processes for polyethylene and compositions of this material

专利摘要:
ABSTRACT Patent of Invention: "PROCESSES FOR POLYETHYLENE AND COMPOSITIONS OF THIS MATERIAL". The present invention relates to a method of preparing polyethylene compositions that comprise the polymerization of ethylene in a first gas phase reactor and the polymerization of ethylene in a second gas phase reactor in the presence of hydrogen, at least one of which is the first and second gas phase reactor comprises a first and a second polymerization zone; characterized by the fact that the hydrogen pressure of the first and second polymerization zones are different, so that at least part of the ethylene in the second circulates through the first and second polymerization zones, and a gas mixture of each polymerization zone is total or partially prevented from entering the other region
公开号:BR112015020142B1
申请号:R112015020142-3
申请日:2014-02-26
公开日:2020-07-07
发明作者:Iakovos Vittorias；Harilaos Mavridis；Gerhardus Meier；Ulf Schueller；Diana Doetsch；Bernd Marczinke
申请人:Basell Polyolefine Gmbh；
IPC主号:

专利说明:

Cross References to Related Orders
[0001] This request claims the benefit of US Provisional Application ("US Provisional Application") No. .61 / 770.049, filed on February 27, 2013, and US Provisional Application No. .61 / 820.382, filed on May 7, 2013, which are incorporated herein in full by reference. Technical Field
[0002] The present invention relates to polymerization processes of ethylene and polyethylene compositions, including those with a density equal to or greater than 0.950 g / cm3, which can be used to produce hollow blow-molded and extruded articles, including , for example, thin-walled articles like bottles. Background of the Invention
[0003] The processability and mechanical properties of polyethylene polymers were obtained by mixing polyethylene materials produced by Cr catalysis with materials produced by Ziegler-Natta catalysis, as disclosed in U.S. Patent 4,536,550 and in the Patent Application International WO 2005/097888. Mechanical mixing does not always produce an ideal polymeric composition, and this has led to the development of methods of simultaneous production of polymers. Such methods allow mixing different polymers at the molecular level. The challenge of balancing the following properties persists: processability, high expansion in the mold with a high quality surface, dimensional stability, ease of processing the molten material under high shear rates, flow instabilities and resistance to environmental stress cracking (RFEA). Summary of the Invention
[0004] In some respects, the present description presents processes for preparing polyethylene compositions that comprise the following steps, in any order: a. supplying at least an initial amount of ethylene to a first gas phase reactor; B. supplying at least an initial amount of a Ziegler-Natta catalyst to the first gas phase reactor to supply at least an initial amount of polyethylene polymer within the first gas phase reactor; ç. transferring at least part of the initial amount of the polyethylene polymer and at least part of the initial amount of the Ziegler-Natta catalyst to a second gas phase reactor; d. supplying at least a second amount of ethylene in the presence of an initial amount of hydrogen to the second gas phase reactor to obtain a second polyethylene polymer to produce a polyethylene composition comprising the first polyethylene polymer and the second polyethylene polymer; characterized by the fact that at least one of the first and second gas phase reactors comprises a first and a second polymerization zone, the first polymerization zone has a first hydrogen pressure and the first hydrogen pressure is different from the second pressure of hydrogen, so that at least part of the second quantity of ethylene travels through the first and second polymerization zones and at least part of the gas mixture of each polymerization zone is totally or partially prevented from entering the other zone. In some configurations, the polymerizing ethylene flows upward through a first polymerization zone, leaves said initial polymerization zone and enters a second polymerization zone, through which the polymerizing ethylene polymer flows downwards under the gravity action, leaves said second polymerization zone and is reintroduced in the first polymerization zone, thus establishing the circulation of the polymerization ethylene polymer in said first and second polymerization zones in at least one of said first and second reactors gas phase. In some configurations, the upward flow through the first polymerization zone occurs under conditions of rapid fluidization or transport. In some configurations, the first polymerization zone comprises a hydrogen to ethylene ratio of about 0.25 to about 1.9. In some configurations, the hydrogen to ethylene ratio is about 0.47. In some configurations, the second polymerization zone comprises a hydrogen to ethylene ratio of about 0.001 to about 0.25. In some configurations, the hydrogen to ethylene ratio is about 0.057. In some configurations, step (c) or step (d) contains one or more comonomers. In some configurations, step (c) and step (d) contain one or more comonomers. In some configurations, the comonomer is a terminal alkene (c <20). In some configurations, the comonomer is 1-hexene. In some configurations, the second polymerization zone comprises a comonomer percentage of about 0.05 to about 0.2%. In some configurations, the comonomer percentage is about 0.09%. In some configurations, the second polymerization zone comprises a comonomer percentage of about 0.2 to about 1.2%. In some configurations, the comonomer percentage is about 0.5%. In some configurations, the process also comprises obtaining a first polyethylene in the first gas phase reactor in the presence of hydrogen. In some configurations, the process also involves obtaining polyethylene in the first and second gas phase reactors in the presence of hydrogen. In some configurations, hydrogen in the second gas phase reactor is less than hydrogen in the first gas phase reactor. In some configurations, the first or second gas phase reactors also comprise propane as an inert diluent. In some configurations, the first and second gas phase reactors also comprise propane as an inert diluent. In some configurations, the first gas phase reactor is heated to a temperature of about 70 ° C to about 95 ° C. In some configurations, the temperature is around 80 ° C. In some configurations, the first gas phase reactor is pressurized at a pressure of 2.5 megapascals ("MPa") to about 3.5 MPa. In some configurations, the pressure is about 2.9 MPa. In some configurations, the second gas phase reactor is heated to a temperature of about 70 ° C to about 95 ° C. In some configurations, the temperature is around 84 ° C. In some configurations, the second gas phase reactor is pressurized at a pressure of 2.0 MPa to about 3.0 MPa. In some configurations, the pressure is about 2.5 MPa. In some configurations, the Ziegler-Natta polymerization catalyst comprises a solid catalyst component characterized by the fact that it comprises a titanium compound in a magnesium support and an organoaluminated compound.In some configurations, the solid catalyst component is produced by placing contact the titanium compound with magnesium chloride or a precursor magnesium compound. In some configurations, the solid catalyst component is heated to a temperature of about 130 ° C to about 150 ° C. In some configurations, the temperature is about 135 ° C to about 150 ° C. In some configurations, the solid catalyst component is produced by placing the titanium compound in contact with magnesium chloride or with a magnesium precursor compound in the presence of an inert medium. In some configurations, the Ziegler-Natta polymerization catalyst also comprises an external electron donor compound. In some configurations, the external electron donor compound is alcohol. In some configurations, the external electron donor compound is ethanol. In some configurations, the Ziegler-Natta polymerization catalyst is prepolymerized with propylene. In some configurations, the Ziegler-Natta polymerization catalyst is prepolymerized with about 1 gram of polypropylene per gram of solid catalyst component. In some configurations, the polyethylene composition comprises a density of about 0.950 g / cm3 to about 0.970 g / cm3, alternatively greater than about 0.950 g / cm3, an MIF / MIP ratio of about 17 to about 25, a shear-induced crystallization index of about 0.15 to about 8 and a long-chain branching index of less than about 0.70. In some configurations, the polyethylene composition also comprises an eta (0.02) of about 30,000 to about 65,000 Pascal.second ("Paxs"). In some configurations, the process produces a polyethylene composition comprising: 1. about 40 to about 60% by weight of an ethylene homopolymer or copolymer with a density equal to or greater than about 0.960 g / cm3 and a flow index (MIE) at 190 ° C under load of 2.16 kilograms of about 5 to about 20 grams for 10 minutes ("g / 10 min"); and 2. about 40 to about 60% by weight of an ethylene homopolymer or copolymer having an MIE value less than the MIE value in (A).
[0005] In some configurations, the MIE of the ethylene copolymer in (B) is less than about 0.5 g / 10 min.
[0006] In another aspect, the present description provides a polyethylene composition characterized by the fact that it comprises: a. a first polyethylene, produced in a first gas phase reactor in the presence of an initial amount of hydrogen; and b. a second polyethylene, produced in a second gas phase reactor in the presence of a second amount of hydrogen, where the second amount of hydrogen is less than the first amount of hydrogen; where the first polyethylene and the second portion of polyethylene are produced in any order and in the presence of a Ziegler-Natta catalyst; where at least one within the first and second gas phase reactors comprises a first and a second polymerization zone, and the first polymerization zone has an initial hydrogen pressure, where the initial hydrogen pressure and the second hydrogen pressure are different so that at least part of the second quantity of ethylene moves through the first and second polymerization zones and at least part of the gas mixture of each polymerization zone is totally or partially prevented from entering the other zone. In some configurations, in at least one of the first and second gas phase reactors referred to, the polymerizing ethylene polymer flows upward through a first polymerization zone, leaves said initial polymerization zone and enters a second polymerization zone , through which the polymerization ethylene polymer flows downwards under the action of gravity, leaves said second polymerization zone and is reintroduced in the first polymerization zone, thus establishing the circulation of the polymerization ethylene polymer referred to above. first and second polymerization zone in at least one of said first and second gas phase reactors. In some configurations, the upward flow through the first polymerization zone occurs under conditions of rapid fluidization or transport. In some configurations, step (a) or step (b) contains one or more comonomers. In some configurations, step (a) and step (b) contain one or more comonomers. In some configurations, the comonomer is a terminal alkene (C≤20). In some configurations, the comonomer is 1-hexene. In some configurations, the process also comprises the initial production of polyethylene in the first gas phase reactor in the presence of hydrogen. In some configurations, the process also involves obtaining polyethylene in the first and second gas phase reactors in the presence of hydrogen. In some configurations, hydrogen in the second gas phase reactor is less than hydrogen in the first gas phase reactor. In some configurations, the first or second gas phase reactors also comprise propane as an inert diluent. In some configurations, the first and second gas phase reactors also comprise propane as an inert diluent. In some configurations, the first gas phase reactor is heated to a temperature of about 70 ° C to about 95 ° C. In some configurations, the temperature is around 80 ° C. In some configurations, the first gas phase reactor is pressurized at a pressure of 2.5 MPa to about 3.5 MPa. In some configurations, the pressure is about 2.9 MPa. In some configurations, the second gas phase reactor is heated to a temperature of about 70 ° C to about 95 ° C. In some configurations, the temperature is around 84 ° C. In some configurations, the second gas phase reactor is pressurized at a pressure of 2.0 MPa to about 3.0 MPa. In some configurations, the pressure is about 2.5 MPa. In some configurations, the Ziegler-Natta polymerization catalyst comprises a solid catalyst component characterized by the fact that it comprises a titanium compound in a magnesium support and an organoaluminated compound. In some configurations, the solid catalyst component is produced by placing the titanium compound in contact with magnesium chloride or with a magnesium precursor compound. In some configurations, the solid catalyst component is heated to a temperature of about 130 ° C to about 150 ° C. In some configurations, the temperature is about 135 ° C to about 150 ° C. In some configurations, the solid catalyst component is produced by placing the titanium compound in contact with magnesium chloride or with a magnesium precursor compound in the presence of an inert medium. In some configurations, the Ziegler-Natta polymerization catalyst also comprises an external electron donor compound. In some configurations, the external electron donor compound is alcohol. In some configurations, the external electron donor compound is ethanol. In some configurations, the Ziegler-Natta polymerization catalyst is prepolymerized with propylene. In some configurations, the solid catalyst component is prepolymerized with about 1 gram of polypropylene per gram of solid catalyst component. In some configurations, the polyethylene composition comprises a density of about 0.950 g / cm3 to about 0.970 g / cm3, alternatively greater than about 0.950 g / cm3, an MIF / MIP ratio of about 17 to about 25, a shear-induced crystallization index of about 0.15 to about 8 and a long-chain branching index of less than about 0.70. In some configurations, the polyethylene composition also comprises an eta (0.02) of about 30,000 to about 65,000 Paxs. In some configurations, the polyethylene composition is characterized by the fact that it comprises: 1. about 40 to about 60% by weight of an ethylene homopolymer or copolymer with a density equal to or greater than about 0.960 g / cm3 and an index of fluidity (MIE) at 190 ° C with a 2.16 kg load of about 5 to about 20 g / 10 min; and 2. about 40% to about 60% by weight of an ethylene homopolymer or copolymer with an MIE value less than the MIE value in (A).
