10 may include a gas distribution plate 28 to assist in uniformly fluidizing the floor and to support the solid particles contained in the fluidized bed. The fluidized medium passing upward through the floor and exiting from the floor removes the reaction heat generated by the exothermic polymerization reaction.

[0031] As shown in Figure 1, the fluid medium flows through the reactor 10 to the deceleration zone 14. Within the deceleration zone 14, most particles fall back into the high-density fluidized bed in the reaction zone 12 due to gravity, while a small amount of fine particles are carried out of the reactor by the fluid medium into the cycle loop.

[0032] The recycled fluid medium is compressed in a compressor 30 and passes through a heat exchanger 24. The heat exchanger 24 is for removing the polymerization reaction heat absorbed by the fluid medium as it passes through the reactor before the fluid medium is returned to the reactor 10. In one embodiment, the reactor 10 may include a fluid flow deflector 32 installed at the inlet to the reactor, which helps to better distribute the fluid medium into the space below the distribution plate 28, preventing the contained polymer particles from settling and agglomerating into solid clumps, and retaining and entraining or re-entraining any particles that might settle or separate and optionally the concentrated liquid. The distribution plate 28 allows the fluid medium to enter the fluid bed in the reaction zone 12 with a uniform rate and uniform amount of supported fine particles and optionally a uniform amount of condensed liquid across the entire cross-sectional area of ​​the reactor.

[0033] The granular polyolefin polymer resin produced by the reaction is discharged from the reactor 10 through line 44.

[0034] In one embodiment, the polymerization catalyst enters the reactor 10 through a nozzle 42 and a line 48.

[0035] The catalyst flow 48 comprises catalyst particles, optionally a suspension such as mineral oil or liquid alkane, and a carrier fluid. The catalyst particles (for example, in the form of a slurry by suspending them in mineral oil) and the carrier fluid can be injected into the reactor 10 through a nozzle 42. Preferably, on a volume basis, the catalyst flow 48 mainly contains the carrier fluid. For example, the carrier fluid preferably accounts for more than 50%, for example more than 60%, for example more than 70%, of the volume of the catalyst flow 48.

[0036] The carrier fluid in the catalyst flow 48 may include monomers, comonomers, inert hydrocarbons, inert gases, or mixtures thereof. In one embodiment, for example, the carrier fluid is a liquid monomer such as liquid propylene. When liquid propylene is used as the carrier fluid, the flow rate of the catalyst flow 48 is generally greater than about 15 kg / hour, for example greater than about 25 kg / hour, for example greater than about 55 kg / hour. When liquid propylene is used as the carrier fluid, the flow rate of the catalyst flow 48 is generally less than about 250 kg / hour, for example less than about 200 kg / hour.

[0037] Alternatively, the carrier fluid may be an inert gas such as nitrogen gas. When nitrogen gas is the carrier fluid, the flow rate of the catalyst flow 48 may generally be greater than about 3 kg / hour, for example greater than about 5 kg / hour, for example greater than about 9 kg / hour, and generally less than about 55 kg / hour, for example less than about 45 kg / hour, for example less than about 30 kg / hour.

[0038] In addition to the catalyst flow 48, as shown in Figure 1, the system may further include a support gas flow 47 separate from the catalyst flow 48 until it is released into the reactor 10. In one embodiment, for example, the support gas flow 47 is supplied to the gas-phase reactor 10 through a nozzle 42 such that the support gas is released at the end of the tube very close to the end of the catalyst injection tube. Typically, the support gas flows through a support tube that is coaxial with the catalyst injection tube.

[0039] If present, the support gas flow generally includes monomers, comonomers, inert hydrocarbons, inert gases, or mixtures thereof. In one embodiment, for example, the support gas may include monomer gases such as olefin gases. In one particular embodiment, for example, the support gas may be vaporized propylene. Preferably, the flow rate of the support gas is greater than about 40 kg / hour, for example, greater than about 50 kg / hour, for example, greater than about 60 kg / hour. Preferably, the flow rate of the support gas is less than about 600 kg / hour, for example, less than about 550 kg / hour, for example, less than about 500 kg / hour.

[0040] In one embodiment, the catalyst system is a Ziegler-Natta catalyst composition. A Ziegler-Natta catalyst composition typically includes a procatalyst containing a transition metal halide (i.e., titanium, chromium, vanadium), a cocatalyst such as an organoaluminum compound, and optionally an external electron donor.

[0041] All different types of Ziegler-Natta catalysts may be used in the methods of the present disclosure. The Ziegler-Natta catalyst comprises a solid catalyst component. The solid catalyst component may include (i) magnesium, (ii) transition metal compounds of elements from groups IV to VIII of the periodic table, (iii) halides, oxyhalides, and / or alkoxides of (i) and / or (ii), and (iv) combinations of (i), (ii), and (iii). Non-limiting examples of suitable catalyst components include halides, oxyhalides, and alkoxides of magnesium, manganese, titanium, vanadium, chromium, molybdenum, zirconium, hafnium, and combinations thereof.

[0042] In one embodiment, the preparation of the catalyst component involves halogenation of a mixed magnesium and titanium alkoxide.

[0043] In various embodiments, the catalyst component is a magnesium partial compound (MagMo), a mixed magnesium-titanium compound (MagTi), or a benzoic acid-containing magnesium chloride compound (BenMag). In one embodiment, the catalyst precursor is a magnesium partial ("MagMo") precursor. The MagMo precursor contains a magnesium partial. Non-limiting examples of preferred magnesium partials include anhydrous magnesium chloride and / or its alcohol adducts, magnesium alkoxides or aryl oxides, mixed magnesium alkoxy halides, and / or carboxylated magnesium dialkoxides or aryl oxides. In one embodiment, the MagMo precursor is a magnesium di(C) 1~4 ) is an alkoxide. In further embodiments, the MagMo precursor is diethoxymagnesium.

[0044] In another embodiment, the catalyst component is a mixed magnesium / titanium compound ("MagTi"). The "MagTi precursor" is a compound of the formula Mg d Ti(OR e ) has fXg, in the formula, R e R' is an aliphatic or aromatic hydrocarbon group having 1 to 14 carbon atoms or COR', and R' is an aliphatic or aromatic hydrocarbon group having 1 to 14 carbon atoms, and each OR e The groups are the same or different, X is independently chlorine, bromine, or iodine, preferably chlorine, d is 0.5 to 56, or 2 to 4, f is 2 to 116, or 5 to 15, and g is 0.5 to 116, or 1 to 3. The precursor is prepared by controlled precipitation, removing the alcohol from the reaction mixture used for its preparation. In one embodiment, the reaction medium comprises a mixture of aromatic liquids, particularly chlorinated aromatic compounds, most particularly chlorobenzene, and alkanols, particularly ethanol. Suitable halogenating agents include titanium tetrabromide, titanium tetrachloride, or titanium trichloride, particularly titanium tetrachloride. Removing the alkanol from the solution used for halogenation precipitates a solid precursor, which has a particularly desirable shape and surface area. Furthermore, the resulting precursor generally has a particularly uniform particle size.

