Polyethylene composition having high swell ratio.
Abstract
The polyethylene composition with an expansion ratio and improved mechanical properties, particularly suitable for preparing blow molded articles, the composition has the following characteristics: 1) density of 0.945 to less than 0.952 g / cm3 2) MIF / MIP ratio of 15 to 30; 3) shear-induced crystallization index of 2.5 to 5.5.

Term
7.1 yearsleft in the term
Expires 22 October 2033.
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8 claims: 7 independent, 1 dependent
- 1REIVINDICACIONES Habiéndose descrito la invención como antecede, se reclama como propiedad lo contenido en las siguientes reivindicaciones:1. Una composición de polietileno, que contiene de 0.05 a 1% en peso de comonómero que se selecciona de olefinas que tienen la fórmula CH2=CHR, en donde R es un radical alquilo, lineal o ramificado, que tiene 1 a 10 átomos de carbono, que comprende: A) 30 a 50% en peso de un homopolímero de etileno con una densidad igual a o mayor de 0.960 g/cm 3 y un índice de flujo fundido a 190°C, con una carga de 2.16 kg, de acuerdo con ISO 1133, de 10 a 35 g/10 min;B) 50 a 70% en peso de un copolímero de etileno que tiene un valor MIE menor que el valor MIE del inciso A): caracterizado porque tiene: 1) una densidad de 0.948 a 0.951 g/cm 3 , determinada de acuerdo con ISO 1183 a 23°C;
- 22) una relación MIF/MIP de 17 a 29, en donde el MIF es el índice de flujo fundido a 190°C, con una carga de 21.60 kg, y el MIP es el índice de flujo fundido a 190°C, con una carga de 5 kg, ambos determinados de acuerdo con ISO 1133;
- 33) un índice de ramificación de cadena larga igual a o mayor a 0.72;
- 44) un FNCT igual a o mayor a 10 horas medido a 4 MPa, 80°C;
- 55) un impacto a la tensión con muesca (-30°C) igual a o mayor de 100 kJ/m 2 , determinado de acuerdo con ISO 8256:2004, con especímenes con 1 muesca doble de acuerdo con el método A;
- 66) velocidad de cizalla crítica para generación de rugosidad mate (190°C) igual a o mayor a 250 s 1 medido utilizando un reómetro con un troquel ranurado de 30 x 3 x 0.3 mm;
- 77) relación de expansión de troquel igual a o mayor de 150%, medido a una velocidad de cizalla de 1440 s' 1 ;
- 88) encogimiento a 1500 s _1 (190°C) igual a o menor de 17%. 2. La composición de polietileno de conformidad con la reivindicación 1, caracterizada porque comprende uno o más copolímeros de etileno. 3. La composición de polietileno de conformidad con la reivindicación 1, caracterizada porque tiene por lo menos una de las siguientes propiedades:un Mw igual a o mayor a 250,000 g/mol;un Mw/Mn de 20 a 30;un índice de ramificación de cadena larga igual a o mayor de 0.80;un MIP de 0.05 a 0.5 g/10 min;y un MIF de 1 a 15 g/10 min. 4. Un proceso para preparar la composición de polietileno de conformidad con la reivindicación 1, caracterizado porque comprende las siguientes etapas, en cualquier orden mutuo: a) polimerizar etileno en un reactor de fase gaseosa en presencia de hidrógeno, la relación molar de hidrógeno/etileno es de 0.5 a 2, la cantidad de monómero de etileno es de 5 a 50% en volumen, en base en el volumen total de gas presente en el reactor de polimerización;b) copolimerizar etileno con uno o más comonómeros en otro reactor en fase gaseosa en presencia de una cantidad de hidrógeno menor que la etapa a);en donde las partículas de polímero en crecimiento fluyen hacia arriba a través de una primera zona de polimerización (tubo de subida) bajo fluidización rápida o condiciones de transporte, abandonando el tubo de subida y entrando a una segunda zona de polimerización (tubo de bajada) a través de la cual fluyen hacia abajo bajo la acción de la gravedad, abandonando el tubo de bajada y son reintroducidas en el tubo de subida, de esta manera se establece una circulación de polímero entre las dos zonas de polimerización, la relación molar de hidrógeno/etileño en la el tubo de subida de la etapa b) está en el intervalo de 0.05 a 0.3, la concentración de etileno está comprendida entre 5 y 15% en volumen en base en el volumen total del gas presente en el tubo de subida, la relación molar de hidrógeno/etileno en el tubo de bajada de la etapa b) está comprendida entre 0.005 y 0.2, la concentración de etileno está comprendida entre 1 y 2 0%, la concentración de comonómero está comprendida entre 0.2 a 1% en volumen, en base en el volumen total de gas presente en la el tubo de bajada;todas las etapas de polimerización se llevan a cabo en presencia de un catalizador de polimerización de Ziegler-Natta soportado sobre MgCla, en donde: i) en la etapa de polimerización a) 30 a 50% en peso de un homopolimero de etileno