[0007] In some configurations, the MIE of the ethylene copolymer in (B) is less than about 0.5 g / 10 min.
[0008] In yet another aspect, the present description provides a polyethylene composition characterized by the fact that it comprises: 1. density ranging from about 0.950 g / cm3 to about 0.970 g / cm3 and, alternatively, is greater than about 0.950 g / cm3; 2. MIF / MIP ratio of about 17 to about 25; 3. shear-induced crystallization index of about 0.15 to about 8; and 4. long chain branched index less than about 0.70.
[0009] In some configurations, the polyethylene composition is characterized by the fact that it also comprises: (E) eta (0.02) of about 30,000 to about 65,000 Pascals per second ("Paxs") and, alternatively, about from 30,000 to about 45,000 Paxs.
[00010] In some configurations, the density is greater than about 0.952 g / cm3. In some configurations, the density is greater than about 0.953 g / cm3. In some configurations, the MIF / MIP ratio is about 19 to about 23. In some configurations, the SIC index is about 0.15 to about 2. In some configurations, the SIC index is from about 0.2 to about 2. In some configurations, the index of long branched chains is about 0.69 or less. In some configurations, the index of long branched chains is about 0.65 or less. In some configurations, the eta (0.02) is about 31,000 to about 43,000 Paxs. In some configurations, the polyethylene composition is characterized by the fact that it also comprises one or more ethylene copolymers. In some configurations, the polyethylene composition is characterized by the fact that it also comprises a comonomer content equal to or less than about 1.2% by weight. In some configurations, the polyethylene composition is produced using a Ziegler-Natta polymerization catalyst. In some configurations, the Ziegler-Natta polymerization catalyst is characterized by comprising the placement of a solid catalyst component in contact with a compound organoaluminated. In some configurations, the Ziegler-Natta polymerization catalyst is characterized by also comprising the addition of an external electron donor compound. In some configurations, the solid catalyst component is characterized by comprising a titanium compound supported by magnesium chloride. In some configurations, the solid catalyst component containing a titanium compound with MgCh or a precursor compound of Mg at a temperature of about 130 ° C to about 150 ° C. In some configurations, the temperature is about 135 ° C to about 150 ° C. In some configurations, the solid catalyst component is produced by placing the titanium compound in contact with MgCh or with an Mg precursor compound in the presence of an inert medium. In some configurations, the polyethylene compound also comprises one or more characteristics among the following: a. Mp equal to or less than about 320,000 grams / mol ("g / mol"); B. Mp / Mn ratio of about 20 to about 30; ç. MIP from about 0.9 to about 2.1 g / 10 min, alternatively from about 1.2 to about 2.1 g / 10 min; and d. FIM of about 20 to about 45 grams / 10 min, alternatively about 26 to about 34 g / 10 min; and
[00011] In some configurations, Mp is equal to or less than about 300,000 g / mol. In some configurations, Mp is about 180,000 g to about 280,000 g / mol. In some configurations, the polyethylene composition is characterized by the fact that it comprises: about 40 to about 60% by weight of an ethylene homopolymer or copolymer with a density equal to or greater than about 0.960 g / cm3 and a fluidity index ( MIE) at 190 ° C with a load of 2.16 kg of about 5 to about 20 g / 10 min; and
[00012] (B) about 40% to about 60% by weight of a homopolymer or ethylene copolymer with an MIE value less than the MIE value in (A).
[00013] In some configurations, the MIE of the ethylene copolymer in (B) is less than about 0.5 g / 10 min.
[00014] In yet another aspect, the present description provides a manufactured article characterized by the fact that it comprises the polyethylene composition of the present description.In some configurations, the article is produced by blowing and extrusion. In some configurations, the articles are hollow articles, alternatively thin-walled and, alternatively, bottles. Brief Description of Drawings
[00015] These and other characteristics, aspects and advantages of the present description will be better understood by reference to the following description and the attached claims, as well as the drawings in the figures, where:
[00016] Figure 1 is an illustrative configuration of a simplified process flow chart in two gas phase reactors connected in series, suitable for use in accordance with various aspects of the ethylene polymerization processes disclosed here to produce various configurations of the polyethylene compositions described here.
[00017] It should be understood that the various configurations are not limited to the arrangements and instrumentation shown in the drawings in the figures. Detailed Description of Settings
[00018] The terms "polyethylene composition", "polyethylene", "ethylene polymer" and related terms are intended to encompass, as alternatives, both a single ethylene polymer and a composition of ethylene polymers, and in particular a composition of two or more components of ethylene polymers. In some embodiments, the polyethylene composition includes two or more polymer components of ethylene with different molecular weights. In some aspects, a composition characterized by the fact that it comprises two or more polymer components of ethylene with different molecular weights can also be described as "bimodal" or "multimodal" polymer in the relevant technique. In some embodiments, the polyethylene composition of the present description is characterized by the fact that it comprises one or more ethylene copolymers. The proportions of the present description are all molar proportions, unless otherwise indicated in an appropriate manner to an individual of ordinary skill in the art.
[00019] When used in the context of a chemical group: "hydrogen" means -H; hydroxy means -OH and "halo" means one or more elements selected independently from the groups formed by -F, -Cl, -Br and -I.
[00020] For the following groups and classes, the following subscripts in parentheses will more specifically define the classes or groups, as follows: "(Cn)" defines the exact number (n) of carbon atoms in the group or class. "(C <n)" defines the maximum number (n) of carbon atoms that can belong to a group or class, the minimum number being the lowest possible for the group in question, eg, it is understood that the minimum number of carbon atoms in groups "alkenyl (c <8)" or in the class "alkene (c <8)" is two. For example, "alkoxy (c <io)" means alkoxy groups with 1 to 10 carbon atoms. (Cn-n ') defines both the minimum number (n) and the maximum number (n') of carbon atoms in the group. Likewise, "alkoxy (C2-io)" refers to alkoxy groups with 2 to 10 carbon atoms.
[00021] As used herein, the term "saturated" means that the compound or group thus modified has no carbon-carbon double bond and no carbon-carbon triple bond, except as noted below. In the case of substituted versions of saturated groups, one or more carbon-oxygen double bonds or a carbon-nitrogen double bond may be present. And when such a bond is present, carbon-carbon double bonds that can occur as part of ketoenolic tautomerism or imine / amine tautomerism are not excluded.
[00022] The term "aliphatic" means, when used without the "substituted" modifier, that the compound or group thus modified is a compound or group of the acyclic or cyclic hydrocarbon type, but not aromatic. In aliphatic compounds or groups, carbon atoms can be joined in straight chains, branched chains or non-aromatic (alicyclic) rings. Aliphatic compounds or groups can be saturated, that is, joined by simple bonds (alkanes / alkyl) or unsaturated , with one or more double bonds (alkenes / alkenyl) or with one or more triple bonds (alkynes / alkynyl).
[00023] The term "alkyl", when used without the "substituted" modifier, refers to a saturated monovalent aliphatic group whose point of attachment is a carbon atom, a linear or branched structure, a cyclical, cyclic or acyclic and no atom other than carbon or hydrogen. Therefore, as used herein, cycloalkyl is a subset of the alkyls where the carbon atom containing the attachment point is also a member of one or more non-aromatic ring structures in which the cycloalkyl group consists exclusively of carbon and hydrogen atoms. used, the term does not exclude the presence of one or more alkyl groups (as permitted by limiting the number of carbon atoms) connected to the ring or ring system. The groups -CH3 (Me), -CH2CH3 (Et), -CH2CH2CH3 (n-Pr or propyl), -CH (CH3) 2 (/ -Pr, 'Pr or isopropyl), -CH (CH2) 2 (cyclopropyl) , -CH2CH2CH2CH3 (n-Bu), -CH (CH3) CH2CH3 (sec-butyl), -CH2CH (CH3) 2 (isobutyl), -C (CHS) 3 (tert-butyl, t-butyl, t-Bu or fBu), -CH2C (CH3) 3 (neopentyl), cyclobutyl, cyclopentyl, cyclohexyl and cyclohexylmethyl are non-limiting examples of alkyl groups. An "alkane" refers to the compound H-R, where R is an alkyl as defined above. When any of these terms is used with the "substituted" modifier, one or more hydrogen atoms are independently replaced by -OH, -F, -Cl, -Br, -I, -NH2, -NO2, -CO2H, -CO2CH3, -CN, -SH, -OCH3, -OCH2CH3, -C (O) CH3, -NHCH3, -NHCH2CH3, -N (CH3) 2, -C (O) NH2, -OC (O) CH3 or - S (O) 2NH2. The following groups are non-limiting examples of substituted alkyl groups: -CH2OH, -CH2CI, -CF3, -CH2CN, -CH2C (O) OH, -CH2C (O) OCH3, -CH2C (O) NH2, -CH2C (O) CH3 , -CH2OCH3, -CH2OC (O) CH3, -CH2NH2, -CH2N (CH3) 2 and -CH2CH2CI. The term "haloalkyl" is a subset of the substituted alkyls, in which one or more hydrogen atoms are replaced by a halogen group and no other atom other than carbon, hydrogen and halogen is present. The -CH2CI group is a non-limiting example of a haloalkyl. The term "fluoroalkyl" is a subset of the substituted alkyls, in which one or more hydrogens are replaced by a fluorine group and no other atom other than carbon, hydrogen and fluorine is present. The -CH2F, -CF3 and -CFkCFs groups are non-limiting examples of fluoroalkyl groups.
[00024] The term "alkenyl", when used without the "substituted" modifier, refers to an unsaturated monovalent aliphatic group whose attachment point is a carbon atom, a linear or branched structure, a cyclical, cyclic or acyclic structure, at least one non-aromatic carbon-carbon double bond, no carbon-triple carbon bond and no atom other than carbon or hydrogen. Some non-limiting examples of alkenyl groups are: -CH = CH2, -CH = CHCH3, -CH = CHCH2CH3, -CH2CH = CH2 (ally), -CH2CH = CHCH3 and -CH = CHCH = CH2. The term "alkenediyl", when used without the "substituted" modifier, refers to an unsaturated bivalent aliphatic group whose attachment points are two carbon atoms, a linear or branched structure, a cyclical, cyclic or acyclic structure, at least one non-aromatic carbon-carbon double bond, no triple carbon-carbon bond and no atom other than carbon or hydrogen. The -CH = CH-, -CH = C (CH3) CH2-, -CH = CHCH2- groups are non-limiting examples of alkenedyl groups. It should be noted that, although the alkenediyl group is aliphatic, it can, if connected by both ends, form part of an aromatic structure. The terms "alkene" and "olefin" are synonymous and refer to a compound of the formula H-R, where R is an alkenyl as defined above. A "terminal alkene" refers to an alkene that has a single carbon-carbon double bond, in which said bond forms a vinyl group at one end of the molecule. When any of these terms is used with the "substituted" modifier, one or more hydrogen atoms are independently replaced by -OH, -F, -Cl, -Br, -I, -NH2, -NO2, -CO2H, -CO2CH3, -CN, -SH, -OCH3, -OCH2CH3, -C (O) CH3, -NHCH3, -NHCH2CH3, -N (CH3) 2, -C (O) NH2, -OC (O) CH3OU -S (O) 2NH2. The -CH = CHF, -CH = CHCI and -CH = CHBr groups are non-limiting examples of substituted alkenyl groups.