[0045] In another embodiment, the catalyst precursor is a benzoic acid-containing magnesium chloride material ("BenMag"). As used herein, "benzoic acid-containing magnesium chloride" ("BenMag") may be a catalyst (i.e., a halogenation catalyst component) containing an internal benzoic acid electron donor. The BenMag material may also contain a titanium moiety, such as titanium halide. The internal benzoic acid donor is unstable and may be replaced by other electron donors during catalyst and / or catalyst synthesis. Non-limiting examples of suitable benzoic acid groups include ethyl benzoate, methyl benzoate, p-methoxyethyl benzoate, p-ethoxymethyl benzoate, p-ethoxyethyl benzoate, and p-chloroethyl benzoate. In one embodiment, the benzoic acid group is ethyl benzoate. In one embodiment, the BenMag catalyst component may be the product of halogenation of any catalyst component (i.e., a MagMo precursor or a MagTi precursor) in the presence of a benzoic acid compound.

[0046] In another embodiment, the solid catalyst component can be formed from a magnesium moiety, a titanium moiety, an epoxy compound, an organosilicon compound, and an internal electron donor. In one embodiment, an organophosphorus compound can also be incorporated into the solid catalyst component. For example, in one embodiment, a halide-containing magnesium compound can be dissolved in a mixture containing an epoxy compound, an organophosphorus compound, and a hydrocarbon solvent. The resulting solution can be treated with a titanium compound in the presence of an organosilicon compound, and optionally with an internal electron donor, to form a solid precipitate. The solid precipitate can then be treated with a further amount of titanium compound. The titanium compound used to form the catalyst has the following chemical formula: Ti(OR) g X 4-g [In the formula, each R is independently a C1-C4 alkyl group, X is Br, Cl, or I, and g is 0, 1, 2, 3, or 4].

[0047] In some embodiments, organosilicon is a monomer compound or a polymer compound. Organosilicon compounds may contain a -Si-O-Si- group in one molecule or between molecules. Other exemplary examples of organosilicon compounds include polydialkylsiloxanes and / or tetraalkoxysilanes. Such compounds may be used individually or in combination. Organosilicon compounds can be used in combination with aluminum alkoxides and internal electron donors.

[0048] The aluminum alkoxides mentioned above may have the formula Al(OR')3 [wherein each R' is a hydrocarbon having up to 20 carbon atoms]. This may include cases where each R' is methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, neopentyl, etc.

[0049] Examples of halide-containing magnesium compounds include magnesium chloride, magnesium bromide, magnesium iodide, and magnesium fluoride. In one embodiment, the halide-containing magnesium compound is magnesium chloride.

[0050] An example of an epoxy compound is formula:

[0051] [ka] (wherein "a" is from 1, 2, 3, 4, or 5, X is F, Cl, Br, I, or methyl, R a Examples include, but are not limited to, glycidyl-containing compounds of which are H, alkyl, aryl, or cyclyl. In one embodiment, the alkyl epoxide is epichlorohydrin. In some embodiments, the epoxy compound is a haloalkyl epoxide or a non-haloalkyl epoxide.

[0052] According to some embodiments, epoxy compounds include ethylene oxide, propylene oxide, 1,2-epoxybutane, 2,3-epoxybutane, 1,2-epoxyhexane, 1,2-epoxyoctane, 1,2-epoxydecane, 1,2-epoxydodecane, 1,2-epoxytetradecane, 1,2-epoxyhexadecane, 1,2-epoxyoctadecane, 7,8-epoxy-2-methyloctadecane, 2-vinyloxirane, 2-methyl-2-vinyloxirane, 1,2 -Epoxy-5-hexene, 1,2-epoxy-7-octene, 1-phenyl-2,3-epoxypropane, 1-(1-naphthyl)-2,3-epoxypropane, 1-cyclohexyl-3,4-epoxybutane, 1,3-butadiene dioxide, 1,2,7,8-diepoxyoctane, cyclopentene oxide, cyclooctene oxide, α-pinene oxide, 2,3-epoxynorbornane, limonene oxide, cyclodecane epoxide, 2,3,5,6-diepoxynorbornane Lunan, styrene oxide, 3-methylstyrene oxide, 1,2-epoxybutylbenzene, 1,2-epoxyoctylbenzene, stilbene oxide, 3-vinylstyrene oxide, 1-(1-methyl-1,2-epoxyethyl)-3-(1-methylvinylbenzene), 1,4-bis(1,2-epoxypropyl)benzene, 1,3-bis(1,2-epoxy-1-methylethyl)benzene, 1,4-bis(1,1-epoxy-1-methylethyl)benzene, epifluoro Hydrin, epichlorohydrin, epibromohydrin, hexafluoropropylene oxide, 1,2-epoxy-4-fluorobutane, 1-(2,3-epoxypropyl)-4-fluorobenzene, 1-(3,4-epoxybutyl)-2-fluorobenzene, 1-(2,3-epoxypropyl)-4-chlorobenzene, 1-(3,4-epoxybutyl)-3-chlorobenzene, 4-fluoro-1,2-cyclohexene oxide, 6-chloro-2,3-epoxybicyclo[2.2.1]Heptane, 4-Fluorostyrene Oxide, 1-(1,2-Epoxypropyl)-3-Trifluorobenzene, 3-Acetyl-1,2-Epoxypropane, 4-Benzoyl-1,2-Epoxybutane, 4-(4-Benzoyl)phenyl-1,2-Epoxybutane, 4,4'-Bis(3,4-Epoxybutyl)benzophenone, 3,4-Epoxy-1-Cyclohexanone, 2,3-Epoxy-5-Oxobicyclo[2.2.1]Heptane, 3-Acetylstyrene Oxide, 4-(1,2-Epoxypropyl)Benzphenone, Glycidylmethyl Glycidyl ether, butyl glycidyl ether, 2-ethylhexyl glycidyl ether, allyl glycidyl ether, ethyl 3,4-epoxybutyl ether, glycidyl phenyl ether, glycidyl 4-tert-butylphenyl ether, glycidyl 4-chlorophenyl ether, glycidyl 4-methoxyphenyl ether, glycidyl 2-phenylphenyl ether, glycidyl 1-naphthyl ether, glycidyl 2-phenylphenyl ether, glycidyl 1-naphthyl ether, glycidyl 4-indolyl ether, glycidyl N-methyl-α- Quinolone-4-yl ether, ethylene glycol diglycidyl ether, 1,4-butanediol diglycidyl ether, 1,2-diglycidyloxybenzene, 2,2-bis(4-glycidyloxyphenyl)propane, tris(4-glycidyloxyphenyl)methane, poly(oxypropylene)triol triglycidyl ether, glycidyl ether of phenol novolac, 1,2-epoxy-4-methoxycyclohexane, 2,3-epoxy-5,6-dimethoxybicyclo[2.2.1]heptane, 4-methoxystyrene oxide, 1-(1,2-epoxybutyl)-2-phenoxybenzene, glycidyl formate, glycidyl acetate, 2,3-epoxybutyl acetate, glycidyl butyrate, glycidyl benzoate, diglycidyl terephthalate, poly(glycidyl acrylate), poly(glycidyl methacrylate), copolymer of glycidyl acrylate with another monomer, copolymer of glycidyl methacrylate with another monomer, 1,2-epoxy-4-methoxycarbonylcyclohexane, 2,3-epoxy-5-butoxycarbonylbicyclo[2.2.1] Heptane, ethyl 4-(1,2-epoxyethyl)benzoate, methyl 3-(1,2-epoxybutyl)benzoate, methyl 3-(1,2-epoxybutyl)-5-phenylbenzoate, N,N-glycidyl-methylacetamide, N,N-ethylglycidylpropionamide, N,N-glycidylmethylbenzamide, N-(4,5-epoxypentyl)-N-methylbenzamide, N,N-diglycylaniline, bis(4-diglycidylaminophenyl)methane, poly(N,N-glycidylmethylacrylamide) The following are selected from the group consisting of 1,2-epoxy-3-(diphenylcarbamoyl)cyclohexane, 2,3-epoxy-6-(dimethylcarbamoyl)bicyclo[2.2.1]heptane, 2-(dimethylcarbamoyl)styrene oxide, 4-(1,2-epoxybutyl)-4'-(dimethylcarbamoyl)biphenyl, 4-cyano-1,2-epoxybutane, 1-(3-cyanophenyl)-2,3-epoxybutane, 2-cyanostyrene oxide, and 6-cyano-1-(1,2-epoxy-2-phenylethyl)naphthalene.

