Polypropylene polymer having an extremely high melt flow rate

Abstract

This invention provides an efficient process for producing high-melt-flow-rate polypropylene polymers. It also provides polypropylene polymer compositions containing high-melt-flow-rate polypropylene polymers that can be used to produce a wide variety of articles, including meltblown webs. [Solution] A polymer composition is provided comprising a polypropylene polymer, wherein the polypropylene polymer has a melt flow rate of more than about 900 g / 10 min, the polypropylene polymer has a molecular weight distribution greater than about 3 and less than about 13, and the polypropylene polymer is free of any peroxides. The polyolefin polymer is produced using a Ziegler-Natta catalyst, and it is not necessary to use peroxides to obtain a high melt flow rate.

Description

[Technical Field]

[0001] (Related applications) This application claims priority to U.S. Provisional Patent Application No. 63 / 075,861, filed on September 9, 2020, the contents of which are incorporated herein by reference. [Background technology]

[0002] Polyolefin polymers are used in a wide variety of applications and fields. For example, polyolefin polymers are thermoplastic polymers that can be easily processed. Polyolefin polymers can also be recycled and reused. Polyolefin polymers are formed from hydrocarbons such as ethylene and alpha-olefins, which are obtained from petrochemicals and are abundantly available.

[0003] Polypropylene polymers, a type of polyolefin polymer, generally have a linear structure based on propylene monomer. Polypropylene polymers can have a variety of different stereospecific configurations. For example, polypropylene polymers can be isotactic, syndiotactic, and atactic. Isotactic polypropylene is perhaps the most common form and can be highly crystalline. Polypropylene polymers that can be produced include polypropylene copolymers, which include homopolymers, modified polypropylene polymers, and polypropylene terpolymers. By modifying polypropylene or copolymerizing propylene with other monomers, a variety of different polymers with desired properties for specific applications can be produced.

[0004] Currently, polypropylene polymers with very high melt flow rates are particularly in demand and needed. The melt flow rate of a polymer generally indicates the amount of molten polymer that flows over a certain period of time at a particular temperature and load. A higher melt flow rate may indicate that the polymer can be easily processed, particularly during extrusion molding, injection molding, and the formation of fibers and films. High melt flow rate polypropylene polymers are particularly well suited for the production of meltblown webs. Meltblown nonwoven webs are generally formed from molten thermoplastic polymer extruded as molten fibers through multiple fine, usually circular, dye capillaries. Once the fibers are formed, they come into contact with a high-speed gas, such as air, which dampens the fibers and reduces their diameter. The meltblown fibers are then deposited on a convergence surface, forming a web of randomly dispersed meltblown fibers. The meltblown fibers may be continuous or discontinuous. Meltblown webs are particularly well suited for use in filtration applications.

[0005] For example, meltblown web can be incorporated into face masks designed to cover the wearer's nose and mouth. When incorporated into face masks, meltblown web is highly effective at protecting the wearer by preventing the passage of viruses and other microorganisms and contaminants. Due to the coronavirus pandemic, face masks are now being worn not only by medical professionals but also by office workers, industrial workers, students, and consumers in virtually all public places.

[0006] Traditionally, to produce polypropylene polymers with high melt flow rates for use in the manufacture of meltblown webs, the polymers were formed using metallocene catalysts or subjected to peroxide decomposition. When using metallocene catalysts, also called single-site catalysts, the polymerization process can be somewhat inefficient in that it is relatively slow and the raw material utilization rate is low. Furthermore, to produce the polymers, Ziegler-Nut... Transitioning between the use of metallocene catalysts and metallocene catalysts in a reactor can be time-consuming and costly. Furthermore, metallocene catalysts may be susceptible to reactor operability issues and may not be compatible with known activity limiters. Metallocene catalysts may also be sensitive to feedstock impurities.

[0007] Peroxide decomposition techniques for producing high-melt-flow, high-speed polypropylene polymers also have various drawbacks. For example, peroxides can be expensive. Furthermore, the peroxide supply during the process must be carefully controlled to ensure that a sufficient amount of peroxide is supplied to achieve stable production of high-melt-flow polymers. In addition, unreacted peroxides may remain in the final material, causing degradation over time. Finally, peroxide decomposition can result in undesirable volatile substances that may need to be removed by thermal oxidation processes to comply with environmental regulations.

[0008] In light of the above, there is a need for more efficient processes for producing high-melt-flow-rate polypropylene polymers. There is also a need for polypropylene polymer compositions containing high-melt-flow-rate polypropylene polymers that can be used to produce all different types of articles, including meltblown webs. [Overview of the project]

[0009] This disclosure generally relates to a process for producing high melt flow rate polyolefin polymers and the polymers produced by that process. High melt flow rate polyolefin polymers can be used in a wide variety of applications. For example, high melt flow rate polymers are particularly well suited for producing extremely fine fibers such as meltblown fibers. In this regard, this disclosure also relates to fibers made from polymers and nonwoven webs made from fibers. In one embodiment, a meltblown web can be produced using the high melt flow rate polymer of this disclosure, which is then incorporated into a face mask to provide protection against airborne microorganisms and contaminants.

[0010] For example, in one embodiment, the disclosure relates to a polymer composition comprising a polypropylene polymer. The polypropylene polymer has a melt flow rate greater than about 900 g / 10 min, for example greater than about 1000 g / 10 min, for example greater than about 1400 g / 10 min, for example greater than about 1800 g / 10 min, for example greater than about 2200 g / 10 min. The melt flow rate of the polypropylene polymer may generally be less than about 9000 g / 10 min, for example less than about 7000 g / 10 min, for example less than about 4000 g / 10 min. The polypropylene polymer has a molecular weight distribution greater than about 2.5, for example about 3 to about 13, for example about 3.5 to about 12. Furthermore, the polypropylene polymer does not contain any peroxides. In one embodiment, the polypropylene polymer is a polypropylene homopolymer.

[0011] The polypropylene polymers of this disclosure may have not only a very high melt flow rate but also a controlled amount of xylene-soluble content. For example, the polypropylene polymer may have a xylene-soluble content of about 6% to about 2% by weight (including all increments of 0.1% between these). In one embodiment, the xylene-soluble content is less than about 6%, for example less than about 4%, for example less than about 3.5%, for example less than about 3%, for example less than about 2.5%, for example less than 2%. A lower xylene-soluble content may offer processing advantages, while a higher amount may produce nonwoven fabrics with a softer feel.