[00025] In some aspects of the present description, one or more of the following abbreviations are used: g / cm3 for grams per cubic centimeter; RFEA for crack resistance by environmental stress; MPa for megapascals; ° C, degrees Celsius; g or gr, grams; g / 10 min, grams for 10 minutes; Paxs, pascals per second; g / mol, grams per mol; RPM, revolutions per minute; % weight, percentage by weight; ppm, parts per million; h or hr, hour (s); m or min, minute (s); m / s, meters per second; rad / s, radians per second; kJ / m2, kilojoules per square meter; dL / g, deciliters per gram; pL, microliters; mm, millimeters; K / min, Kelvin per minute; s or sec, seconds; mg, milligrams; ml or ml, milliliters; mg / L, milligrams per liter; kg / h, kilograms per hour; g / h, grams per hour; and nm, nanometers.
[00026] In some embodiments, the ethylene polymer or ethylene polymer composition of the present description is defined by the polymeric properties described herein. In some embodiments, the addition of other components, including additives commonly employed in the art, can modify one or more of said polymer properties, and polymers comprising such additional components are specifically included. In some configurations, the polyethylene polymerization methods of the description do not require mechanical mixing of two components obtained using two different polymerization catalysts
[00027] The MIF / MIP ratio provides a rheological measure of the molecular weight distribution. MIF and MIP are standard metrics, which are known to those skilled in the art. Both measurements are defined as the fluidity index (g / 10 minutes) measured at T = 190 ° C with a load of 21.6 kg or with a load of 5.0 kg, as found in ISO 1133.
[00028] Another measure of the molecular weight distribution is provided by the ratio Mp / Mn, where Mp is the average molar mass by weight and Mn is the average molar mass by number, both measured by gel permeation chromatography (GPC, "gel permeation chromatography "), as explained in the examples. The methods for determining such metrics are defined in the Examples section and provided by ISO 16014-1, -2 and -4 in the edition published in 2003. In some configurations, the Mp / Mn values of the polyethylene composition of the present description vary from about 20 to about 30.
[00029] In some configurations, a polyethylene composition according to the present description also comprises one or more of the following additional characteristics: - Mp equal to or less than about 320,000 g / mol, more preferably equal to or less than about 300,000 g / mol and, in particular, from about 280,000 g / mol to about 180,000 g / mol; - Mz / Mp greater than 4, in particular more than 4.25; MIP from about 0.9 to about 2.1 g / 10 min, alternatively from about 1.2 to about 1.9 g / 10 min; - FIM of about 20 to about 45 g / 10 min, alternatively from about 26 to about 34 g / 10 min; - MIE (fluidity index at 190 ° C with a load of 2.16 kg according to ISO 1133): less than 5 grams / 10 minutes, in particular less than about 1 g / 10 min; - Titanium content of about 0.5 to about 4 parts per million (or "ppm") by weight; - Magnesium content of about 5 to about 15 ppm by weight; - Comonomer content equal to or less than about 1.2% by weight, in particular from about 0.05% to about 1.2% by weight, in relation to the total weight of the composition.
[00030] - ILO at 200 ° C (oxidative induction time according to ASTMDE308) of more than 6 minutes, and in particular more than 10 minutes; and
[00031] - CIT (whiteness index according to ASTM E308) of more than 80.
[00032] In some configurations, the polyethylene composition may also comprise a comonomer or comonomers present in ethylene copolymers, which are generally selected from olefins of formula CH2 = CHR, characterized by R being an alkyl (c <i2) or substituted alkyl (c <i2). Some non-limiting examples of comonomers are propylene, 1-butene, 1-pentene, 4-methylpent-1-ene, 1-hexene, 1-octene and 1-decene. In some configurations, the comonomer is 1-hexene.
[00033] The density of a polyethylene composition can be used to determine possible applications of the polymer. In some configurations, the density of the polyethylene compositions according to the present description is: - about 0.950 to about 0.970 g / cm3 or from about 0.950 to about 0.960 g / cm3 or from about 0.950 to about 0.959 g / cm3; - from about 0.952 to about 0.970 g / cm3 or from about 0.952 to about 0.960 g / cm3 or from about 0.950 to about 0.959 g / cm3; - from about 0.953 to about 0.970 g / cm3 or from about 0.950 to about 0.960 g / cm3 or from about 0.953 to about 0.959 g / cm3;
[00034] In some respects, the index of long branched chains of the present description may influence the applications of the polymer. The index of long branched chains is defined as the ratio between the mean square radius of the rotation Rg, measured by GPC-MALLS, and the mean quadratic radius of the rotation of a linear PE with the same molecular weight or as defined in the Examples. In some embodiments, the LCBI ranges for the polyethylene composition of the present description range from about 0.70 to about 0.50. In some configurations, the LCBI range is about 0.69 to about 0.50. In some configurations, the LCBI range is about 0.65 to about 0.50.
[00035] In some embodiments, the polyethylene composition comprises two polyethylene homopolymers or copolymers or a homopolymer and copolymer. In some configurations, one polyethylene component comprises from about 1% to about 99% by weight of the total weight, and the other polyethylene component comprises the remaining percentage of the total weight. In a preferred embodiment, the present composition comprises: about 40% to about 60% by weight of an ethylene homopolymer or copolymer with a density equal to or greater than about 0.960 g / cm3 and an MIE melt index at 190 ° C with a load of 2.16 kg, according to ISO 1133, from about 5 to about 20 g / 10 min; and about 40% to about 60% by weight of an ethylene copolymer with an MIE lower than the MIE of (A), preferably less than about 0.5 g / 10 min.
[00036] In some configurations, (A) comprises a homopolymer. The percentages above are shown in relation to the total weight of (A) + (B), provided that the total weight is not more than 100 percent. The amount of comonomer in (B) is preferably 0.1% to 2% by weight relative to the total weight of (B).
[00037] In some respects, the present polyethylene composition is used to prepare hollow blow-molded and extruded articles. In some configurations, the polyethylene composition is used to produce small blow-molded articles. Some non-limiting examples of small molded articles by blow are bottles, tubes, seals, guides, boxes and containers. In some configurations, polyethylene compositions require less than about 100 ppm to zero oxygen during pelleting. Without being restricted to any theory, a low oxygen concentration during pelletization improves the color of the resin and the viability of the manufacture, in addition to reducing the propensity for formation of gels in the resin, thus expanding the possible applications of the composition. Other uses of a polyethylene composition of the present description would be recognized by persons skilled in the art and are based on the exact properties of the ethylene composition produced. In some configurations, the polyethylene composition comprises one or more of the following desirable characteristics: - Mold expansion ratio equal to or greater than about 160%; in particular from about 160% to about 185%; and preferably from about 162% to about 170%; - Notch tensile impact test (T = -30 ° C) of about 80 kilojoules per square meter ("kJ / m2") or greater; Charpy aCN (T = -30 ° C) of 4 or more; - Resistance to fracture by environmental stress measured by FNCT of 4 MPa / 80 ° C> about two hours.
[00038] In some configurations, the polyethylene composition of the present description can be processed in a molten state under high levels of shear rate without suffering pressure fluctuations or flow instabilities. This makes it useful for preparing hollow blow-molded and extruded articles.
[00039] The polyethylene composition described in the present description can be prepared using various types of polymerization processes, including, without limitation, gas phase, solution phase, multiphase or fluidized bed polymerization processes. In addition, the polyethylene composition can also be prepared using any catalyst known to improve polyolefin production, including, without limitation, a Ziegler-Natta catalyst, a metallocene or a chromium-based catalyst. In some preferred configurations, the polyethylene composition of the present description can be prepared by a gas phase polymerization process in the presence of a Ziegler-Natta catalyst.
[00040] A Ziegler-Natta catalyst comprises the product of the reaction of an organometallic compound of groups 1, 2 or 13 of the Periodic Table of elements with a transition metallic compound of groups 4 to 10 of the Periodic Table of elements (new notation) . In particular, the transition metal of the compound can be selected from the compounds Ti, V, Zr, Cr and Hf and, preferably, be supported by MgCh. In some configurations, the catalyst comprises the reaction product of said organometallic compound of group 1, 2 or 13 of the Periodic Table of elements with a solid catalyst component comprising a Mg compound supported by MgCh. In some configurations, organometallic compounds contain Al, B and / or Li. In some configurations, organometallic compounds are organoaluminated compounds. In some configurations, such organoaluminated compounds include aluminoxanes or trialkylalumin.
[00041] In certain configurations, polyethylene compositions according to the present description can be obtained using a Ziegler-Natta polymerization catalyst. In some configurations, the Ziegler-Natta catalyst is supported by MgCh. In some configurations, the Ziegler-Natta catalyst is the product of the reaction between: a solid catalyst component comprising a Ti compound supported by MgCh; (b) an organoaluminated compound; and, optionally, (c) an external EDext electron donor compound.
[00042] In certain configurations, the titanium compound used in the Ziegler-Natta polymerization catalyst is a titanium (IV) salt. In some configurations, titanium compounds are the tetrahalides of compounds with the formula TiXn (OR1) 4-n, where 0 <n <3, X is halogen and R1 is an alkyl group (c <w). In some configurations, titanium compounds are titanium tetrachloride or titanium tetralcoxylate.
[00043] In the solid catalyst component, several different solid supports can be used, including salts of magnesium, silica, alumina, titanium oxide or other inert porous material with high surface area. In some configurations, basic support is MgCh. In some configurations, MgCh contains small amounts of other carriers, but so that MgCh constitutes more than 50% of the solid support. The use of MgCh or MgCh obtained from precursor compounds of Mg that can be transformed into MgCh by reaction with halogenating compounds is contemplated. In some configurations, MgCh is used actively as a support for Ziegler-Natta catalysis, as taught in U.S. Patents 4,298,718 and 4,495,338, which are hereby incorporated by reference. Without being restricted to any theory, the magnesium dihalides in active form used as support or co-support are characterized by X-ray spectra in which the most intense diffraction line that appears in the portion of the inactive halide spectrum contained in the card of reference ASTM is less intense and wider. In some configurations, the reduced intensity and the widening of the more intense diffraction lines cause the line to be replaced by a halo-shaped peak, whose maximum intensity is shifted towards smaller angles in relation to the more intense line.
[00044] In some configurations, polyethylene compositions according to the present description are prepared using catalysts characterized by the fact that the solid catalyst component is obtained by placing the titanium compound in contact with MgCh or with an Mg compound precursor at a temperature of 130 to 150 ° C. In some configurations, the preparation comprises placing the titanium compound in contact with MgCl2 or the precursor Mg compound in an inert environment. In some configurations, the temperature is preferably from about 135 to about 150 ° C. Contact with the titanium compound can be made one, two, three, four or more times. In some configurations, contact with the titanium compound is carried out for a total period of about one hour to about 4 hours. The preparation of the solid catalyst can comprise raising the temperature over a period of time from about 30 minutes to about two hours and then maintaining the reaction at that temperature for a period of time from about 30 minutes to about two hours .