[0053] Examples of organophosphorus compounds include phosphate esters such as trialkyl phosphate esters. Such compounds have the formula:

[0054] [ka] [In the formula, R1, R2, and R3 are each independently methyl, ethyl, and linear or branched (C3~C) 10 It can be represented by [selected from the group consisting of alkyl groups]. In one embodiment, the trialkyl phosphate ester is tributyl phosphate ester.

[0055] In yet another embodiment, substantially spherical MgCl2-nEtOH adducts may be formed by a spray crystallization process. In this process, a MgCl2-nROH molten material with n = 1 to 6 is sprayed inside a container while an inert gas is introduced to the top of the container at a temperature of 20 to 80°C. The molten droplets are moved to a crystallization region where the inert gas is introduced at a temperature of -50 to 20°C, crystallizing the molten droplets into spherical, non-aggregated solid particles. The spherical MgCl2 particles are then sorted into desired sizes. Undesirable size particles can be recycled. In a preferred embodiment for catalyst synthesis, the spherical MgCl2 precursor has an average particle size between about 8 to 150 micrometers, preferably 10 to 100 micrometers, and most preferably 10 to 30 micrometers (Malvern d 50 ) has.

[0056] The catalyst component can be converted into a solid catalyst by halogenation. Halogenation involves contacting the catalyst component with a halogenating agent in the presence of an internal electron donor. Halogenation converts the magnesium portion present in the catalyst component into a magnesium halide support on which the titanium portion (such as a titanium halide) is deposited. While we do not wish to be bound by any particular theory, it is thought that during halogenation, the internal electron donor (1) adjusts the position of titanium on the magnesium-based support, (2) promotes the conversion of the magnesium and titanium portions to their respective halides, and (3) adjusts the crystal size of the magnesium halide support during the conversion. Therefore, providing an internal electron donor results in a catalyst composition with improved stereoselectivity.

[0057] In one embodiment, the halogenating agent is of formula Ti(OR e ) f X h (In the formula, R eX is defined as above, f is an integer from 0 to 3, h is an integer from 1 to 4, and f + h is 4. In one embodiment, the halogenating agent is titanium halide (TiCl4). In a further embodiment, halogenation is carried out in the presence of a chlorinated or non-chlorinated aromatic liquid, such as dichlorobenzene, o-chlorotoluene, chlorobenzene, benzene, toluene, or xylene. In yet another embodiment, halogenation is carried out by using a mixture of halogenating agent and a chlorinated aromatic liquid, the mixture containing 40 to 60 volume percent of the halogenating agent, such as TiCl4.

[0058] The reaction mixture may be heated during halogenation. The catalyst and halogenating agents are initially brought into contact at a temperature below about 10°C, e.g., below 0°C, e.g., below -10°C, e.g., below -20°C, e.g., below -30°C. The initial temperature is generally above about -50°C, e.g., above -40°C. The mixture is then heated at a rate of 0.1 to 10.0°C / min, or at a rate of 1.0 to 5.0°C / min. The internal electron donor may be added later, after the initial contact period between the halogenating agent and the catalyst. The halogenation temperature is 20°C to 150°C (or any value or partial range between them), or 0°C to 120°C. Halogenation may be continued for a period of 5 to 60 minutes, or 10 to 50 minutes, with the internal electron donor substantially absent.

[0059] The manner in which the catalyst component, halogenating agent, and internal electron donor come into contact can vary. In one embodiment, the catalyst component is first contacted with a mixture containing a halogenating agent and a chlorinated aromatic compound. The resulting mixture may be stirred and heated as needed. Next, the internal electron donor is added to the same reaction mixture without isolating or recovering the precursor. The above process can be carried out in a single reactor with the addition of various components controlled by automated process control.

[0060] In one embodiment, the catalyst component is brought into contact with an internal electron donor before reacting with the halogenating agent.

[0061] The contact time between the catalyst component and the internal electron donor is at least 10 minutes, at least 15 minutes, at least 20 minutes, or at least 1 hour at a temperature of at least -30°C, or at least -20°C, or at least 10°C to a maximum of 150°C, a maximum of 120°C, a maximum of 115°C, or a maximum of 110°C.

[0062] In one embodiment, the catalyst component, the internal electron donor, and the halogenating agent are added simultaneously or substantially simultaneously.

[0063] The halogenation procedure may be repeated one, two, three, or more times as needed. In one embodiment, the resulting solid material is recovered from the reaction mixture and is contacted once or more times for at least about 10 minutes, or at least about 15 minutes, or at least about 20 minutes, and up to about 10 hours, or up to about 45 minutes, or up to about 30 minutes, at a temperature of at least about -20°C, or at least about 0°C, or at least about 10°C to a maximum of about 150°C, or up to about 120°C, or up to about 115°C, in the absence (or presence) of the same (or different) internal electron donor components as the mixture of halogenating agents in the chlorinated aromatic compound.

[0064] Following the halogenation procedure described above, the resulting solid catalyst composition is separated from the reaction medium used in the final process by filtration, for example, to produce a wet filter cake. The wet filter cake can then be rinsed or washed with a liquid diluent to remove unreacted TiCl4, and may be dried to remove any remaining liquid if necessary. Typically, the resulting solid catalyst composition is washed once or more times with a “washing liquid,” which is a liquid hydrocarbon such as isopentane, isooctane, isohexane, hexane, pentane, or octane. The solid catalyst composition is then separated and dried, or may be slurried in hydrocarbons, particularly relatively heavy hydrocarbons such as mineral oil for further storage or use.