[0012] The polypropylene polymers of this disclosure may have a weight-average molecular weight (Mw) of less than about 100,000 g / mol, for example less than about 80,000 g / mol, and generally greater than about 20,000 g / mol, for example greater than about 40,000 g / mol. The rimer may have a number-average molecular weight (Mn) of less than approximately 10,000 g / mol.

[0013] According to this disclosure, polypropylene polymers can be catalyzed with Ziegler-Natta catalysts, or in other words, produced in the presence of a Ziegler-Natta catalyst. In one embodiment, the Ziegler-Natta catalyst may include an internal electron donor comprising a substituted phenylenediester.

[0014] The Ziegler-Natta catalyst may include a solid catalyst component, a selective control agent, and optionally an activity limiter. The solid catalyst component may include a combination of a magnesium moiety, a titanium moiety, and an internal electron donor. The internal electron donor may be one of the above, or a phthalate compound. In one embodiment, the selective control agent includes an organosilicon compound. For example, the selective control agent may include propyltriethoxysilane, diisobutyldimethoxysilane, n-propyltrimethoxysilane, or a mixture thereof. In one embodiment, the activity limiter (ALA) includes isopropyl myristate or pentyl valerate (PV).

[0015] In one embodiment, the reactor temperature can be increased to increase the melt flow rate, decrease the weight-average molecular weight, and reduce the molecular weight distribution. The above properties can facilitate the fiber blowing process during the production of melt-blown webs. Polymers produced by this process can produce fibers at ultra-low denier and / or higher processing rates. Furthermore, nonwoven webs made from this polymer are dimensionally stable and do not exhibit necking during production and handling.

[0016] In one embodiment, the solid catalyst component may further include organosilicon compounds and / or epoxy compounds. In yet another embodiment, the solid catalyst component may include organophosphorus compounds.

[0017] As described above, the polymer compositions of this disclosure are particularly well suited for manufacturing fibers and films. According to this disclosure, fibers having a diameter of less than about 5 microns, for example less than about 2 microns, for example less than about 1 micron, for example less than 0.5 microns, such as meltblown fibers, can be manufactured. Meltblown webs can be made from these fibers. Meltblown webs can be used to constitute all kinds of products, including face masks.

[0018] This disclosure also relates to a process for producing olefin polymers. This process involves polymerizing a propylene monomer in the presence of a Ziegler-Natta catalyst. The catalyst may include a solid catalyst component, a selectivity control agent, and optionally an activity limiter. The solid catalyst component may include a magnesium moiety, a titanium moiety, and an internal electron donor. The selectivity control agent may include an organosilicon compound. This process can produce polypropylene polymers having a melt flow rate of more than about 900 g / 10 min. Furthermore, this process can be carried out without the use of peroxides during polymer formation.

[0019] In one embodiment, the hydrogen ratio to other components in the reactor may be relatively high. Increasing the hydrogen ratio can increase the melt flow rate of the polymer produced. The xylene soluble content is controlled by changing the amount of external electron donors present, i.e., the amounts of both the selectivity control agent and the activity limiting agent. When the xylene soluble content is low and the melt flow is high, more external electron donors can be supplied to the reactor. In one embodiment, the external electron donor mixture may contain a mixture of pentyl valerate and propyltriethoxysilane in a molar ratio of about 50:50 to about 70:30. The reactor temperature is 72°C or higher, for example, 80°C. It can reach up to 90°C.

[0020] One problem typically encountered in the past as the melt flow rate increases is the occurrence of higher fineness levels in the resin powder. However, polymers manufactured according to this disclosure may contain fine powder in amounts of less than about 8% by weight, for example less than about 7% by weight, for example less than 6% by weight.

[0021] Other features and aspects of this disclosure are discussed in more detail below. [Brief explanation of the drawing]

[0022] A complete and implementable disclosure of the present invention, including the best mode for those skilled in the art, is described in more detail in the remainder of this specification, including by reference to the accompanying drawings. [Figure 1] This is a perspective view of a face mask that may be made from the polymer composition disclosed herein. [Figure 2] The following are some graphs showing the results obtained in the following examples, illustrating the relationship between melt flow rate and H2 / C3 molar ratio. [Figure 3] The following are some graphs showing the results obtained in the examples below, illustrating the relationship between melt flow rate and xylene soluble content. [Figure 4] The following graph shows some of the results obtained in the examples below, illustrating the relationship between fine powder and melt flow rate. [Modes for carrying out the invention]

[0023] Definitions and Test Procedures The melt flow rate (MFR), as used herein, is measured for propylene polymers at 230°C at a weight of 2.16 kg according to the ASTM D1238 test method. The melt flow rate can be measured in pellet form or in reactor powder form. When measuring reactor powder, a stabilizing package containing 2000 ppm of CYANOX2246 antioxidant (methylenebis(4-methyl-6-tert-butylphenol)), 2000 ppm of IRGAFOS168 antioxidant (tris(2,4-di-tert-butylphenyl) phosphite), and 1000 ppm of acid scavenger ZnO may be added.

[0024] For high-melt flow rate polymers, the test diode may be smaller, as shown below:

[0025] [Table 1]

[0026] [Table 2]

[0027] Calculations for polypropylene polymers:

[0028] [Table 3]

[0029] Particle size can be measured using a sieve test. The sieve test is performed using a GRADEX particle size analyzer, which is commercially available from Rotex Global. The average particle size based on weight fraction is determined from the particle size distribution obtained from the GRADEX particle size analyzer.

[0030] Fine powder is defined as the weight fraction of polymer particles that pass through a GRADEX 120 mesh (125 microns).

[0031] Xylene solubles (XS) are found in polypropylene random copolymer resins. This method is defined as the weight percentage of resin remaining in the solution after dissolving a lipid sample in high-temperature xylene and cooling the solution to 25°C. It is also known as the gravimetric XS method according to ASTM D5492-06, which uses a 60-minute precipitation time, and is referred to herein as the “wet method.”