[00045] In some configurations, the contact of MgCl2 or the precursor Mg compound with titanium is carried out in the presence of an electron donor compound. Some non-limiting examples of electron donor compounds are compounds that contain an isolated pair of electrons or a liquid negative dipole on their molecular surface. In some configurations, the electron donor compound used to prepare the said Ziegler-Natta catalysts is preferably selected from the group formed by ethers, esters, amines, ketones, nitriles, silanes and their respective mixtures.
[00046] In some configurations, a precursor to MgCl2 can be used as the initial Mg compound. In some configurations, the Mg compound has the formula MgR'2, where R 'is alkyl (C≤20), substituted alkyl (C≤20), OR, OCOR or chlorine, where R is alkyl (C≤20) ), substituted alkyl (C≤20), with the proviso that the R 'are not both chlorines. In addition, Lewis adducts between MgCl2 and the appropriate Lewis bases can also be used as precursor Mg compounds. A particular and preferred class consists of MgCl2 (R''OH) m adducts in which the R "is an alkyl (C <20) or alkylated) substituted in is about 0.1 to about 6. In some configurations, m is about 0.5 to about 3. In some configurations, m is about 0.5 to about 2. Adducts of this type can be obtained by mixing alcohol and MgCh in the presence of an inert hydrocarbon immiscible with the adduct, operating under stirring conditions at the melting temperature of the adduct (100-130 ° C), then the emulsion is quickly cooled, causing the adduct to solidify with spherical particle formation. spherical adducts are described, for example, in U.S. Patent No. 4,469,648; US Patent No. 4,399,054 and in International Patent Application WO 98/44009, which are incorporated herein by reference. spherulization is the spray cooling described, for example, in U.S. Patent No. 5.10 0.849 and 4.829.034, which are both incorporated by reference.
[00047] In some configurations, adducts of MgCl2 «(EtOH) m in which the m ranges from about 0.15 to about 1.7 are obtained by subjecting adducts with a higher alcohol content to a process of thermal de-alcoholisation . The de-alcoholization process can be carried out under nitrogen flow at temperatures between about 50 and about 150 ° C until the alcohol content is reduced to the above value. This process is described, for example, in European Patent EP 395083, which is incorporated herein. In some configurations, the de-alcoholization process can be carried out chemically by placing the adduct in contact with compounds capable of reacting with alcohol groups.
[00048] In some configurations, these de-alcoholized adducts are also characterized by porosity (measured by the mercury method) with pores with radii of up to 0.1 pm and pore volumes between 0.15 and 2.5 cm3 / g. In some configurations, the pore volume range ranges from about 0.25 to about 1.5 cm3 / g.
[00049] The solid can be recovered by separating the suspension using conventional methods (such as decantation followed by removal of the liquid, filtration or centrifugation) and can be subjected to solvent washes. In some configurations, the solid waste is washed with liquid inert hydrocarbons. In other configurations, the solid waste is washed using more polar solvents (which have, for example, a higher dielectric constant), including halogenated hydrocarbons.
[00050] In some configurations, said solid catalyst component is converted into catalysts for polymerization of olefins when reacted, according to known methods, with an organometallic compound of group 1, 2 or 13 of the Periodic Table of elements. In some configurations, the organometallic compound is an organoaluminated compound. In some configurations, the organoaluminated compound is AI (YI) 3, where Yi is an alkylate), a hydride or a halide. In some configurations, the organoaluminated compound is a trialkylaluminium compound. Some non-limiting examples of trialkylaluminium compounds are triethylalumin, triisobutylalumin, tri-n-butylalumin, tri-n-hexylalumin and tri-n-octylalumin. The use of alkyl aluminum halides, alkyl aluminum hydrides or alkyl aluminum sesquichlorides, such as AIEt2CI and AhEtaCh in admixture with said trialkyl aluminum compounds is also contemplated.
[00051] In some configurations, the catalyst can be prepolymerized according to known techniques by producing reduced amounts of polyolefins prior to the polymerization necessary to achieve the present description. In some configurations, the polyolefin is polypropylene or polyethylene. The amount of prepolymer produced can vary from about 0.5 grams per gram of component a) to about 500 grams per gram of component a). In some configurations, the amount of prepolymer produced is about 1 gram per gram of solid catalyst.
[00052] In some aspects of the present description, the polyethylene compositions according to the present description can be prepared using a polyethylene catalyst described above in a process characterized by comprising the following steps: a. supplying at least an initial amount of ethylene to a first gas phase reactor; B. supplying at least an initial amount of a Ziegler-Natta catalyst to the first gas phase reactor to supply at least an initial amount of polyethylene polymer within the first gas phase reactor; ç. transferring at least part of the initial amount of the polyethylene polymer and at least part of the initial amount of the Ziegler-Natta catalyst to a second gas phase reactor; supplying at least a second amount of ethylene in the presence of an initial amount of hydrogen to the second gas phase reactor to obtain a second polyethylene polymer to produce a polyethylene composition characterized in that it comprises the first polyethylene polymer and the second polymer of polyethylene; characterized by the fact that at least one of the first and second gas phase reactors comprises a first and a second polymerization zone, the first polymerization zone has a first hydrogen pressure and the first hydrogen pressure is different from the second pressure of hydrogen, so that at least part of the second quantity of ethylene travels through the first and second polymerization zones and at least part of the gas mixture of each polymerization zone is totally or partially prevented from entering the other zone. In some configurations, in at least one of the first and second gas phase reactors, the growing polymer particles flow upwards through a first polymerization zone (hereinafter also called riser) under conditions of rapid fluidization or transport, leaving the riser and enter a second polymerization zone (hereinafter also called downcomer), through which they flow down under the action of gravity, leave the downcomer and are reintroduced into the riser, thus establishing a polymer circulation between the two polymerization zones. In some configurations, the polymerization of ethylene in step (a) or in step (d) also comprises a comonomer. In some configurations, the polymerization of ethylene in step (a) also comprises hydrogen.
[00053] In the first polymerization zone (riser), rapid fluidization conditions are created by adding a gas mixture containing one or more olefins (ethylene and comonomers) at a rate higher than the transport speed of the polymeric particles. The flow of said gas mixture is preferably comprised between about 0.5 and about 15 meters per second ("m / s") and more preferably from about 0.8 to about 5 m / s. The terms "transport speed" and "fast fluidization conditions" are well known in the art. For an alternative definition of these terms, see, for example, D. Geldart, 1986, which is incorporated by reference.
[00054] In some aspects of the present description, a restriction is introduced between the first polymerization zone (riser) and the second polymerization zone (downcomer). In some configurations, the restriction leads to individual flow conditions in each of the polymerization zones. In some configurations, the individual flow conditions comprise the variation of the concentration of hydrogen or comonomer in the polymerization zone. In some configurations, the restriction comprises a barrier. In some configurations, the barrier is a gaseous or liquid barrier. In some configurations, the gas mixture originating from the riser is partially or totally prevented by the barrier from entering the downcomer. In some configurations, the necessary condition to create a barrier can be realized by introducing a gas in the upper part of the downcomer and / or a liquid mixture with a different composition than the gas mixture present in the riser. In some configurations, this mixture of gas and liquid is fed to the top of the downcomer, replacing all or part of the gas mixture interspersed between the polymer particles that enter the downcomer. In addition, in some configurations the flow rate of the gas and liquid mixture can be regulated so that a gas flow forms a countercurrent to the flow of polymeric particles at the top of the downcomer.
[00055] In some aspects of the present description, the barrier in the second polymerization zone is a gas barrier. Without being restricted to any theory, the countercurrent flow of gas that acts as a barrier to the gas mixture originating from the riser, which is trapped between the polymeric particles because the established upward gas flow has the effect of preventing the gas mixture in the riser enter the downcomer. In some configurations, the mix of different compositions fed to the top of the downcomer can be partially or totally liquefied. The liquefied gas mixture can also be sprayed on the downcomer so that evaporation of the liquid in the polymerization zone provides the necessary gas flow.
[00056] In some aspects of the present description, the barrier in the second polymerization zone is a liquid barrier. In some configurations, the barrier comprises the introduction of a liquid solution at the entrance of the downcomer. Without being restricted to any theory, the liquid solution extracts the gas mixture from the polyethylene riser, so that the concentrations of hydrogen and comonomer in the downcomer approximate those of the liquid solution. In some configurations, the liquid barrier originates from the recycled flow of unreacted gas molecules from the riser.
[00057] In one aspect, in the second polymerization zone (downcomer), the polymeric particles flow under gravity and in a more dense form so that the density of the solid reaches high values (mass of polymer per reactor volume). In some configurations, these density levels can approximate the apparent density of the polymer. Currently, the applicant believes that the polymer flows vertically downward through the downcomer creating a "blocking flow" (compacted flow mode), so that only small amounts of gas are interspersed between the polymer particles. In some configurations, the process produces, from step (a), an ethylene polymer with a lower molecular weight than the ethylene copolymer obtained in step (d).
[00058] In one aspect of the present description, polymerization of ethylene to produce a relatively low molecular weight ethylene polymer (step a) is carried out upstream of the copolymerization of ethylene with a comonomer in order to produce a weight ethylene copolymer relatively high molecular weight (step e). In some configurations, step (a) is a gas mixture comprising ethylene, hydrogen and an inert gas, which are introduced into a first gas phase reactor. In some configurations, the gas phase reactor is a fluid phase gas phase reactor. In some configurations, polymerization is carried out in the presence of the Ziegler-Natta catalyst described above. In some configurations, no comonomer is introduced into the gas phase reactor and a highly crystalline ethylene homopolymer is obtained in step (a); In other configurations, a minimum amount of comonomer can be introduced in the first gas phase reactor, with the proviso that the degree of copolymerization in step a) is limited so that the density of the ethylene polymer obtained in step (a) is not less than 0.960 g / cm3.
[00059] In some configurations, the use and the amount of hydrogen depends on the specific catalyst used. In some configurations, the amount of hydrogen used is adequate to obtain in step (a) an ethylene polymer with an MIE fluidity index of 5 to 20 g / 10 min. To obtain the MIE range above in step (a), the hydrogen / ethylene molar ratio used can be from about 0.5: 1 to about 3: 1, and the amount of ethylene monomer ranges from 2% to 15 % by volume according to the total volume of gas present in the polymerization reactor. In some configurations, the amount of ethylene monomer is about 5% to about 10% by volume. The remaining portion of the introduced mixture is represented by inert gases and one or more comonomers, if any. In some configurations, inert gases are required to dissipate the heat generated by the polymerization reaction. In some configurations, any inert gas can be employed. In some configurations, the inert gas is selected from hydrogen or saturated hydrocarbons. In some configurations, the inert gas is propane.