[0065] In one embodiment, the resulting solid catalyst composition has a titanium content of about 1.0 wt% to about 6.0 wt% or about 1.5 wt% to about 4.5 wt% or about 2.0 wt% to about 3.5 wt% based on the total solid weight. The weight ratio of titanium to magnesium in the solid catalyst composition is preferably about 1:3 to about 1:160, or about 1:4 to about 1:50, or about 1:6 to 1:30. In one embodiment, internal electron donors may be present in the catalyst composition in a molar ratio of internal electron donors to magnesium of about 0.005:1 to about 1:1, or about 0.01:1 to about 0.4:1. The weight percentages are based on the total weight of the catalyst composition.

[0066] The catalyst composition may be further treated by one or more of the following procedures before or after the isolation of the solid catalyst composition. If desired, the solid catalyst composition may be contacted (halogenated) with an additional amount of titanium halide compound. This may be replaced with an acid chloride such as phthaloyl dichloride or benzoyl chloride under metathesis conditions, or it may be rinsed, washed, heat-treated, or aged. The aforementioned further procedures may be combined in any order, used separately, or not used at all.

[0067] As described above, the catalyst composition may include a combination of a magnesium moiety, a titanium moiety, and an internal electron donor. The catalyst composition is produced by the halogenation procedure described above, which converts the catalyst component and the internal electron donor into a combination of a magnesium moiety and a titanium moiety incorporating the internal electron donor. The catalyst component from which the catalyst composition is formed may be any of the catalyst precursors described above, including a magnesium moiety precursor, a mixed magnesium / titanium precursor, a benzoic acid-containing magnesium chloride precursor, a magnesium, titanium, epoxy, and phosphorus precursor, or a spherical precursor.

[0068] Various different types of internal electron donors can be incorporated into the solid catalyst component. In one embodiment, the internal electron donor is an aryl diester such as a phenylene-substituted diester. In one embodiment, the internal electron donor may have the following chemical structure:

[0069] [ka] In the formula, R1, R2, R3, and R4 are each hydrocarbyl groups having 1 to 20 carbon atoms, and these hydrocarbyl groups have a branched or linear structure or include cycloalkyl groups having 7 to 15 carbon atoms; E1 and E2 may be the same or different, and are selected from the group consisting of alkyl groups having 1 to 20 carbon atoms, substituted alkyl groups having 1 to 20 carbon atoms, aryl groups having 1 to 20 carbon atoms, substituted aryl groups having 1 to 20 carbon atoms, or inert functional groups having 1 to 20 carbon atoms and optionally including heteroatoms; X1 and X2 are each O, S, alkyl groups, or NR5; and R5 is either a hydrocarbyl group having 1 to 20 carbon atoms or hydrogen.

[0070] As used herein, the terms "hydrocarbyl" and "hydrocarbon" refer to substituents containing only hydrogen and carbon atoms, including branched or unbranched saturated or unsaturated cyclic, polycyclic, condensed, or acyclic species, and combinations thereof. Non-limiting examples of hydrocarbyl groups include alkyl groups, cycloalkyl groups, alkenyl groups, alkadienyl groups, cycloalkenyl groups, cycloalkadienyl groups, aryl groups, aralkyl groups, alkylaryl groups, and alkynyl groups.

[0071] As used herein, the terms “substituted hydrocarbyl” and “substituted hydrocarbon” refer to a hydrocarbyl group substituted with one or more non-hydrocarbyl substituents. Non-limiting examples of non-hydrocarbyl substituents are heteroatoms. As used herein, “heteroatom” refers to an atom other than carbon or hydrogen. Heteroatoms can be non-carbon atoms from groups IV, V, VI, and VII of the periodic table. Non-limiting examples of heteroatoms include halogens (F, Cl, Br, I), N, O, P, B, S, and Si. Substituted hydrocarbyl groups also include halohydrocarbyl groups and silicon-containing hydrocarbyl groups. As used herein, the term “halohydrocarbyl” group refers to a hydrocarbyl group substituted with one or more halogen atoms. As used herein, the term “silicon-containing hydrocarbyl group” refers to a hydrocarbyl group substituted with one or more silicon atoms. Silicon atoms may or may not be present in the carbon chain.

[0072] In one embodiment, the substituted phenylenediester has the following structure (I).

[0073] [ka]

[0074] In one embodiment, structure (I) includes isopropyl groups R1 and R3, R2, R4, and R5-R 14 Each of them is hydrogen.

[0075] In one embodiment, structure (I) is R1, R5, and R 10 Each of these contains a methyl group, and R3 is a t-butyl group. R2, R4, R6~R9, and R 11 ~R 14 Each of them is hydrogen.

[0076] In one embodiment, structure (I) is R1, R7, and R 12 Each of these contains a methyl group, and R3 is a t-butyl group. R2, R4, R5, R6, R8, R9, R10 , R 11 , R 13 , and R 14 Each of them is hydrogen.

[0077] In one embodiment, structure (I) contains R1 as a methyl group and R3 is a t-butyl group. R7 and R 12 Each of these is an ethyl group. R2, R4, R5, R6, R8, R9, R 10 , R 11 , R 13 , and R 14 Each of them is hydrogen.

[0078] In one embodiment, structure (I) is R1, R5, R7, R9, R 10 , R 12 , and R 14 Each of these contains a methyl group, and R3 is a t-butyl group. R2, R4, R6, R8, R 11 , and R 13 Each of them is hydrogen.

[0079] In one embodiment, structure (I) contains R1 as a methyl group and R3 is a t-butyl group. R5, R7, R9, R 10 , R 12 , and R 14 Each of these is an i-propyl group. R2, R4, R6, R8, R 11 , and R 13 Each of them is hydrogen.

[0080] In one embodiment, the substituted phenylene aromatic diesters are R1-R1, as described in detail in U.S. Patent No. 8,536,372, which is incorporated herein by reference. 14 It has a structure selected from the group consisting of structures (II) to (V), which include each of the substitutes of the respective.

[0081] In one embodiment, structure (I) includes a methyl group R1, and R3 is a t-butyl group. R7 and R 12 Each of these is an ethoxy group. R2, R4, R5, R6, R8, R9, R 10 , R 11, R 13 , and R 14 Each of them is hydrogen.

[0082] In one embodiment, structure (I) includes a methyl group R1, and R3 is a t-butyl group. R7 and R 12 Each of these is a fluorine atom. R2, R4, R5, R6, R8, R9, R 10 , R 11 , R 13 , and R 14 Each of them is hydrogen.

[0083] In one embodiment, structure (I) includes a methyl group R1, and R3 is a t-butyl group. R7 and R 12 Each of these is a chlorine atom. R2, R4, R5, R6, R8, R9, R 10 , R 11 , R 13 , and R 14 Each of them is hydrogen.

[0084] In one embodiment, structure (I) includes a methyl group R1, and R3 is a t-butyl group. R7 and R 12 Each of these is a bromine atom. R2, R4, R5, R6, R8, R9, R 10 , R 11 , R 13 , and R 14 Each of them is hydrogen.

[0085] In one embodiment, structure (I) includes a methyl group R1, and R3 is a t-butyl group. R7 and R 12 Each of these is an iodine atom. R2, R4, R5, R6, R8, R9, R 10 , R 11 , R 13 , and R 14 Each of them is hydrogen.