[0032] The ASTM D5492-06 method described above can be adapted to determine the xylene-soluble portion. Generally, the procedure consists of weighing 2 g of the sample and dissolving the sample in 200 mL of o-xylene in a 400 mL flask fitted with a 24 / 40 fitting. The flask is connected to a water condenser, the contents are stirred, and the mixture is heated under nitrogen (N2) reflux, and reflux is maintained for a further 30 minutes. The solution is then cooled in a temperature-controlled water bath at 25°C for 60 minutes to allow crystallization of the xylene-insoluble fraction. Once the solution has cooled and the insoluble fraction has precipitated from the solution, separation of the xylene-soluble portion (XS) from the xylene-insoluble portion (XI) is achieved by filtration through 25 micron filter paper. 100 mL of the filtrate is collected in a pre-weighed aluminum pan, and o-xylene is evaporated from this 100 mL of filtrate under a stream of nitrogen. Once the solvent has evaporated, place the pan and contents in a 100°C vacuum oven for 30 minutes or until dry. Then, let the pan cool to room temperature and weigh it. The xylene-soluble portion is XS (wt%) = [(m³-m²)] * 2 / m1] * Calculated as 100, where m1 is the original weight of the sample used, m2 is the weight of the empty aluminum pan, and m3 is the weight of the pan and residue (asterisks elsewhere in this and the disclosure). * (This indicates that the identified terms or values ​​are multiplied.)

[0033] XS can also be measured according to the Viscotek method as follows: 0.4 g of polymer is dissolved in 20 mL of xylene with stirring at 130°C for 60 minutes. The solution is then cooled to 25°C, and after 60 minutes, the insoluble polymer fraction is filtered off. The resulting filtrate is analyzed by flow injection polymer analysis using a Viscotek ViscoGEL H-100-3078 column with a THF mobile phase flowing at 1.0 mL / min. The column is equipped with a Viscotek viscometer and refractometer detector for light scattering, operating at 45°C. The instrument is coupled to a Model 302 Triple Detector Array. Instrument calibration is maintained using Viscotek PolyCAL® polystyrene standards. A polypropylene (PP) homopolymer, such as Dow 5D98 of biaxially oriented polypropylene (BOPP) grade, is used as a reference material to ensure that Viscotek instruments and sample preparation procedures provide consistent results. Values ​​for reference polypropylene homopolymers such as 5D98 are initially derived from tests using the ASTM method identified above.

[0034] The weight-average molecular weight (Mw), number-average molecular weight (Mn), molecular weight distribution (Mw / Mn) (also known as "MWD"), and higher average molecular weight (Mz and Mz+1) are measured by GPC according to the GPC analysis method for polypropylene. The polymer is measured using an IR5 MCT (high-sensitivity cadmium mercury telluride, thermoelectric cooled IR detector), a four-capillary viscometer of Polymer Char, an octagonal MALLS of Wyatt, and three Agilent Plgel Olexis (13um). Analysis was performed using High Temperature GPC. The oven temperature was set to 150°C. The solvent was nitrogen-purged 1,2,4-trichlorobenzene (TCB) containing approximately 200 ppm of 2,6-di-t-butyl-4-methylphenol (BHT). The flow rate was 1.0 mL / min, and the injection volume was 200 pl. A sample concentration of 2 mg / mL was prepared by dissolving the sample in N2-purged and preheated TCB (containing 200 ppm of BHT) at 160°C for 2 hours with gentle stirring.

[0035] The GPC column set is calibrated by running 20 polystyrene standards with narrow molecular weight distributions. The molecular weights (MW) of the standards range from 266 to 12,000,000 g / mol, and the standards were contained in six “cocktail” mixtures. Each standard mixture has separation between individual molecular weights for at least 10 years. Polystyrene standards are prepared at a rate of 0.005 g in 20 mL of solvent for molecular weights of 1,000,000 g / mol or more, and at a rate of 0.001 g in 20 mL of solvent for molecular weights less than 1,000,000 g / mol. The polystyrene standards are dissolved at 160°C for 60 minutes with stirring. The narrow standard mixtures are run first, followed by the components with the highest molecular weights to minimize the effects of decomposition. Logarithmic molecular weight calibration is generated using a quartic polynomial fit as a function of elution volume. The equivalent molecular weight of polypropylene was calculated using the following formula with the reported Mark-Houwink coefficients for polypropylene (Th.G.Scholte, NLJ Meijerink, HMS Schoffeleers, and AMG Brands, J.Appl. Polym. Sci., 29, 3763-3782 (1984)) and polystyrene (EPOtocka, RJ Roe, NY Hellman, PMMuglia, Macromolecules, 4, 507 (1971)):

[0036]

number

[0037] [Table 4]

[0038] (Detailed explanation) Those skilled in the art will understand that this discussion is for illustrative purposes only and is not intended to limit broader aspects of the disclosure.

[0039] Generally, this disclosure relates to a process for producing high melt-flow rate polyolefin polymers, particularly polypropylene polymers including polypropylene homopolymers, polypropylene random copolymers, and polypropylene block copolymers. The process of this disclosure makes it possible to produce polypropylene polymers having melt-flow rates greater than about 900 g / 10 min, for example greater than about 1200 g / 10 min, for example greater than about 1500 g / 10 min, for example greater than about 1800 g / 10 min, for example greater than about 2200 g / 10 min, without the need to use a single-site catalyst and / or any peroxide. The melt-flow rate may be up to about 7000 g / 10 min. Thus, the process of this disclosure enables the production of polypropylene polymers with very high melt-flow rates in a highly efficient manner. This disclosure also relates to polyolefin polymers produced from this process.

[0040] Polyolefin polymers, such as polypropylene polymers with very high melt flow rates, are well-suited for use in a variety of different applications for manufacturing a wide range of different articles and products. High melt flow rate polymers generally have excellent flow properties that facilitate the processing of the polymer, even in extrusion or molding processes of very small dimensions. For example, high melt flow rate polyolefin polymers are very suitable for forming small fibers and thin films. For example, polyolefin polymers made according to this disclosure are particularly well-suited for forming meltblown fibers and meltblown nonwoven webs. Such fibers may be continuous or discontinuous and may have a fiber diameter of less than about 5 microns, e.g., less than about 3 microns, e.g., less than about 2 microns, e.g., less than 1 micron. Meltblown nonwoven webs made from these fibers have excellent filtration properties and are well-suited for use as barrier layers. For example, meltblown webs made according to this disclosure can create excellent barriers against fluids, airborne contaminants, and microorganisms such as viruses. As a result, meltblown webs made according to this disclosure are particularly well-suited for incorporation into protective clothing and garments.