[00060] In some configurations of the present description, the operational conditions of the polymerization reactor in step (a) are characterized by the fact that it comprises an operating temperature of about 50 to about 120 ° C. In some configurations, the operating temperature is around 65 to 100 ° C. In some configurations, the operating pressure of the polymerization reactor in step (a) is about 0.5 to about 10 MPa. In some configurations, the operating pressure is about 2.0 to about 3.5 MPa. In some configurations, the operating temperature is about 80 ° C and the operating pressure is about 2.9 MPa.
[00061] In some configurations, the ethylene polymer obtained in step (a) represents 40% to 60% by weight of the total ethylene polymer produced in the process as a whole, that is, in the first and second reactors connected in series .
[00062] In some configurations, the ethylene polymer obtained in step (a) and the interspersed gas are subjected to a gas and solid separation step in order to prevent the gas mixture that leaves the first polymerization reactor to enter the reactor step (d) (second gas phase polymerization reactor). In some configurations, the gas mixture can be recycled by returning to the first polymerization reactor while the separated ethylene polymer is sent to the reactor in step (d). In some configurations, an appropriate point for introducing the polymer into the second reactor is the portion that connects the riser to the downcomer, in which the solid concentration is especially low, so that the flow conditions are not adversely affected.
[00063] In some configurations, the operating temperature in step (d) is about 65 to about 95 ° C, and the pressure is about 1.5 to about 4.0 MPa. In some configurations, in the second gas phase reactor, ethylene is copolymerized with one or more comonomers. In addition, in some configurations the reactor in step (d) is operated so that different conditions for monomers and hydrogen concentrations are created in the riser and downcomer.
[00064] In some aspects of the present description, the gas mixture interspersed in the polymer particles that comes from the riser in step (d) can be partially or totally prevented from entering the downcomer, in order to obtain two different zones of gas composition. In some configurations, the two zones of different gas composition are obtained by introducing a gas and / or liquid mixture into the downcomer through a tube positioned at an appropriate point on the downcomer. In some configurations, the tube is placed on top of it. In some configurations, the gas and / or liquid mixture has an appropriate composition, different from that of the gas mixture present in the riser, so that two different gas composition zones are created. In some configurations, the flow of the gas and / or liquid mixture it can be regulated to produce an upward gas flow that flows in the opposite direction to the flow generated by the polymer particles. In some configurations, the separation is more effective at the top of it, so that the flow acts as a barrier to the gas mixture interspersed in the polymer particles originating from the riser. In particular, the ability to introduce a mixture with a low hydrogen content in order to produce higher molecular weight polymers in the downcomer is especially advantageous. One or more copolymers can be introduced into the downcomer of step (d), optionally at the same time as ethylene, propane or other inert gases.
[00065] In some configurations, the hydrogen / ethylene molar ratio in the downcomer of step (d) is about 0.005 to about 0.2 and the ethylene concentration per volume is about 1% to about 20% per volume, or comonomer concentration is from 0.2% to 1% by volume based on the total volume of gas present referred to downcomer. In some configurations, the ethylene concentration is about 3 to about 10%. In some configurations, the remainder of the gas volume consists of propane or other inert gases. In some configurations, the present description provides the ability to produce relatively high amounts of comonomer, which is incorporated into the high molecular weight polyethylene fraction.
[00066] In some configurations the polymer particles originating from the downcomer are reintroduced into the riser in step (d). In some configurations, the comonomer concentration drops to a range of 0.1% to 0.5% by volume, based on the total volume of gas present in the riser. In some configurations, the content and identity of the comonomer are controlled in order to obtain the final polyethylene with the desired density. In some configurations, the riser contains hydrogen and ethylene in a molar ratio of about 0.2 to about 1 or an ethylene concentration of about 5% to about 15% by volume relative to the total volume of gas present in the riser. In some configurations, the remainder of the total volume of gas present in the riser consists of propane or other inert gases. EXAMPLES
[00067] The following Examples are included to demonstrate specific configurations of the present description. Those skilled in the art should realize that the techniques described in the following examples represent techniques that the inventor found to work well in the practice of this description and, therefore, can be considered specific modes for their practice. However, those skilled in the art should, by virtue of this description, note that many changes can be made to the specific configurations described here with a similar or similar result, without departing from the spirit and scope of this description.
[00068] Except where otherwise indicated or suggested, the following experimental methods have been used to determine the characteristic properties reported in the detailed description and examples. Density
[00069] The density is determined according to ISO 1183 at 23 ° C. Determination of the molecular weight distribution
[00070] The determination of the molar mass distributions and the means of Mn, Mp, Mz and Mp / Mn derived from them was carried out by high temperature gel permeation chromatography using a method described in ISO 16014-1, 16014-2 , 16014-4, 2003 editions. The specific details mentioned in the ISO standards are as follows: 1,2,4-trichlorobenzene (TCB) as a solvent, apparatus and solutions at a temperature of 135 ° C and detection of concentrations using the infrared IR-4 from PolymerChar (Valencia, Paterna 46980, Spain), which can be used with TCB. A WATERS Alliance 2000 equipped with a SHODEX UT-G back column and SHODEX UT 806 M (3x) and SHODEX UT 807 separation columns (Showa Denko Europe GmbH, Konrad-Zuse-Platz 4, 81829 Munich, Germany) connected in series was employed. The solvent was vacuum distilled into nitrogen and stabilized with 0.025% by weight of 2,6-di-tert-butyl-4-methylphenol. The flow rate used was 1 ml / min, the injection was 500 pl and the polymer concentration was in the range 0.01% <conc. <0.05% w / w. The molecular weight calibration was established using monodispersed polystyrene (PS) standards from Polymer Laboratories (currently Agilent Technologies, Herrenberger Str. 130, 71034 Boeblingen, Germany) in the range of 580 g / mol to 11,600,000 g / mol and also with hexadecane. The calibration curve was then adapted for polyethylene (PE) using the universal calibration method (Benoit et al., 1967, which is incorporated by reference). The Mark-Houwing parameters used for the same were: for PS, kps = 0.000121 dL / g and aps = 0.706; for PE, kpE = 0.000406 dL / g, QPE = 0.725, valid with TCB at 135 ° C. Data recording, calibration and calculation were performed with NTGPC_Control_V6.02.03 and NTGPC_V6.4.24 (hs GmbH, HauptstraBe 36, D-55437 Ober-Hilbersheim, Germany) respectively. Shear-induced crystallization test
[00071] This method was used to determine the shear-induced crystallization (SIC) initiation time of the polymer, or Udo, sic. The fused samples are pressed at 200 ° C for 4 minutes at 200 bar in a laboratory press until 1 mm thick plates are formed. Then, the samples are cut into 25 mm diameter discs and placed in a two-plate oscillatory rheometer. A Anton Paar Physica MCR 301 rotary rheometer was used.
[00072] Then, the sample is melted inside the test geometry at 190 ° C for 4 minutes and cooled to approximately 10 Kelvin / minute until it reaches the test temperature T = 125 ° C and is annealed for 5 minutes. Thus, shear was applied with a constant shear rate, and the shear rate was monitored as a function of time. The experiment was repeated applying a shear rate at a time, ranging from 0.05 to 0.5 seconds1. The SIC start time, tinkle, sic, was brought to the point where the viscosity had increased up to 50% of its equilibrium value q at 125 ° C. The equilibrium value is the average viscosity of the molten sample and under constant shear measured at a specific temperature.
[00073] The log tinício, sic vs. graph. log of the shear rate shows a linear function (of type y = Ax + B), which is extrapolated to a shear rate of 1000 seconds1 (relevant to the process) to determine the tin value, sic to 1000. Then, the SIC index is calculated according to the following ratio: SIC index = (tinium, SIC @ 1000 xt start, quiescent) / (MIF)
[00074] Tinium, quiescent (in seconds) indicates the start of crystallization at a temperature of 125 ° C under quiescent conditions, that is, without shear, measured in the isothermal mode in a differential scanning calorimetry apparatus, as explained below . The MIF is the fluidity index (g / 10 min) measured at T = 190 ° C with a load of 21.6 kilograms according to ISO 1133. The same protocol is described in Vittorias, 2010; Wo and Tanner, 2010; and Derakhshandeh and Hatzikiriakos, 2012, which are hereby incorporated by reference. Isothermal DSC
[00075] Tinium, quiescent is the start time when there is no deformation applied at 125 ° C and is determined by the iso-DSC method (differential isothermal scanning calorimetry). It is measured at 125 ° C on a TA Instruments Q2000 DSC apparatus. The determination of quiescent tinium is performed using the commercially available software TA Universal Analysis 2000. The sample preparation and assembly were in accordance with DIN EN ISO 11357-1: 2009 and ISO 11357-3: 1999. Complex shear viscosity
[00076] The complex shear viscosity is measured at an angular frequency of 0.02 radians per second ("rad / s") and at 190 ° C as follows. The fused samples are pressed for 4 minutes at 200 ° C and 200 bar on 1 mm thick plates. Samples of 25 mm diameter discs are stamped and placed on the rheometer preheated to 190 TIC. Measurement can be performed by any commercially available rotational rheometer. The Anton Paar MCR300 model was used with two plate configuration. The so-called frequency sweep was carried out (after four minutes of annealing the sample at the measuring temperature) at T = 190 71C under 5% stress amplitude, measuring and analyzing the response of the material to stress at excitation frequencies co 670 to 0.02 rad / s. Standardized basic software is used to calculate rheological properties, that is, storage module G ', loss module G ", phase delay õ (= arctan (G" / G')) and complex viscosity q * as a function of the applied frequency, specifically q * (co) = [G '(co) 2 + G "(co) 2] 1/2 / co. The value of the latter in the applied frequency co of 0.02 rad / s is the eta (0.02). fluidity index
[00077] The fluidity index is determined according to ISO 1133 at 190 ° C with the specified load. For MIP, the load is 5 kilograms; for MIF, the load is 21.6 kilograms. long chain branching index (LCBI)
[00078] The LCB index corresponds to the branching factor g 'measured at a molecular weight of 106 g / mol. The branching factor g ', which allows the determination of long chain branches when Mp is high, was measured by gel permeation chromatography (GPC) coupled with multi-angular scattering of laser light (MALLS, “multi- angle laser-light scattering "), as described below. The parameter g 'is the relation between the mean of the squares of the turning radii in relation to a linear polymer with the same molecular weight. Linear molecules have g 'equal to 1, and values less than 1 indicate the presence of LCB. The values of g 'as a function of the molecular weight M were calculated using the equation: g' (M) = <Rg2> sample, M / <Rg2> ref. linear, M where <Rg2>, M is the mean of the square of the turning radius for the fraction with molecular weight M.
[00079] The turning radius for each fraction eluted in GPC (as described above, but with a flow rate of 0.6 ml / min in a column filled with 30 pm particles) is measured by analyzing the light scattering over several angles. Therefore, from this MALLS configuration it is possible to determine the molecular weight Meo <Rg2> sample.M, in addition to defining g 'in the presence of the measure M = 106 g / mol. The <Rg2> ref. linear, M is calculated by the relationship established between the turning radius and the molecular weight for a solution of linear polymers (Zimm and Stockmayer WH 1949) and confirmed by measuring a PE reference with the same apparatus and the same methodology described. The same protocol is described in Zimm and Stockmayer, 1949 and in Rubinstein and Colby, 2003, which are incorporated by reference.
[00080] Atomic absorption spectrometry (for determining Mg content)