[0086] In one embodiment, structure (I) includes a methyl group R1, and R3 is a t-butyl group. R6, R7, R 11 , and R 12Each of them is a chlorine atom. R2, R4, R5, R8, R9, R 10 、R 13 、and R 14 are each hydrogen.

[0087] In one embodiment, structure (I) contains R1 which is a methyl group, and R3 is a t-butyl group. R6, R8, R 11 、and R 13 are each chlorine atoms. R2, R4, R5, R7, R9, R 10 、R 12 、and R 14 are each hydrogen.

[0088] In one embodiment, structure (I) contains R1 which is a methyl group, and R3 is a t-butyl group. R2, R4, and each of R5 to R 14 is a fluorine atom.

[0089] In one embodiment, structure (I) contains R1 which is a methyl group, and R3 is a t-butyl group. Each of R7 and R 12 is a trifluoromethyl group. R2, R4, R5, R6, R8, R9, R 10 、R 11 、R 13 、and R 14 are each hydrogen.

[0090] In one embodiment, structure (I) contains R1 which is a methyl group, and R3 is a t-butyl group. Each of R7 and R 12 is an ethoxycarbonyl group. R2, R4, R5, R6, R8, R9, R 10 、R 11 、R 13 、and R 14 are each hydrogen.

[0091] In one embodiment, R1 is a methyl group and R3 is a t-butyl group. Each of R7 and R 12 is an ethoxy group. R2, R4, R5, R6, R8, R9, R 10 、R 11 、R 13 、and R​​14 Each of them is hydrogen.

[0092] In one embodiment, structure (I) includes a methyl group R1, and R3 is a t-butyl group. R7 and R 12 Each of these is a diethylamino group. R2, R4, R5, R6, R8, R9, R 10 , R 11 , R 13 , and R 14 Each of them is hydrogen.

[0093] In one embodiment, structure (I) includes a methyl group R1, and R3 is a 2,4,4-trimethylpentan-2-yl group. R2, R4, and R5~R 14 Each of them is hydrogen.

[0094] In one embodiment, structure (I) comprises R1 and R3, each of which is a sec-butyl group. R2, R4, and R5~R 14 Each of them is hydrogen.

[0095] In one embodiment, structure (I) includes R1 and R4, which are methyl groups, respectively. R2, R3, R5-R9, and R 10 ~R 14 Each of them is hydrogen.

[0096] In one embodiment, structure (I) includes R1, which is a methyl group. R4 is an i-propyl group. R2, R3, R5-R9, and R 10 ~R 14 Each of them is hydrogen.

[0097] In one embodiment, structure (I) comprises R1, R3, and R4, each of which is an i-propyl group. R2, R5-R9, and R 10 ~R 14 Each of them is hydrogen.

[0098] In another embodiment, the internal electron donor may be a phthalate compound. For example, the phthalate compound may be dimethyl phthalate, diethyl phthalate, dipropyl phthalate, diisopropyl phthalate, dibutyl phthalate, diisobutyl phthalate, diamyl phthalate, diisoamyl phthalate, methylbutyl phthalate, ethylbutyl phthalate, or ethylpropyl phthalate.

[0099] In addition to the solid catalyst components described above, the Ziegler-Natta catalyst system of this disclosure may also include a co-catalyst. The co-catalyst may include hydrides of aluminum, lithium, zinc, tin, cadmium, beryllium, and magnesium, alkyl, or aryl groups, and combinations thereof. In one embodiment, the co-catalyst is a hydrocarbyl aluminum co-catalyst represented by the formula R3Al, where each R is an alkyl, cycloalkyl, aryl, or hydride group, at least one R is a hydrocarbyl group, two or three R groups can be linked to a cyclic group to form a heterocyclic structure, each R may be the same or different, and each R being a hydrocarbyl group has 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms. In further embodiments, each alkyl group may be linear or branched, and such hydrocarbyl groups may be mixed groups, i.e., the groups may contain alkyl, aryl, and / or cycloalkyl groups. Non-limiting examples of suitable radicals include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, neopentyl, n-hexyl, 2-methylpentyl, n-heptyl, n-octyl, isooctyl, 2-ethylhexyl, 5,5-dimethylhexyl, n-nonyl, n-decyl, isodecyl, n-undecyl, and n-dodecyl.

[0100] Non-limiting examples of suitable hydrocarbyl aluminum compounds include: triisobutylaluminum, tri-n-hexylaluminum, diisobutylaluminum hydride, di-n-hexylaluminum hydride, isobutylaluminum dihydride, n-hexylaluminum dihydride, diisobutylhexylaluminum, isobutyldihexylaluminum, trimethylaluminum, triethylaluminum, tri-n-propylaluminum, triisopropylaluminum, tri-n-butylaluminum, tri-n-octylaluminum, tri-n-decylaluminum, and tri-n-dodecylaluminum. In one embodiment, the co-catalyst is selected from triethylaluminum, triisobutylaluminum, tri-n-hexylaluminum, diisobutylaluminum hydride, and di-n-hexylaluminum hydride.

[0101] In one embodiment, the co-catalyst is triethylaluminum. The molar ratio of aluminum to titanium is about 5:1 to about 500:1, or about 10:1 to about 200:1, or about 15:1 to about 150:1, or about 20:1 to about 100:1. In another embodiment, the molar ratio of aluminum to titanium is about 45:1.

[0102] A suitable catalyst composition may comprise a solid catalyst component, a co-catalyst, and an external electron donor, which may be a mixed external electron donor (M-EED) of two or more different components. Suitable external electron donors or “external donors” include one or more selectivity regulators (SCAs) and / or one or more activity limiters (ALAs). As used herein, an “external donor” is a composition comprising components, or mixtures of components, that are added independently of pro-catalyst formation that modifies catalytic performance. As used herein, an “activity limiter” is a composition that reduces catalytic activity as the polymerization temperature rises above a threshold temperature (e.g., a temperature above approximately 95°C) in the presence of the catalyst. A “selectivity regulator” is a composition that improves the tacticity of a polymer, and improved tacticity is generally understood to mean increased tacticity, decreased xylene soluble content, or both. It should be understood that the above definitions are not mutually exclusive, and a single compound may be classified as both, for example, an activity limiter and a selectivity regulator.

[0103] The selectivity control agent according to this disclosure is generally an organosilicon compound. For example, in one embodiment, the selectivity control agent may be an alkoxysilane.

[0104] In one embodiment, the alkoxysilane is of the general formula:SiR m (OR') 4-m (I) may be present in the formula, where R is independently a hydrocarbyl or amino group substituted with, for each occurrence, hydrogen or, optionally, one or more substituents containing one or more heteroatoms of Group 14, 15, 16, or 17, wherein R contains up to 20 atoms excluding hydrogen and halogens, and R' is C 1~4 It is an alkyl group, and m is 0, 1, 2, or 3. In one embodiment, R is C 6~12 Aryl, alkyl, or aralkyl, C 3~12 Cycloalkyl, C 3~12 Branched alkyl, or C 3~12 It is a cyclic or acyclic amino group, and R' is C 1~4It is alkyl, and m is 1 or 2. In one embodiment, for example, the second selectivity control agent may include n-propyltriethoxysilane. Other selectivity control agents that can be used include propyltriethoxysilane or diisobutyldimethoxysilane.