[0041] Referring to Figure 1, for example, an embodiment of a face mask 10 that can be fabricated using the meltblown web of the present disclosure is shown. The face mask 10 includes a body portion 12 attached to straps 14 and 16. The straps 14 and 16 are designed to extend around the wearer's ears to hold the body portion 12 over the wearer's nose and mouth. The body portion 12 can be fabricated from the meltblown web of the present disclosure. For example, the body portion 12 can be fabricated from a single layer of meltblown material. Alternatively, the meltblown web of the present disclosure can be one of several layers used to form the body portion 12. For example, in one embodiment, the body portion 12 may include a meltblown layer of the present disclosure placed between two outer layers.

[0042] The polypropylene polymers of this disclosure, which may be polypropylene homopolymers, are produced using a Ziegler-Natta catalyst. The catalyst generally comprises a solid catalyst component combined with a selectivity control agent. Optionally, the catalyst may also include an activity limiter. The catalyst is activated during polymerization using a co-catalyst. The solid catalyst component may also vary depending on the specific application. Generally, the solid catalyst component of this disclosure comprises a magnesium moiety, a titanium moiety, and an internal electron donor. In one embodiment, the solid catalyst component may optionally include organophosphorus compounds, organosilicon compounds, and epoxy compounds. The internal electron donor may include a phthalate compound or a substituted phenylenediester.

[0043] The selectivity control agents used in accordance with this disclosure are organosilicon compounds. The use of selectivity control agents is expected to facilitate the production of polymers with very high melt flow rates, while also producing polymer products with high bulk density, low fineness, and good handling properties. In one embodiment, organosilicon compounds can be used together with activity limiting agents such as pentyl valerate. Both the selectivity control agent and the activity limiting agent can be considered as external electron donors, forming a mixed external electron donor. The molar ratio of activity limiting agent to selectivity control agent may be about 40:60 to about 80:20, for example, about 50:50 to about 70:30. Using the mixed external electron donor, the xylene soluble content can be controlled, particularly by adding a larger amount of the mixed external electron donor, to achieve a higher hydrogen ratio in the reactor.

[0044] In one embodiment, the process for producing the polymer can be carried out in a gas-phase reactor. The catalyst used in this process has been found to produce high-melt-flow-rate polymers while still operating at relatively low hydrogen partial pressures compared to previous processes. For example, in one embodiment, the hydrogen partial pressure in the reactor can be maintained below 60 psi, e.g., below about 58 psi. Similarly, reducing the propylene partial pressure during the process can increase the melt-flow rate of the polymer produced.

[0045] The reactor temperature can also be controlled and manipulated to optimize polymer production. For example, in one embodiment, the reactor temperature may be about 68°C to about 75°C. Alternatively, higher temperatures can be used. For example, in another embodiment, the reactor temperature may be above about 75°C, for example above 80°C, for example above 85°C, for example above 90°C, and generally below about 95°C. Higher reactor temperatures can increase the hydrogen response and thus enable the production of polymers with higher melt flow rates at lower hydrogen concentrations compared to operating the reactor at lower temperatures.

[0046] In one embodiment, the hydrogen ratio to other components in the reactor may be relatively high. As described above, the xylene soluble content is controlled by changing the amount of external electron donors present, i.e., the amounts of both the selectivity control agent and the activity limiting agent. When the xylene soluble content is low and the melt flow is high, more external electron donors can be supplied to the reactor. It has been found that polymers with extremely high melt flow rates can be produced by combining a high hydrogen concentration in the presence of external electron donors and using specific catalyst systems as described below.

[0047] The process of this disclosure can produce polypropylene polymers having a melt flow rate generally greater than about 900 g / 10 min. For example, the melt flow rate of the polymer may be between about 900 g / 10 min and about 9000 g / 10 min, for example, between about 900 g / 10 min and about 7000 g / 10 min, including all increments of 5 g / 10 min in between. In certain embodiments, the melt flow rate of the polypropylene polymer may be greater than about 1000 g / 10 min, for example, greater than about 1200 g / 10 min, for example, greater than about 1400 g / 10 min, for example, greater than about 1800 g / 10 min, for example, greater than about 2200 g / 10 min. The polypropylene polymer may be a polypropylene homopolymer. Polypropylene copolymers, including polypropylene random copolymers and polypropylene block copolymers, can also be formed by this process. The comonomer may include ethylene or butylene.

[0048] By using the Ziegler-Natta catalyst system, polypropylene polymers with a molecular weight distribution generally greater than approximately 2.5 can be formed. The molecular weight distribution can generally be greater than approximately 3, e.g., greater than approximately 3.5, e.g., greater than approximately 4, e.g., greater than approximately 4.5, and generally less than approximately 13, e.g., less than approximately 12, e.g., less than approximately 10. Maintaining a molecular weight distribution of approximately 3 to approximately 10 can offer various advantages when manufacturing nonwoven webs. For example, maintaining a molecular weight distribution within the above range results in dimensionally stable webs that do not become bottlenecks during manufacturing and handling. It can be manufactured.

[0049] Polypropylene polymers prepared in accordance with this disclosure generally have a controlled xylene soluble content. For example, a polypropylene polymer may have a xylene soluble content of less than about 6%, e.g., less than about 4.5%, e.g., less than about 4%, e.g., less than about 3.5%, e.g., less than about 3%, e.g., less than about 2.5%, e.g., less than 2%. The xylene soluble content may be greater than about 3% by weight, e.g., greater than about 4% by weight.

[0050] Polypropylene polymers can also have relatively low molecular weights. Molecules determined from GPC can be, for example, less than about 100,000 g / mol, for example less than about 80,000 g / mol, for example less than about 70,000 g / mol, and greater than about 10,000 g / mol, for example greater than about 20,000 g / mol, for example greater than about 30,000 g / mol, for example greater than about 40,000 g / mol.

[0051] As described above, polypropylene polymers are catalyzed with Ziegler-Natta catalysts. The catalyst may include solid catalyst components that can be varied depending on the specific application.

[0052] The solid catalyst component may include (i) magnesium, (ii) a transition metal compound of an element of Groups IV to VIII of the periodic table, (iii) a halide, an oxyhalide, and / or an alkoxide of (i) and / or (ii), and (iv) a combination 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.

[0053] In one embodiment, the preparation of the catalyst component includes halogenation of a mixed magnesium and titanium alkoxide.

[0054] 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 portion. Non-limiting examples of suitable magnesium portions include magnesium chloride anhydrous and / or its alcohol adduct, magnesium alkoxide or aryloxide, mixed magnesium alkoxy halide, and / or carboxylated magnesium dialkoxide or aryloxide. In one embodiment, the MagMo precursor is magnesium di(C 1~4 ) alkoxide. In a further embodiment, the MagMo precursor is diethoxymagnesium.