[00081] This method was used to determine residual Mg and was carried out with a Varian spectrometer (currently Agilent) AAS 220FS. The samples were homogeneous, and all measurements were performed in duplicate. For sample preparation, 250 milligrams (± 0.1 milligrams) of the sample are weighed and placed in the tubes. For the solution, 6 mL of concentrated HNO3 is added and the tube is sealed and introduced into a microwave oven (MLS Start 1500). The heating program used depends on the shape of the sample. For 0 granules: 5 minutes at 50 ° C 15 minutes at 150 ° C 10 minutes at 200 ° C -10 minutes at 210 ° C For 0 powder: 5 minutes at 50 ° C - »20 minutes at 150 ° C 15 minutes a200 ° C - »10 minutes at 210 ° C
[00082] Then, the tubes are allowed to cool to at least 60 ° C and the dissolved samples are transferred to 50 ml volumetric flasks with the addition of a solution of 5 ml of lanthanum chloride and 50 ml of ultrapure water. The measurement is best performed at a wavelength of 285.2 nm with an absorbance in the range of 0.0100 to 0.3500 nm. If necessary, samples can be further diluted to reach this range. The measurement is carried out with an air and acetylene flame with flow rates of 13.5 and 2 liters per minute ("L / min"), respectively. For calibration, samples of concentration between 0.01 milligrams per liter ("mg / L") to 1 mg / L are prepared and measured appropriately (from commercially available Mg reference solutions). Determination of Ti content
[00083] The residual content of Ti in the polymer was determined using the mass balance of the polymerization process. Comonomer content
[00084] The comonomer content is determined by infrared according to ASTM D 6248 98 using a Fourier transform infrared spectrophotometer (FT-IR, "Fourier transform infrared") Bruker's Tensor 27 calibrated with a chemometric model for determination of ethyl or butyl side chains in PE having butene or hexene as comonomers, respectively. The result was compared with the comonomer content estimated from the mass balance of the polymerization process and found to be compatible. Expansion ratio
[00085] The expansion ratio of the studied polymers is measured using a capillary rheometer Gõttfert Rheotester2000 and Rheograph25 at T = 190 ° C equipped with a commercial mold 30/2/2/20 (total length 30 mm, active length 2 mm , diameter 2 mm, C / D = 2/2 and entry angle of 20 °) and an optical device (laser Göttfert diode) to measure the wire thickness and extruded. The sample was melted in a capillary tube at 190 ° C for 6 minutes and extruded with the piston at a speed corresponding to the resulting shear rate in the mold of 1440 seconds S The extrudate was cut (by a Göttfert automatic cutter device) at a distance of 150 mm from the mold in the moment when the piston reached a position 96 mm from the mold inlet, the diameter of the mold outlet as a function of time, U maximum value corresponds to the D e xtr uated ■ The expansion ratio is determined by the calculation. SR - (D e xtr u d D o Dmold) 100% / Dmold, where D moide is the corresponding diameter at the exit of the mold, a diameter that is measured by a laser diode. Notch Tensile Impact Test
[00086] The tensile strength to impact is determined according to ISO 8256: 2004 using type 1 samples with two notches according to method A. The tested samples (4 × 10 × 80 mm) are cut from a compression molded sheet prepared in accordance with the requirements of ISO 1872-2 (average cooling rate 15 K / min and high pressure during the cooling phase). The samples to be tested are grooved on two slides with a V-notch at 45º. The depth is 2 ± 0.1 mm, the radius of curvature at the notch angle 1.0 ± 0.05 mm and the free length between the presses 30 ± 2 mm. Before measuring, all samples tested are conditioned at a constant temperature of -30 ° C for a period of two to three hours. The procedure for measuring tensile strength to impact with energy correction according to method A is described in ISO 8256. Fracture resistance by environmental stress according to the notched creep test (FNCT, "full notch creep test")
[00087] The environmental stress fracture resistance test of polymer samples is determined according to the international standard ISO 16770 (FNCT) in aqueous surfactant solution.From the polymer sample, a 10 mm compression-molded sheet thick is prepared. Then, the bars with square cross section (10 x 10 x 100 mm) are grooved with a razor blade on the four sides perpendicular to the direction of tension. A carving device described by M. Fleissner in Kunststoffe 77 (1987), pp. 45 was used to create a fine groove 1.6 mm deep. The applied load is calculated from the tensile strength divided by the area of the initial ligament. The ligament area is the remaining area = total cross-sectional area of the sample minus the notch area. In the sample for FNCT: 10 x 10 mm2 - 4 times the area of the trapezoidal notch = 46.24 mm2 (the rest of the cross section for the crack failure / propagation process). The test sample was loaded under the standard conditions suggested in ISO 16770 under a constant load of 4 MPa at 80 ° C in a solution in water at 2% (by weight) of the nonionic surfactant ARKOPAL N100. The time to rupture of the test sample is measured. Charpy aCN
[00088] The determination of fracture resistance is performed by an internal method on test bars measuring 10 x 10 x 80 mm that had been sawn from a 10 mm thick compression-molded sheet.Six of these test bars were grooved in the center with a razor blade using the grooving device mentioned above for FNCT. The depth of the notches was 1.6 mm. The measurement is performed basically according to the Charpy measurement method and with ISO 179-1, using modified test samples and modified impact geometry (distance between the supports). All test samples are conditioned under the measuring temperature of -30 ° C for a period of 2 to 3 hours. Then, a test sample is immediately placed on the support of a pendulum impact tester according to ISO 179-1.The distance between the supports is 60 mm. The fall of the 2 J hammer starts with the fall angle set to 160 °, pendulum length 225 mm and impact speed 2.93 m / s. The fracture resistance value is measured in kJ / m2 and according to the quotient of the impact energy consumed and the initial transversal area of the notch, aCN. Only values for complete fractures or hinge fractures can be used as a basis for a common dignified (see suggestion in ISO 179-1). EXAMPLE 1 Process preparation
[00089] In Example 1, a process configuration of the present description was performed under continuous conditions in an installation comprising two gas phase reactors connected in series, as illustrated in Figure 1.
[00090] In example 1, the solid catalyst component was prepared as follows: an adduct of magnesium chloride and alcohol containing about 3 moles of alcohol was prepared according to the method described in example 2 of United States Patent No. . 4,399,054, which is incorporated by reference, but operating at 2000 RPM instead of 10,000 RPM. The adduct was subjected to heat treatment under a nitrogen flow at a temperature range of 50 to 150 ° C until it reached a 25% alcohol content by weight. In a 2 liter round flask with four necks purged with nitrogen, 1 liter of TiCU was introduced at about 0 ° C. Then, at approximately equal temperature, 70 grams of a spherical MgCh / EtOH adduct containing 25% by weight of ethanol and prepared as described below was added during mixing. The temperature was raised to about 140 ° C in about two hours and maintained for about 60 minutes. Then, the stirring was stopped, the solid was allowed to settle and the supernatant liquid was removed by siphoning.
[00091] Then, the solid residue was washed once with heptane at 80 ° C, five times with hexane at 25 ° C and vacuum dried at 30 ° C. Polymerization
[00092] A sufficient amount of solid catalyst component prepared according to the synthetic route described above was prepolymerized with propylene in an amount of 1 gram of polypropylene per gram of catalyst component, according to the method described in Example 7 of the International Application WO 01/85803, which is incorporated herein by reference.
[00093] The prepolymerized solid catalyst component was prepared at 8 grams per hour ("g / h") was prepared as described above and introduced, using 5 kilograms per hour ("kg / h") of liquid propane, in a pre-contact apparatus in which triisobutylaluminum (TIBA) was dosed. The weight ratio of alkyl aluminum and the solid catalyst component was 2.5: 1. The pre-contraction step was performed under mixing at 25 ° C with a total residence time of 120 minutes.
[00094] In relation to Figure 1, for illustrative purposes, the catalyst was introduced into a first gas phase polymerization reactor 1 in Figure 1 by tube 10. In reactor 1, at least an initial amount of ethylene was polymerized using H2 as molecular weight regulator in the presence of propane as an inert diluent. Reactor 1 received 41.5 kg / h of ethylene and 65 g / h of hydrogen through tube 9 after passing through a compressor 2 and a condenser 3. No comonomer was introduced in reactor 1. In an optional configuration, the hydrogen, ethylene and propane can be reintroduced into reactor 1 through tube 4 through compressor 2 and through condenser 3 from a recycling tube 13 (shown dashed because this flow is optional) of the first gas polymerization reactor 1.
[00095] Polymerization was carried out at a temperature of 80 ° C and under pressure of 2.9 MPa. The operating conditions of reactor 1 are summarized in Table 1. The polymer obtained in reactor 1 was discharged discontinuously by tube 11, separated from the gas in a gas separator and solid 12 and reintroduced in the second gas phase reactor 20 by tube 14 In some configurations of the present description, the gas separated from the separator 12 can be introduced into the reactor 1 through the recycling tube 13 (which appears dashed because this flow is optional) or removed from the system by the tube 15.
[00096] The polymer produced in the first reactor had an MIE flow rate around 10 g / 10 min and a density of 0.966 kg / dm3.
[00097] The second reactor 20 was operated under polymerization conditions of about 84 ° C and a pressure of 2.5 MPa. 9 kg / h of ethylene, 6 g / h of hydrogen and 0.8 kg / h of 1-hexene 33 from the second reactor 20 were introduced into the downcomer (also called the second polymerization zone 20) via tube 46. Also introduced in the recycling system through tube 45, through tube 44, 5 kg / h of propane, 27 kg / h of ethylene and 5 g / h of hydrogen. After passing through a compressor in the second reactor 47, the propane, ethylene and hydrogen were distributed through the tube 56 and directed to a first condenser of the second reactor 48 and to a second condenser of the second reactor 49.
[00098] Currently, the applicant believes that, in order to extend the molecular weight distribution of the final ethylene polymer, the second reactor 20 was operated by establishing different conditions for monomer and hydrogen concentrations in a riser (also here called the second zone of polymerization) 32 and in a downcomer 33. Currently, the applicant believes that the different conditions were obtained by introducing tube 52, 330 kg / h of a liquid flow (liquid barrier) in a part, portion or upper region of the downcomer 33 The liquid flow 52 had a different composition than the gas mixture present in the riser 32. The various concentrations of monomers and hydrogen in the riser 32 and in the downcomer 33 of the second reactor 20 and the composition of the liquid barrier are shown in Table 2. The liquid flow of tube 52 comes from the condensation step in the second condenser of the second reactor 49 in working conditions of 46 ° C and 2.5 MPa, where a part of the recycling flow through the tube 57 it is cooled and partially condensed. As shown in Figure 1, a separation vessel 50 and a pump 51 are placed, in that order, downstream of the second condenser of the second reactor 49. In addition, the hydrogen, ethylene and / or comonomer can be recycled by the system through the pipe 55, entering riser 32 or downcomer 33 through compressor 47 and condenser 48. The final polymer was discharged continuously through tube 54.
[00099] The polymerization process in the second reactor produced relatively high molecular weight polyethylene fractions. In Table 3, the properties of the final product are specified. Currently, the applicant believes that Table 3 illustrates that the flow rate of the final product is lower compared to the ethylene resin produced in the first reactor, showing the formation of high molecular weight fractions in the second reactor.
[000100] The first reactor produced around 50% by weight (division by weight%) of the total amount of the final polyethylene resin produced in the first and second reactors. At the same time, the polymer obtained had a relatively wide molecular weight distribution, which is indicated by a MIF / MIP ratio equal to 21.8. COMPARATIVE EXAMPLE 1
[000101] The polymer of this comparative example is a prior art polyethylene composition prepared with Cr catalyst in a closed loop reactor. Table 1: Operating conditions of the first reactor
Observations: H2: hydrogen gas; C2H4: ethylene; Table 2: Operating conditions of the second reactor