[0105] In one embodiment, the catalyst system may include an activity limiter (ALA). The ALA suppresses or otherwise prevents malfunctions in the polymerization reactor, ensuring the continuation of the polymerization process. Typically, the activity of the Ziegler-Natta catalyst increases with increasing reactor temperature until it reaches very high levels. The Ziegler-Natta catalyst also typically maintains high activity near the melting point of the resulting polymer. The heat generated by the exothermic polymerization reaction can cause agglomeration from the polymer particles, which can ultimately lead to the interruption of the polymer manufacturing process. The ALA reduces catalytic activity at high temperatures, thereby preventing reactor malfunctions, reducing (or preventing) particle agglomeration, and ensuring the continuation of the polymerization process.

[0106] The activity limiting agent may be a carboxylic acid ester. Aliphatic carboxylic acid esters are C4-C 30 It may be an aliphatic acid ester, a mono or poly(two or more) ester, linear or branched, saturated or unsaturated, or any combination thereof. C4~C 30 Aliphatic acid esters may also be substituted with substituents containing one or more heteroatoms of group 14, 15, or 16. Preferred C 4~C30 Non-limiting examples of aliphatic acid esters include aliphatic C 4~30 C of monocarboxylic acid 1~20 Alkyl esters, aliphatic C 8~20 C of monocarboxylic acid 1~20 Alkyl esters, aliphatic C 4~20 C of monocarboxylic acids and dicarboxylic acids 1~4 Allyl mono and diesters, aliphatic C 8~20 C of monocarboxylic acids and dicarboxylic acids 1~4 Alkyl esters, and C2~100 (Poly)glycol or C 2~100 (Poly)glycol ether C 4~20 Examples include mono- or polycarboxylate derivatives. In a further embodiment, C4-C 30 Aliphatic acid esters include laurate, myristate, palmitate, stearate, oleate, sebacate, (poly)(alkylene glycol) mono or diacetate, (poly)(alkylene glycol) mono or dimyristate, (poly)(alkylene glycol) mono or dilaurate, (poly)(alkylene glycol) mono or dioleate, glyceryl tri(acetate), C 2~40 This may be glyceryl triesters of aliphatic carboxylic acids, and mixtures thereof. In further embodiments, C4-C 30 The aliphatic esters are isopropyl myristate, di-n-butyl sebacate, and / or pentyl valerate.

[0107] In one embodiment, the selective control agent and / or activity limiter may be added separately to the reactor. In another embodiment, the selective control agent and activity limiter may be mixed together beforehand and then added to the reactor as a mixture. In addition, the selective control agent and / or activity limiter may be added to the reactor in different ways. For example, in one embodiment, the selective control agent and / or activity limiter may be added directly to the reactor, such as a fluidized bed reactor. Alternatively, the selective control agent and / or activity limiter may be added indirectly to the reactor volume by being supplied, for example, through a cycle loop (e.g., line 22 in Figure 1). The selective control agent and / or activity limiter may be combined with the reactor cycle gas in the cycle loop before being supplied to the reactor.

[0108] In addition to the Ziegler-Natta catalyst, the process of this disclosure may also use a metallocene catalyst. The metallocene catalyst may include "half-sandwich" and "full-sandwich" compounds having one or more Cp ligands (isoglobal ligands with cyclopentadienyl and cyclopentadieny) bonded to at least one group 3 to 12 metal atom, and one or more leaving groups bonded to at least one metal atom.

[0109] A Cp ligand is one or more rings or ring systems, at least a portion of which include π-bonding systems such as cycloalkadienyl ligands and heterocyclic analogs. The rings or ring systems typically include atoms selected from group 13-16 atoms, and in some embodiments, the atoms constituting the Cp ligand are selected from carbon, nitrogen, oxygen, silicon, sulfur, phosphorus, germanium, boron, aluminum, and combinations thereof, with carbon constituting at least 50% of the ring members. For example, the Cp ligands may be selected from substituted and unsubstituted cyclopentadienyl ligands and isoglobal ligands to cyclopentadienyl. Non-limiting examples of such ligands include cyclopentadienyl, cyclopentaphenantrenyl, indenyl, benzoindenyl, fluorenyl, octahydrofluorenyl, cyclooctatetraenyl, cyclopentacyclododecene, phenanthrindenyl, 3-benzofluorenyl, 9-phenylfluorenyl, 8-H-cyclopento[a]acenaphtyrenyl, 7-H-dibenzofluorenyl, indeno[1,2-9]anthrene, thiophenoindenyl, thiophenofluorenyl, their hydrogenated versions (e.g., 4,5,6,7-tetrahydroindenyl, or "H4Ind"), their substituted versions (discussed and described in more detail below), and their heterocyclic versions.

[0110] The metal atom "M" of the metallocene compound may be selected from group 3-12 atoms and lanthanide group atoms, or from group 3-10 atoms, or from Sc, Ti, Zr, Hf, V, Nb, Ta, Mn, Re, Fe, Ru, Os, Co, Rh, Ir, and Ni, or from group 4, 5, and 6 atoms, or it may be a Ti, Zr, or Hf atom, or it may be Hf, or it may be Zr. The oxidation state of the metal atom "M" may be in the range of 0 to +7, or it may be +1, +2, +3, +4, or +5, or it may be +2, +3, or +4. Unless otherwise indicated, the group bonded to the metal atom "M" is such that the following structure and the compound described in the structure are electrically neutral. The Cp ligand(s) form at least one chemical bond with the metal atom M to form the "metallocene catalyst component". Cp ligands differ from leaving groups bonded to metal atoms M in that they are less susceptible to substitution / extraction reactions.

[0111] In one embodiment, the metallocene catalyst is given by the following formula: (C5R x ) y R' z (C5R m MQ n-y-1 [In the formula, M is a metal in groups IIIB to VIII of the periodic table of elements, (C5R x ) and (C5R m ) is the same or different cyclopentadienyl or substituted cyclopentadienyl group bonded to M, R is either the same or different, and is a hydrocarbyl group such as an alkyl, alkenyl, aryl, alkylaryl, or arylalkyl group containing hydrogen or 1 to 20 carbon atoms, or two carbon atoms are linked together to form a C4 to C6 ring. R' is a C1-C4 substituted or unsubstituted alkylene group, dialkyl or diarylgermanium or silicon, or two (C5R x ) and (C5R m) an alkyl, arylphosphine, or amine group that bridges the ring, Q is a hydrocarbyl group such as an aryl, alkyl, alkenyl, alkylaryl, or arylalkyl group having 1 to 20 carbon atoms, a hydrocarboxyl group having 1 to 20 carbon atoms, or a halogen, and may be the same or different from each other. z is either 0 or 1, y is 0, 1, or 2. If y is 0, then z is 0, n is 0, 1, 2, 3, or 4 depending on the valence state of M. [ny is greater than 1] is expressed as [this].