[0055] In another embodiment, the catalyst component is a mixed magnesium / titanium compound (“MagTi”). The “MagTi precursor” has the formula Mg d Ti(OR e )fX g , where R e is an aliphatic or aromatic hydrocarbon radical having 1 to 14 carbon atoms, or COR’, where R’ is an aliphatic or aromatic hydrocarbon radical having 1 to 14 carbon atoms, and each OR eThe 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. Removal of 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 has a particularly desirable particle size. It is uniform.

[0056] 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 can 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, ethyl p-methoxybenzoate, methyl p-ethoxybenzoate, ethyl p-ethoxybenzoate, and p-chlorobenzoate. In one embodiment, the benzoate 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.

[0057] 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 may have 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.

[0058] In some embodiments, the organosilicon is a monomer compound or a polymer compound. The organosilicon compound may contain the -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 alone or in combination. The organosilicon compound can be used in combination with aluminum alkoxides and internal electron donors.

[0059] The aluminum alkoxides mentioned above may also have the formula AI(OR')3, where each R' is individually a hydrocarbon having up to 20 carbon atoms. This may include cases where each R' is individually methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, neopentyl, etc.

[0060] 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.

[0061] Examples of epoxy compounds include, but are not limited to, glycidyl-containing compounds of the following formulas:

[0062] [ka] In the formula, "a" is 1, 2, 3, 4, or 5, X is F, Cl, Br, I, or methyl, and R a The compound is 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.

[0063] 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; 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(1,2-Epoxy-1-Methylethyl)benzene; Epifluorohydrin; 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; Glycidyl methyl 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-Ethyl Selected from the group consisting of glycidylpropionamide; N,N-glycidylmethylbenzamide; N-(4,5-epoxypentyl)-N-methylbenzamide; N,N-diglycylaniline; bis(4-diglycidylaminophenyl)methane; poly(N,N-glycidylmethylacrylamide); 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.

[0064] As organophosphorus compounds, for example, phosphate esters such as trialkyl phosphate esters can be used. Such compounds can be represented by the following formula:

[0065] [ka] In the formula, R1, R2, and R3 are each independently methyl, ethyl, and a linear or branched (C3-C3) chain. 10) Selected from the group consisting of alkyl groups. In one embodiment, the trialkyl phosphate ester is tributyl phosphate ester.

[0066] In yet another embodiment, substantially spherical MgCl2-nEtOH adducts can 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 carried out at a temperature of 20 to 80°C at the top of the container. 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 approximately 15 to 150 microns, preferably 20 to 100 microns, and most preferably between 35 to 85 microns (Malvern d 50 )

[0067] 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 microcrystalline size of the magnesium halide support during the conversion. Therefore, providing an internal electron donor improves stereoselectivity. This yields a catalyst composition.

[0068] In one embodiment, the halogenating agent is of formula Ti(OR e ) f X h Titanium halide having the following properties, where R eAnd X are 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 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 a halogenating agent and a chlorinated aromatic liquid, the mixture containing 40 to 60 volume percent of the halogenating agent, such as TiCl4.

[0069] The reaction mixture can 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 higher than about -50°C, e.g., higher than about -40°C. The mixture is then heated at a rate of 0.1–10.0°C / min or at a rate of 1.0–5.0°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–150°C (or any value or partial range between them), or 0°C–120°C. Halogenation may be continued for a period of 5–60 minutes, or 10–50 minutes, with the internal electron donor substantially absent.

[0070] 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 can 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.

[0071] In one embodiment, the catalyst component is brought into contact with an internal electron donor before reacting with the halogenating agent.

[0072] 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, up to 150°C, up to 120°C, up to 115°C, or up to 110°C.

[0073] In one embodiment, the catalyst component, the internal electron donor, and the halogenating agent are added simultaneously or substantially simultaneously.

[0074] The halogenation procedure can 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.

[0075] After the halogenation procedure described above, the obtained 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 is then washed with a rinsing liquid diluent to remove unreacted TiCl4. The solid catalyst composition can be prepared and, if necessary, dried to remove any residual liquid. 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 slurried in hydrocarbons, particularly relatively heavy hydrocarbons such as mineral oil for further storage or use.

[0076] 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.

[0077] 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, and may be washed with water or other means, heat-treated, or aged. The aforementioned further procedures may be combined in any order, used separately, or not used at all.

[0078] 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 into which the internal electron donor is incorporated. The catalyst component from which the catalyst composition is formed may be any of the above-mentioned catalyst precursors, including a magnesium moiety precursor, a mixed magnesium / titanium precursor, a benzoate-containing magnesium chloride precursor, a magnesium, titanium, epoxy, and phosphorus precursor, or a spherical precursor.

[0079] Various different types of internal electron donors may 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: [ka]

[0080] (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, and alkyl groups) The group is NR5, where R5 is a hydrocarbyl group having 1 to 20 carbon atoms, or hydrogen.

[0081] 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.

[0082] 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. The silicon atoms may or may not be present in the carbon chain.

[0083] In one embodiment, the substituted phenylenediester has the following structure (I):

[0084] [ka]

[0085] In one embodiment, structure (I) includes isopropyl groups R1 and R3, R2, R4, and R5-R 14 Each of them is hydrogen.

[0086] 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.

[0087] 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, R 10, R 11 , R 13 , and R 14 Each of them is hydrogen.

[0088] In one embodiment, structure (I) includes R1 as a methyl group and R3 as 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.

[0089] 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.

[0090] In one embodiment, structure (I) contains R1 as a methyl group and R3 as 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.

[0091] 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.

[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 an ethoxy group. R2, R4, R5, R6, R8, R9, R 10 , R 11 , R13 , and R 14 Each of them is hydrogen.

[0093] 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.

[0094] 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.

[0095] 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.

[0096] 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.

[0097] In one embodiment, structure (I) includes a methyl group R1, and R3 is a t-butyl group. R6, R7, R 11 , and R 12 Each of these is a chlorine atom. R2, R4, R5, R8, R9, R10 , R 13 , and R 14 each is hydrogen.

[0098] In one embodiment, structure (I) includes R1 which is a methyl group, and R3 is a t-butyl group. R6, R8, R 11 , and R 13 each is a chlorine atom. R2, R4, R5, R7, R9, R 10 , R 12 , and R 14 each is hydrogen.