Observations: H2: hydrogen gas; C2H4: ethylene; C6H12: hexene Table 3: Final polymer properties of Example 1 and Comparative Example 1
Observations: * Arkopal N100 in 2% aqueous solution
[000102] Although the present description and its advantages have been described in detail, it is understood that several modifications, substitutions and changes can be made in it without departing from the spirit and scope of the description, as defined in the attached claims. In addition, it is not intended that the scope of this request be limited to specific configurations of processes, machines, manufacturing, material composition, means, methods and steps described in the specification. As individuals ordinarily versed in the technique will quickly perceive from the description contained in the present description, the processes, machines, manufacture, composition of matter, means, methods or steps, existing or that will be developed in the future, that basically perform the same function or obtain basically the same result as the corresponding configurations described here can be used in accordance with the present description. Likewise, it is intended that the attached claims include in its scope such processes, machines, manufacturing, material compositions, means, methods or stages. References
[000103] The following references, insofar as they provide exemplary procedures or other details in addition to those presented here, are hereby incorporated specifically by reference. U.S. Patent 4,298,718; US patent 4,399,054; US Patent 4,469,648; US Patent 4,495,338; US Patent 4,536,550; U.S. Patent 4,829,034; U.S. Patent 5,100,849; International patent application WO 1994/012568; International patent application WO 1998/044009; International patent application WO 2001/085803; International patent application WO 2005/097888; European patent 395,083; Geldart, "Gas Fluidization Technology," J. Wiley & Sons, Ltd., p 155, 1986; Benoit, et al., J. Polymer Sci., Phys. Ed., 5: 753, 1967; Vittorias, "Correlation among structure, processing and product properties," Würzburger Tage, Wolfgang Kunze TA Instruments, Germany, 2010; Wo and Tanner, "The impact of blue organic and inorganic pigments on the crystallization and rheological properties of isotactic polypropylene," Rheol. Acta, 49:75, 2010; Derakhshandeh and Hatzikiriakos, "Flow- induced crystallization of high-density polyethylene: the effects of shear and uniaxial extension," Rheol. Acta, 51: 315-327, 2012; Rubinstein and Colby, "Polymer Physics," Oxford University Press, 2003 'Zimm and Stockmayer, "The dimensions of chain molecules containing branches and rings," J Chem Phys, 17, 1949.