[0112] Exemplary but non-limiting examples of metallocenes represented by the above formula include dialkylmetallocenes, such as bis(cyclopentadienyl)titaniumdimethyl, bis(cyclopentadienyl)titaniumdiphenyl, bis(cyclopentadienyl)zirconiumdimethyl, bis(cyclopentadienyl)zirconiumdiphenyl, bis(cyclopentadienyl)hafniumdimethyl and diphenyl, bis(cyclopentadienyl)titaniumdi-neopentyl, bis(cyclopentadienyl)zirconiumdi-neopentyl, bis(cyclopentadienyl)zirconiumdi-neopentyl, bis(cyclo (Cyclopentadienyl)titanium dibenzyl, bis(cyclopentadienyl)zirconium dibenzyl, bis(cyclopentadienyl)vanadium dimethyl; monoalkyl metallocene, e.g., bis(cyclopentadienyl)titanium methyl chloride, bis(cyclopentadienyl)titanium ethyl chloride, bis(cyclopentadienyl)titanium phenyl chloride, bis(cyclopentadienyl)zirconium methyl chloride, bis(cyclopentadienyl)zirconium ethyl chloride, bis(cyclopentadienyl)zirconium Titanium phenyl chloride, bis(cyclopentadienyl)titanium methyl bromide; trialkyl metallocenes, e.g., cyclopentadienyltitanium trimethyl, cyclopentadienylzirconium triphenyl, and cyclopentadienylzirconium trineopentyl, cyclopentadienylzirconium trimethyl, cyclopentadienylhafnium triphenyl, cyclopentadienylhafnium trineopentyl, and cyclopentadienylhafnium trimethyl; monocyclopentadienyltitanocenes, e.g., penta Methylcyclopentadienyltitanium trichloride, pentaethylcyclopentadienyltitanium trichloride; bis(pentamethylcyclopentadienyl)titanium diphenyl, carbenes represented by the formula bis(cyclopentadienyl)titanium=CH2, and derivatives of this reagent; substituted bis(cyclopentadienyl)titanium(IV) compounds, e.g., bis(indenyl)titanium diphenyl or dichloride, bis(methylcyclopentadienyl)titanium diphenyl or dihalides; dialkyl, trialkyl,Tetraalkyl and pentaalkylcyclopentadienyltitanium compounds, e.g., bis(1,2-dimethylcyclopentadienyl)titanium diphenyl or dichloride, bis(1,2-diethylcyclopentadienyl)titanium diphenyl or dichloride; silicon, phosphine, amine or carbon-bridged cyclopentadiene complexes, e.g., dimethylsilyldicyclopentadienyltitanium diphenyl or dichloride, methylphosphinedicyclopentadienyltitanium diphenyl or dichloride, methylenedicyclopenta Dienyltitanium diphenyl or dichloride and other dihalide complexes; and crosslinked metallocene compounds, such as isopropyl(cyclopentadienyl)(fluorenyl)zirconium dichloride, isopropyl(cyclopentadienyl)(octahydrofluorenyl)zirconium dichloride, diphenylmethylene(cyclopentadienyl)(fluorenyl)zirconium dichloride, diisopropylmethylene(cyclopentadienyl)(fluorenyl)zirconium dichloride, diisobutylmethylene(cyclopentadienyl) (Fluorenyl) zirconium dichloride, cyclohexyllidene (cyclopentadienyl) (fluorenyl) zirconium dichloride, cyclohexyllidene (cyclopentadienyl) (fluorenyl) zirconium dichloride, diisopropylmethylene (2,2,5-dimethylcyclopentadienyl) (fluorenyl) zirconium dichloride, isopropyl (cyclopentadienyl) (fluorenyl) hafnium dichloride, diphenylmethylene (cyclopentadienyl) (fluorenyl) hafnium dichloride, diisopropylmethylene Teylene (cyclopentadienyl)(fluorenyl) hafnium dichloride, diisobutylmethylene (cyclopentadienyl)(fluorenyl) hafnium dichloride, cyclohexyllidene (cyclopentadienyl)(fluorenyl) hafnium dichloride, cyclohexyllidene (cyclopentadienyl)(fluorenyl) hafnium dichloride, diisopropylmethylene (2,5-dimethylcyclopentadienyl)(fluorenyl) hafnium dichloride, isopropyl(cyclopentadienyl)(fluorenyl) titanium dichloride,Diphenylmethylene (cyclopentadienyl)(fluorenyl) titanium dichloride, diisopropylmethylene (cyclopentadienyl)(fluorenyl) titanium dichloride, diisobutylmethylene (cyclopentadienyl)(fluorenyl) titanium dichloride, cyclohexyllidene (cyclopentadienyl)(fluorenyl) titanium dichloride, cyclohexyllidene (cyclopentadienyl)(fluorenyl) titanium dichloride, diisopropylmethylene (2,5-dimethylcyclopentadienyl fluorenyl Renyl)titanium dichloride, racemic mixture - ethylenebis(1-indenyl)zirconium(IV) dichloride, racemic mixture - ethylenebis(4,5,6,7-tetrahydro-1-indenyl)zirconium(IV) dichloride, racemic mixture - dimethylsilylbis(1-indenyl)zirconium(IV) dichloride, racemic mixture - dimethylsilylbis(4,5,6,7-tetrahydro-1-indenyl)zirconium(IV) dichloride, racemic mixture - 1,1,2,2-tetramethylsilanilenbis(1-indenyl)zirconium (IV) Dichloride, Racemic - 1,1,2,2-Tetramethylsilanilenbis(4,5,6,7-Tetrahydro-1-indenyl)zirconium(IV) Dichloride, Racemic - Dimethylsilylbis(2-Methyl-4-t-Butyl-1-Cyclopentadienyl)zirconium(IV) Dichloride, Racemic - Ethylenebis(1-indenyl)hafnium(IV) Dichloride, Racemic - Ethylenebis(4,5,6,7- Tetrahydro-1-indenyl)hafnium(IV) dichloride, racemic -dimethylsilylbis(1-indenyl)hafnium(IV) dichloride, racemic -dimethylsilylbis(4,5,6,7-tetrahydro-1-indenyl)hafnium(IV) dichloride, racemic -1,1,2,2-tetramethylsilanilenbis(1-indenyl)hafnium(IV) dichloride, racemic -1,1,2,2-tetramethylsilanilenbis(4,5,6,7-tetrahydro-1-indenyl)hafnium(IV), dichloride,Ethylidene(1-indenyl-2,3,4,5-tetramethyl-1-cyclopentadienyl)hafnium(IV) dichloride, racemic mixture - ethylenebis(1-indenyl)titanium(IV) dichloride, racemic mixture - ethylenebis(4,5,6,7-tetrahydro-1-indenyl)titanium(IV) dichloride, racemic mixture - dimethylsilylbis(4,5,6,7-tetrahydro-1-indenyl)titanium(IV) dichloride, racemic mixture - dimethylsilylbis(4,5,6,7-tetrahydro-1-indenyl) Examples include tetrahydro-1-indenyl)titanium(IV) dichloride, racemic-1,1,2,2-tetramethylsilanilenbis(1-indenyl)titanium(IV) dichloride, racemic-1,1,2,2-tetramethylsilanilenbis(4,5,6,7-tetrahydro-1-indenyl)titanium(IV) dichloride, and ethylidene(1-indenyl-2,3,4,5-tetramethyl-1-cyclopentadienyl)titanium(IV) dichloride.