[0099] In one embodiment, structure (I) includes R1 which is a methyl group, and R3 is a t-butyl group. R2, R4 and R5 to R 14 each is a fluorine atom.

[0100] In one embodiment, structure (I) includes R1 which is a methyl group, and R3 is a t-butyl group. R7 and R 12 each is a trifluoromethyl group. R2, R4, R5, R6, R8, R9, R 10 , R 11 , R 13 , and R 14 each is hydrogen.

[0101] In one embodiment, structure (I) includes R1 which is a methyl group, and R3 is a t-butyl group. R7 and R 12 each is an ethoxycarbonyl group. R2, R4, R5, R6, R8, R9, R 10 , R 11 , R 13 , and R 14 each is hydrogen.

[0102] In one embodiment, R1 is a methyl group and R3 is a t-butyl group. R7 and R 12 each is an ethoxy group. R2, R4, R5, R6, R8, R9, R 10 , R 11 , R 13 , and R 14 each is hydrogen.

[0103] In one embodiment, structure (I) includes R1 which is a methyl group, and R3 is a t-butyl group. Each of R7 and R 12 is a diethylamino group. Each of R2, R4, R5, R6, R8, R9, R 10 , R 11 , R 13 , and R 14 is hydrogen.

[0104] In one embodiment, structure (I) includes R1 which is a methyl group, and R3 is a 2,4,4-trimethylpentan-2-yl group. Each of R2, R4 and R5~R 14 is hydrogen.

[0105] In one embodiment, structure (I) includes R1 and R3, each of which is a sec-butyl group. Each of R2, R4 and R5~R 14 is hydrogen.

[0106] In one embodiment, structure (I) includes R1 and R4 which are each a methyl group. Each of R2, R3, R5~R9 and R 10 ~R 14 is hydrogen.

[0107] In one embodiment, structure (I) includes R1 which is a methyl group. R4 is an i-propyl group. Each of R2, R3, R5~R9 and R 10 ~R 14 is hydrogen.

[0108] In one embodiment, structure (I) includes R1, R3, and R4, each of which is an i-propyl group. Each of R2, R5~R9 and R 10 ~R 14 is hydrogen.

[0109] 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.

[0110] In addition to the solid catalyst components described above, the catalyst systems of this disclosure may also include cocatalysts. Cocatalysts may include hydrides of aluminum, lithium, zinc, tin, cadmium, beryllium, and magnesium, alkyl, or aryl, and combinations thereof. In one embodiment, the cocatalyst is a hydrocarbyl aluminum cocatalyst represented by the formula R3Al, where each R is an alkyl, cycloalkyl, aryl, or hydride radical, at least one R is a hydrocarbyl radical, two or three R radicals can be joined to a cyclic radical to form a heterocyclic structure, each R may be the same or different, and each R being a hydrocarbyl radical has 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms. In further embodiments, each alkyl radical may be linear or branched, and such hydrocarbyl radicals may be mixed radicals, i.e., radicals 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-decyl.

[0111] 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.

[0112] 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.

[0113] For example, suitable catalyst compositions may include solid catalyst components, co-catalysts, and mixed external electron donors (M-EEDs) of two or more different components. Examples of external electron donors include one or more activity limiters (ALAs) and / or one or more selectivity regulators (SCAs). 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., above about 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. The above definitions are not mutually exclusive, and it should be understood that a single compound may be classified as both, for example, an activity limiter and a selectivity regulator.

[0114] The selectivity controllers according to this disclosure are generally organosilicon compounds. For example, in one embodiment, the selectivity controller may be an alkoxysilane.

[0115] In one embodiment, the alkoxysilane is of the general formula:SiR m (OR') 4-m (I) may have, where R is independently, for each occurrence, a hydrocarbyl or amino group substituted with one or more substituents containing hydrogen or, optionally, one or more heteroatoms of Group 14, 15, 16, or 17, and 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-chain 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.

[0116] 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 as the reactor temperature rises. 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 causes polymer particles to form aggregates. This can lead to problems, which may ultimately result in the interruption of the polymer formation process. ALA reduces catalytic activity at high temperatures, thereby preventing reactor malfunctions, reducing (or preventing) particle aggregation, and ensuring the continuation of the polymerization process.

[0117] The activity limiting agent may be a carboxylic acid ester. Aliphatic carboxylic acid esters are C4-C 30 It can be an aliphatic acid ester, a mono or poly(two or more) ester, a linear or branched chain, 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 C4-C 30 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 C 2~100(Poly)glycol or C 2~100 (Poly)glycol ether C4~ 20 Examples include mono- or polycarboxylate derivatives. In further embodiments, 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 ester is isopropyl myristate or di-n-butyl sebacate.

[0118] 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. Furthermore, 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, for example, by supplying it through a cycle loop. The selective control agent and / or activity limiter may be bound to catalyst particles in the cycle loop before being supplied to the reactor.

[0119] The catalyst system of this disclosure, as described above, can be used to produce olefin-based polymers. The process involves contacting an olefin with the catalyst system under polymerization conditions.

[0120] One or more olefin monomers can be introduced into a polymerization reactor and reacted with a catalyst system to form a fluidized bed of polymers, such as polymer particles. The olefin monomer may be, for example, propylene. Any suitable reactor can be used, including fluidized bed reactors, stirred gas reactors, moving packed bed reactors, multizone reactors, bulk phase reactors, slurry reactors, or combinations thereof. Suitable commercially available reactors include UNIPOL reactors, SPHERIPOL reactors, and SPHERIZONE reactors.

[0121] As used herein, “polymerization conditions” refers to temperature and pressure parameters within a polymerization reactor suitable for promoting polymerization between a catalyst composition and an olefin to form a desired polymer. The polymerization process may be a gas-phase, slurry, or bulk polymerization process operating in one or more reactors.

[0122] In one embodiment, polymerization occurs by gas-phase polymerization. As used herein, “gas-phase polymerization” is the passage of a fluidized medium containing one or more monomers through a fluidized bed of polymer particles maintained in a fluidized state by the fluidized medium, in the presence of a catalyst. Fluidization, "fluidized," or "fluidized" is a gas-solid contact process in which a bed of fine polymer particles is lifted and agitated by an upward flow of gas.