权利要求:
Claims (17)
[0001]
1. Process for preparing a polyethylene composition, characterized by the fact that it comprises the following steps: (a) supplying at least an initial amount of ethylene to a first gas phase reactor; (b) supplying at least a first initial amount of a Ziegler-Natta catalyst to the first gas phase reactor to produce at least a first initial amount of polyethylene polymer within the first gas phase reactor; (c) transferring at least a part of the first initial amount of the polyethylene polymer and at least a part of the first initial amount of the Ziegler-Natta catalyst to a second gas phase reactor; (d) supplying at least a second amount of ethylene in the presence of a first initial amount of hydrogen to the second gas phase reactor to obtain a second polyethylene polymer to produce a polyethylene composition comprising the first polyethylene polymer and the second polymer of polyethylene, wherein the polyethylene composition comprises a density greater than 0.950 g / cm3, an MIF / MIP ratio of 17 to 25, a long chain branching index of 0.70 and a SIC index of 0.15 to 8, in which the SIC index is determined according to the following relationship: SIC index = (tinnitus, SIC @ 1000 xt start, quiescent) / (MIF) in which tinium, sic @ 1000 is measured in seconds and is the time required for the crystallization start at a shear rate of 1000 s'1, t start, quiescent is measured in seconds and is the time of crystallization start at a temperature of 125 ° C without shear, determined in the isothermal mode by differential scanning calorimetry; wherein at least one of the first or the second gas phase reactor comprises a first and a second polymerization zone, the first polymerization zone having a first hydrogen pressure and the second polymerization zone having a second hydrogen pressure, in that the first hydrogen pressure is different from the second hydrogen pressure, so that at least part of the second amount of ethylene travels through the first and second polymerization zones and at least part of the gas mixture in each polymerization zone is total or partially prevented from entering the other zone, where the polyethylene composition comprises: (A) 40% to 60% by weight of an ethylene homopolymer or copolymer with density equal to or greater than 0.960 g / cm3 and a fluidity index ( MIE) at 190 ° C with a load of 2.16 kg of 5 to 20 grams / 10 minutes; and (B) 40% to 60% by weight of an ethylene homopolymer or copolymer with an MIE value less than the MIE value in (A).
[0002]
Process according to claim 1, characterized by the fact that it comprises the first polymerization zone under conditions of rapid fluidization or transport.
[0003]
Process according to claim 1, characterized by the fact that step (a) and / or step (d) further comprise one or more comonomers.
[0004]
Process according to claim 1, characterized by the fact that the first gas phase reactor and / or the second gas phase reactor further comprise the ethylene being polymerized in an inert diluent.
[0005]
Process according to claim 1, characterized by the fact that the first and the second gas phase reactors are heated to a temperature ranging from 70 ° C to 95 ° C.
[0006]
Process according to claim 1, characterized in that the Ziegler-Natta catalyst comprises a solid catalyst component comprising a titanium compound on a magnesium support and an organoaluminated compound.
[0007]
7. Process according to claim 6, characterized by the fact that the solid catalyst component is produced by contacting the titanium compound with magnesium chloride or a magnesium precursor compound and heated until it reaches a temperature ranging from 130 ° C to 150 ° C.
[0008]
8. Process according to claim 1, characterized by the fact that the SIC index ranges from 0.15 to 2.
[0009]
9. Polyethylene composition, characterized by the fact that it comprises: (a) a first polyethylene, produced in a first gas phase reactor in the presence of an initial amount of hydrogen; and (b) a second polyethylene, produced in a second gas phase reactor in the presence of a second amount of hydrogen, in which the second amount of hydrogen is less than the first amount of hydrogen; wherein the first polyethylene and the second polyethylene are produced in any order and in the presence of a Ziegler-Natta catalyst; wherein at least one of the first or second gas phase reactors comprises a first and a second polymerization zone, the first polymerization zone having a first hydrogen pressure and the second polymerization zone having a second hydrogen pressure, wherein the first hydrogen pressure is different from the second hydrogen pressure, so that at least part of the second amount of ethylene moves through the first and second polymerization zones and at least part of the gas mixture in each polymerization zone is totally or partially prevented to enter the other zone; and where the polyethylene composition also comprises a SIC index from 0.15 to 8 and the fact that the SIC index is determined according to the following relationship: SIC index = (tinium, SIC @ 1000 xt start, quiescent) / (MIF) where tinium, sic @ 1000 is measured in seconds and is the time required for crystallization to start under a shear rate of 1000 s'1, the beginning, quiescent is measured in seconds and is the time for crystallization to start. at a temperature of 125 ° C without shear, determined in the isothermal mode by differential scanning calorimetry; wherein the polyethylene composition comprises: (A) 40% to 60% by weight of an ethylene homopolymer or copolymer with density equal to or greater than 0.960 g / cm3 and a fluidity index (MIE) at 190 ° C with a load of 2.16 kilograms of 5 to 20 grams / 10 minutes; and (B) 40% to 60% by weight of an ethylene homopolymer or copolymer with an MIE value less than the MIE value in (A).
[0010]
Polyethylene composition according to claim 9, characterized in that it comprises the first polymerization zone under conditions of rapid fluidization or transport.
[0011]
Polyethylene composition according to claim 9, characterized in that the first polyethylene and the second polyethylene contain one or more comonomers.
[0012]
Polyethylene composition according to claim 9, characterized in that the first gas phase reactor and the second gas phase reactor are heated to a temperature ranging from 70 ° C to 95 ° C.
[0013]
Polyethylene composition according to claim 9, characterized in that the Ziegler-Natta catalyst comprises a solid catalyst component comprising a titanium compound in a magnesium support and an organoaluminated compound.
[0014]
Polyethylene composition according to claim 9, characterized in that the polyethylene composition comprises a density of more than 0.950 g / cm3, an MIF / MIP ratio of 17 to 25, a SIC index of 0.15 to 2 and a long chain branch index less than 0.70.
[0015]
15. Polyethylene composition according to claim 9, characterized by the fact that it comprises: (A) 40% to 60% by weight of an ethylene homopolymer or copolymer with density equal to or greater than 0.960 g / cm3 and an index of fluidity (MIE) at 190 ° C with a load of 2.16 kilograms of 5 to 20 grams / 10 minutes; and (B) 40% to 60% by weight of an ethylene homopolymer or copolymer with an MIE value less than the MIE value in (A), where the polyethylene composition comprises: (i) density above 0.950 g / cm3 ; (ii) MIF / MIP ratio of 17 to 25; (iii) i) SIC index from 0.15 to 8, where the SIC index is determined according to the following relation: SIC index = (tinium, SIC @ 1000 xt start, quiescent) / (MIF) where tinium, sic @ 1000 is measured in seconds and is the time needed to start crystallization at a shear rate of 1000 s'1, t start, quiescent is measured in seconds and is the time to start crystallization at 125 ° C without shear, determined in the isothermal mode by differential scanning calorimetry; (vi) an index of long branched chains less than 0.70.
[0016]
16. Polyethylene composition according to claim 15, characterized by the fact that it comprises: an eta (0.02) ranging from 30,000 to 65,000 Pascals per second, where the eta (0.02) is the complex shear viscosity at an angular frequency of 0.02 rad / s, measured by an oscillatory dynamic double plate rotational rheometer at a temperature of 190 ° C.
[0017]
17. Polyethylene composition according to claim 15, characterized by the fact that it also comprises at least one characteristic among the following: (a) Mp equal to or less than 320,000 grams / mole ("g / mol"); (b) MP / Mn ratio of 20 to 30; (c) MIP of 0.9 to 2.1 grams / 10 minutes; (d) MIF of 20 to 45 grams / 10 minutes; (e) comonomer content equal to or less than 1.2% by weight; and (f) SIC index ranging from 0.15 to 2.

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US11098139B2|2018-02-28|2021-08-24|Chevron Phillips Chemical Company Lp|Advanced quality control tools for manufacturing bimodal and multimodal polyethylene resins|

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法律状态:
2018-02-27| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|

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2019-12-10| B06U| Preliminary requirement: requests with searches performed by other patent offices: procedure suspended [chapter 6.21 patent gazette]|

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2020-04-14| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|

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2020-07-07| B16A| Patent or certificate of addition of invention granted [chapter 16.1 patent gazette]|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 26/02/2014, OBSERVADAS AS CONDICOES LEGAIS. |

优先权:

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申请号 | 申请日 | 专利标题

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US201361770049P| true| 2013-02-27|2013-02-27|

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US61/770,049|2013-02-27|

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US201361820382P| true| 2013-05-07|2013-05-07|

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US61/820,382|2013-05-07|

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PCT/US2014/018748|WO2014134193A1|2013-02-27|2014-02-26|Polyethylene processes and compositions thereof|

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