[0113] An activator can also be used in conjunction with the metallocene catalyst. The activator may be, for example, an aluminoxane. Possible activators include those with the following general formula: M 3 M 4 v X 2 c R 3 b-c Further comprising the co-catalyst, [In the formula, M 3 These are metals of groups IA, IIA, and IIIA of the periodic table, and M 4 is a metal in group IA of the periodic table, where v is a number between 0 and 1, and each X 2 is any halogen, c is a number from 0 to 3, and each R 3 Examples include those having a monovalent hydrocarbon group or hydrogen, b being a number from 1 to 4, and bc being at least 1.

[0114] Compounds having only one Group IA, Group IIA, or Group IIIA metal suitable for carrying out the present invention include the following formula: M 3 R 3 k [In the formula, M 3 These are metals of Group IA, Group IIA, or Group IIIA, such as lithium, sodium, beryllium, barium, boron, aluminum, zinc, cadmium, and gallium. k is M 3 It is equal to 1, 2, or 3 depending on the valence, and this valence is usually M 3 It depends on the specific family to which it belongs (i.e., IA, IIA, or IIIA), Each R 3 This includes compounds having any monovalent hydrocarbon group. 3 As an example of the basis, the above-mentioned R in relation to equation (V) 3 One of the following is a possible explanation.

[0115] This disclosure may be better understood by referring to the following examples. [Examples]

[0116] Test method: The melt flow rate was measured according to ASTM D1238-01 under conditions of a 2.16 kg load and 230°C.

[0117] The gas flow velocity (SGV) was measured using a Venturi apparatus.

[0118] The composition of the fluid medium was measured by online GC, and this was frequently calibrated with a check gas to ensure that the sum of all components was between 99% and 101%.

[0119] Using the BWR (Benedict-Webb-Rubin) equation, the gas density (ρ) is calculated using the gas composition, temperature, and pressure. g ) was calculated immediately.

[0120] The total pressure was measured using a pressure gauge commonly used in the chemical industry.

[0121] Description of the catalyst used: Catalyst 1 was prepared according to Example 4 of U.S. Patent Application Publication No. 2010 / 0173769(A1).

[0122] Catalyst 2 was prepared in accordance with U.S. Patent Application Publication No. 20200283553(A1).

[0123] Catalyst 3 was prepared according to Example 10 of U.S. Patent No. 9,593,182.

[0124] Catalyst 4 was prepared in accordance with U.S. Patent No. 5,604,172.

[0125] Description of the external electron donor used: Donor 1 was fabricated according to Example J1 of U.S. Patent Application Publication No. 2011 / 0152067(A1).

[0126] Donor 2 was fabricated according to Example H1 of U.S. Patent Application Publication No. 2011 / 0152067(A1).

[0127] Donor 3 was fabricated according to Example IE1 of U.S. Patent Application Publication No. 2019 / 0194438(A1).

[0128] Donor 4 was fabricated according to Example B1 of U.S. Patent Application Publication No. 2011 / 0152067(A1).

[0129] Donor 5 was fabricated according to Example I1 of U.S. Patent Application Publication No. 2011 / 0152067(A1).

[0130] Various polypropylene random copolymers were produced in a commercial-scale fluidized bed reactor. The operating conditions for each experiment are listed in Table 1 below. In addition, the stability of the reaction operation was evaluated for each experiment. Experiments 10 and 11 are comparative examples.

[0131] Atty. Reference number GRAC-59-P (W10297-00)

[0132] [Table 1]

[0133] These and other modifications and changes to the present invention can be implemented by those skilled in the art without departing from the spirit and scope of the invention as more specifically described in the appended claims. In addition, it should be understood that the various embodiments may be interchangeable in whole or in part. Furthermore, those skilled in the art will understand that the foregoing description is merely illustrative and is not intended to limit the invention to what is further described in such appended claims. The present invention includes the following embodiments. [1] A process for producing a polypropylene random copolymer in a fluidized bed reactor, comprising supplying a fluid medium into a reactor vessel containing a bed of catalytically active polyolefin particles, wherein the fluid medium comprises propylene gas, C2 and / or C4-C8α-olefin comonomers, hydrogen, and at least one inert gas.

number

[10] The process according to [1], wherein the fluid medium contains propane in an amount of about 6 mol% or more.

[11] The process according to [1], wherein the fluid medium contains nitrogen in an amount of about 11 mol% or more.

[12] The process according to [1], wherein the fluid medium contains nitrogen and propane in such an amount that the sum of the mole percent of nitrogen and the mole percent of propane is more than approximately 10%.

[13] The density of the aforementioned fluid medium is approximately 55 kg / m³ 3 The process described in [1] is superfluous.

[14] The process according to [1], wherein the condensation level of the reactor circulating gas when it enters the reactor is about 20% by weight or less.

[15] ρ g Approximately 70 kg / m 3 The process described in [1] is as follows:

[16] The process according to [1], wherein propane constitutes less than 25 mol% of the fluid medium.

Claims

1. A process for producing a polypropylene random copolymer in a fluidized bed reactor, comprising supplying a fluidized medium into a reactor vessel containing a bed of catalytically active polyolefin particles, wherein the fluidized medium comprises propylene gas, C2 and / or C4-C8α-olefin comonomers, hydrogen, and at least one inert gas. [Math 1] The momentum flux of the aforementioned fluid medium, as defined, is 7.0 N / m ２ That is all, in the formula, ρ ｇ A process wherein is the density of the fluid medium, SGV is the gas emptying velocity of the fluid medium, the condensation level of the reactor circulating gas when it enters the reactor is 17% by weight or less, and the polypropylene random copolymer contains propylene monomer units in an amount of 80 to 99.5 mol%.

2. The momentum flux of the aforementioned fluid medium is 8.3 N / m³. ２ The process described in claim 1 is as described above.

3. The process according to claim 1, wherein the inert gas includes nitrogen.

4. The process according to claim 1, wherein the inert gas comprises propane.

5. The process according to claim 1, further comprising supplying the catalyst into the reaction vessel.

6. The process according to claim 1, wherein the SGV is 0.34 m / second or more.

7. The process according to claim 1, wherein the comonomer comprises ethylene.

8. The process according to claim 1, wherein the comonomer comprises 1-butene.

9. The process according to claim 1, wherein the fluid medium contains propane in an amount of 6 mol% or more.

10. The process according to claim 1, wherein the fluid medium contains nitrogen in an amount of 11 mol% or more.

11. The process according to claim 1, wherein the fluid medium contains nitrogen and propane in an amount such that the sum of the mole percent of nitrogen and the mole percent of propane exceeds 10%.

12. The density of the aforementioned fluid medium is 55 kg / m³ ３ The process described in claim 1, which is a super-process.

13. ρ ｇ 70 kg / m ３ The process according to claim 1, which is as follows:

14. The process according to claim 1, wherein propane constitutes less than 25 mol% of the fluid medium.

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