[0123] Fluidization occurs in a bed of particulate matter when an upward flow of fluid through the gaps in the bed of particles acquires a pressure difference and increased frictional resistance that exceeds the weight of the particulate matter. Thus, a “fluidized bed” is a plurality of polymer particles suspended in a fluidized state by a flow of a fluidizing medium. The “fluidizing medium” is one or more olefin gases, optionally a carrier gas (e.g., H2 or N2), and optionally a liquid (e.g., hydrocarbon) rising through a gas-phase reactor.

[0124] A typical gas-phase polymerization reactor (or gas-phase reactor) includes a vessel (i.e., reactor), a fluidized bed, a distribution plate, inlet and outlet piping, a compressor, a circulating gas cooler or heat exchanger, and a product discharge system. The vessel includes a reaction zone and a rate reduction zone, each of which is located on the distribution plate. The bed is located in the reaction zone. In one embodiment, the fluidized medium includes propylene gas and at least one other gas such as an olefin and / or a carrier gas such as hydrogen or nitrogen.

[0125] In one embodiment, contact occurs by supplying the catalyst composition to the polymerization reactor and introducing the olefin into the polymerization reactor. In one embodiment, the co-catalyst can be mixed (pre-mixed) with the catalyst composition before introducing the catalyst composition into the polymerization reactor. In another embodiment, the co-catalyst is added to the polymerization reactor independently of the catalyst composition. The independent introduction of the co-catalyst into the polymerization reactor may occur simultaneously with, or substantially simultaneously with, the supply of the catalyst composition.

[0126] In one embodiment, the polymerization process may include a pre-activation step, which involves contacting the catalyst composition with a co-catalyst and a selectivity control agent and / or activity limiter before activation. Subsequently, the resulting pre-activated catalyst stream is introduced into the polymerization reaction zone and contacted with the olefin monomer to be polymerized. Optionally, additional amounts of selectivity control agents and / or activity limiters may be added.

[0127] This process may include mixing a selective control agent (and optionally an activity limiter) with the catalyst composition. The selective control agent can form a complex with the co-catalyst and be mixed (premixed) with the catalyst composition before contact between the catalyst composition and the olefin. In another embodiment, the selective control agent and / or activity limiter may be added independently to the polymerization reactor. In one embodiment, the selective control agent and / or activity limiter may be supplied to the reactor via a cycle loop.

[0128] The above process can be used to produce polypropylene polymers having a very high melt flow rate. Furthermore, it is possible to produce polymers with a relatively small amount of fine powder and a relatively high bulk density. The bulk density may be, for example, greater than about 0.30 g / cc, for example greater than about 0.4 g / cc, for example greater than about 0.42 g / cc, for example greater than about 0.45 g / cc. The bulk density is generally less than about 0.6 g / cc, for example less than about 0.5 g / cc, for example less than about 0.4 g / cc.

[0129] The polypropylene polymer prepared in accordance with this disclosure can then be incorporated into various polymer compositions for manufacturing molded articles. The polymer compositions may generally contain more than about 70% by weight of high-melt flow rate polypropylene polymer, for example, more than about 80% by weight, for example more than about 90% by weight, or for example more than about 95% by weight. The polymer compositions may contain a variety of different additives and components. For example, the polymer composition may contain one or more antioxidants. For example, in one embodiment, the polymer composition contains a sterically hindered phenolic antioxidant and / or a phosphite antioxidant. The polymer composition may also contain acid scavengers such as calcium stearate. Furthermore, the polymer composition may contain colorants, UV stabilizers, and the like. Each of the above additives can generally be present in the polymer composition in an amount of about 0.015 to about 2% by weight.

[0130] Alternatively, high melt-flow rate polypropylene polymers can be used as processing aids. Processing aids may include fluids, lubricants, release agents, waxes, etc., to improve the melt-flow properties of other polymers. In this embodiment, the high melt-flow rate polypropylene polymer of the present disclosure may be present in the polymer composition in an amount of about 2% to about 50% by weight (including all 1% increments between these amounts). For example, the high melt-flow rate polypropylene polymer may be present in the polymer composition in an amount of less than about 30% by weight, e.g., less than about 25% by weight, e.g., less than about 20% by weight, e.g., less than about 10% by weight, and generally more than about 5% by weight. Polymers that can be combined with high melt-flow rate polypropylene polymers include other low melt-flow rate polypropylene polymers, polyethylene polymers, polyester polymers, etc.

[0131] This disclosure may be better understood by referring to the following examples.

[0132] Examples Using two different catalysts, Catalyst A and Catalyst B, various different high-melt flow rate polypropylene homopolymers were produced in accordance with this disclosure. Samples 13-18 below were produced using Catalyst B, which is the LYNX 1010 catalyst commercially available from WRGrace and Company. The LYNX 1010 catalyst contains a solid catalyst component comprising a magnesium moiety, a titanium moiety, an epoxy compound, and an organosilicon compound. The LYNX 1010 catalyst contains a phthalate compound as an internal electron donor.

[0133] Samples 1-12 and 19-21 below were prepared using catalyst A, which has similar solid catalyst components but uses a non-phthalate-substituted phenylenediester internal electron donor.

[0134] Both catalyst systems were used with a selective control agent. The selective control agent used was propyltriethoxysilane. The selective control agent was used together with pentyl valerate as an activity limiter. The molar ratio of selective control agent to activity limiter was 40:60.

[0135] Polymerization was carried out in a fluidized bed of gaseous phase equipped with a compressor and cooler connected to a cycle gas line.

[0136] Polypropylene resin powder was produced in a fluidized bed reactor using the above catalyst in combination with triethylaluminum (TEAI) as a co-catalyst.

[0137] The fluidized bed reactor was operated under the following conditions: Reactor temperature: 72°C for Examples 1-17, or 80°C for Example 18. Floor weight: 68-72 pounds Gas tower velocity: 1.0~1.6 ft / sec

[0138] All polymers were produced with a hydrogen-to-monomer ratio of approximately 0.11 to 0.23. All produced polymers had a xylene-soluble content of 1.5% to 6% by weight and a molecular weight distribution greater than 2.5. Catalyst productivity ranged from 10 to 40 tons per kg of catalyst, averaging approximately 20 tons / kg. Polymers with extremely high melt flow rates were produced without the need for peroxides. Polymer particle size was measured using a GRADEX sieve test.

[0139] The following samples were prepared, and the following results were obtained:

[0140] [Table 5]

[0141] [Table 6]

[0142] As shown above, all samples had a melt flow rate exceeding 900 g / 10 min. The highest melt flow was 8,152 g / 10 min. The results are also shown in Figures 2-4. As shown in Figure 4, the amount of fine powder generated during the process was relatively low.

[0143] As shown above, higher reactor temperatures are beneficial. Sample 18 was prepared at 80°C, while samples 1-17 were prepared at 72°C. Comparing Examples 14 and 18, both the molecular weight distribution (MWD) and Mw are lower at higher reactor temperatures, the melt flow rate is higher, but the hydrogen ratio remains almost the same.

[0144] As shown in the table below, further samples were prepared using catalyst A at a higher reactor temperature.

[0145] [Table 7]

[0146] Materials prepared using both catalysts A and B were evaluated on a meltblown line to produce fibers with the average fiber diameters shown in Table 6.

[0147] [Table 8]

[0148] 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.

Claims

1. A polymer composition, A polymer composition comprising a polypropylene polymer, wherein the polypropylene polymer has a melt flow rate of more than about 900 g / 10 min, the polypropylene polymer has a molecular weight distribution greater than about 3 and less than about 13, and the polypropylene polymer is free of any peroxides.

2. The polymer composition according to claim 1, wherein the polypropylene polymer has a melt flow rate of about 1,000 g / 10 min to about 7,000 g / 10 min.

3. The polymer composition according to claim 1 or 2, wherein the polypropylene polymer has a melt flow rate of more than about 1400 g / 10 min, for example more than about 1800 g / 10 min, for example more than about 2200 g / 10 min.

4. The polymer composition according to claim 1, wherein the polypropylene polymer has a weight-average molecular weight of less than 100,000 g / mol.

5. The polymer composition according to claim 1, wherein the polypropylene polymer has a number average molecular weight of less than 10,000 g / mol.

6. The polymer composition according to any one of claims 1 to 5, wherein the polypropylene polymer is a polypropylene homopolymer, a polypropylene random copolymer, or a polypropylene block copolymer.

7. The polymer composition according to any one of claims 1 to 6, wherein the polypropylene polymer has a xylene-soluble content of less than about 6.0% by weight, for example less than about 5% by weight, for example less than about 4% by weight, for example less than about 3% by weight, for example less than about 2.5% by weight.

8. The polymer composition according to any one of claims 1 to 7, wherein the polypropylene polymer has a xylene-soluble content of less than about 2% by weight.

9. The polymer composition according to any one of claims 1 to 8, wherein the polypropylene polymer is catalyzed with Ziegler-Natta catalyst.

10. The polymer composition according to claim 9, wherein the polypropylene polymer is catalyzed in the presence of a Ziegler-Natta catalyst containing an internal electron donor, and the internal electron donor contains a substituted phenylenediester or phthalate compound.

11. The polymer composition according to any one of claims 1 to 10, wherein the polypropylene polymer is present in the composition in an amount exceeding about 70% by weight, for example, exceeding about 80% by weight, for example, exceeding about 90% by weight, for example, exceeding about 95% by weight.

12. The polymer composition according to any one of claims 1 to 10, wherein the polypropylene polymer comprises a processing aid in combination with at least one other polymer having a lower melt flow rate, and the polypropylene polymer is contained in the composition in an amount of less than about 50% by weight, for example less than about 20% by weight, for example less than about 10% by weight.

13. The polymer composition according to claim 12, wherein the polypropylene polymer comprises a wax, a lubricant, a mold release agent, or a flow aid.

14. The polymer composition according to any one of claims 1 to 13, wherein the polypropylene polymer is catalyzed in the presence of a Ziegler-Natta catalyst, the Ziegler-Natta catalyst comprises a solid catalyst component, a selectivity control agent, and optionally an activity limiting agent, and the solid catalyst component comprises a magnesium moiety, a titanium moiety, and an internal electron donor.

15. The polymer composition according to claim 14, wherein the solid catalyst component further comprises an organosilicon compound and an epoxy compound.

16. The polymer composition according to claim 14 or 15, wherein the selectivity control agent comprises an organosilicon compound.

17. The polymer composition according to claim 16, wherein the selectivity control agent comprises propyltriethoxysilane, diisobutyldimethoxysilane, n-propyltrimethoxysilane, or a mixture thereof, and is used in combination with an activity limiting agent.

18. A fiber made from a polymer composition according to any one of claims 1 to 17, wherein the fiber has a diameter of less than about 5 microns.

19. A meltblown web composed of nonwoven meltblown fibers, wherein the meltblown fibers are produced from a polymer composition according to any one of claims 1 to 17.

20. A process for producing a polypropylene polymer, comprising polymerizing a propylene monomer in the presence of a Ziegler-Natta catalyst, wherein the Ziegler-Natta catalyst comprises a solid catalyst component, a selectivity control agent, and optionally an activity limiting agent, the solid catalyst component comprises a magnesium moiety, a titanium moiety, and an internal electron donor, the selectivity control agent comprises an organosilicon compound, a polypropylene polymer having a melt flow rate of more than about 900 g / 10 min is formed, and no peroxide is used during the process of forming the polypropylene polymer.

21. The process according to claim 20, wherein the solid catalyst component further comprises an organosilicon compound and an epoxy compound.

22. The process according to claim 20 or 21, wherein the internal electron donor comprises a substituted phenylenediester or phthalate compound.

23. The process according to any one of claims 20 to 22, wherein the selectivity control agent comprises an organosilicon compound, and a polypropylene polymer having a melt flow rate of more than 1000 g / 10 min is formed.

24. The process according to any one of claims 20 to 23, wherein the polypropylene polymer is a polypropylene homopolymer having a xylene-soluble content of less than about 4.5%, for example, less than about 2%.

25. The process according to any one of claims 20 to 24, wherein the H2 / C3 molar ratio during polymerization is about 0.1 to about 0.

3.

26. The process according to any one of claims 20 to 25, wherein the cocatalyst and the external electron donor are supplied to the polymerization reactor in a molar ratio of about 1.5 to about 15.

27. The process according to any one of claims 20 to 26, wherein the reactor temperature during polymerization is approximately 65°C to approximately 95°C.

28. The process according to claim 20, wherein the temperature is increased in order to increase the melt flow rate.

29. The process according to any one of claims 20 to 28, wherein the polymer obtained is a polypropylene random copolymer or polypropylene block copolymer containing ethylene or butylene as a comonomer.

30. The process according to claim 20, wherein the propylene partial pressure is reduced in order to increase the melt flow rate of the polypropylene polymer.

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