A) con una densidad igual o mayor a 0.960 g/cm 3 y un índice de flujo fundido MIE a 190°C, con una carga de 2.16 kg, de acuerdo con ISO 1133, de 10 a 35 g/10 min es polimerizado;ii) en la etapa de polimerización b) 50 a 70% en peso del copolimero de etileno B) que tiene un valor MIE menor que el valor MIE de A) es polimerizado;el catalizador de Ziegler-Natta comprende el producto de reacción de: a) el componente de catalizador sólido comprende un compuesto de Ti y un compuesto donador de electrones ED soportado sobre MgCls;b) un compuesto de organo-Al;el componente de catalizador sólido se prepara al primero poner en contacto el compuesto de titanio con el MgCla, o un compuesto de Mg precursor, y de esta manera preparar un producto intermedio a') que contiene un compuesto 5 de titanio soportado sobre MgC12, producto intermedio a') el cual después se pone en contacto con el compuesto ED el cual se agrega a la mezcla de reacción solo.
Independent claims8
226 paragraphs in 2 sections, as filed
COMPOSITION OF POLYETHYLENE THAT HAS A HIGH DILATATION PROPORTION
DESCRIPTION OF THE INVENTION
The present invention provides a polyethylene composition suitable for preparing various types of formed articles. In particular, due to its superior processability, high expansion of the extrudate with a high quality surface and stability of dimension of the final article, resistance to breakage due to environmental degradation (FNCT) and impact resistance, The present composition is suitable for preparing hollow blow molded articles, such as drums, containers and gasoline storage tanks.
The present invention also relates to a multi-stage polymerization process for preparing the polyethylene composition.
An additional and important advantage of the polyethylene composition of the present invention is that it can be melt processed at unusually high shear rate values, which means high processing speeds and / or reduced melting processing temperatures, without encountering instabilities. of flow that generally produce unacceptable defects in the formed articles (for example, shark skin or flow breakage), even in
Ref. 256167 absence of processing aids.
In addition, the rapid crystallization kinetics of the present composition, which provides a critical contribution to its superior processing capacity, also provides an unusual reduced shrinkage of the formed articles, which allows for extraordinary dimensional stability.
Therefore, the composition of the present invention provides an incomparable balance of mechanical properties and processability with respect to the polyethylene compositions known for the same use, as disclosed in particular in US 6201078.
In fact, the polymers described in US6201078 reach a relatively low equilibrium of proportion of expansion and tensile strength due to environmental degradation as shown in the examples.
The problem of achieving high impact resistance by reducing flow instabilities and improving dimensional stability (reducing shrinkage) is not mentioned in the document.
Therefore, the present invention provides a polyethylene composition having the following characteristics:
1) density of 0.945 to less than 0.952 g / cm<sup>3</sup>, preferably 0.948 to 0.951 g / cm<sup>3</sup>, determined in accordance with ISO 1183 at 23 ° C;
2) MIF / MIP ratio from 15 to 30, in particular from 17 to 29, where MIF is the melt flow rate at 190 ° C with a load of 21.60 kg and MIP is the melt flow rate at 190 ° C with a load of 5 kg, both determined in accordance with ISO 1133;
3) SIC index of 2.5 to 5.5, preferably 2.5 to 4.5, more preferably 3.2 to 3.9;
where the SIC index is the shear induced crystallization index, determined in accordance with the following relationship:
Index SIC = (tcomienzo, SIC at 1000 X t start, rest) / (HLMI) where tcomienzo, sic at 1000 is measured in seconds and is the time required for the beginning of crystallization at a shear rate of 1000 s<sup>-</sup> * ·, The t start, rest is measured in seconds and is the crystallization start time at a temperature of 125 ° C without shear, determined in isothermal mode by differential scanning calorimetry (DSC); HLMI is the melt flow rate determined at 190 ° C with a load of 21.6 kg, in accordance with ISO 1133.
The term "polyethylene composition" is intended to cover, as alternatives, the simple ethylene polymer and the ethylene polymer composition, in particular a composition of two or more components of ethylene polymer, preferably with different molecular weights, the composition is also called bimodal polymer or multimodal in the relevant technique.
Typically the polyethylene composition of the present invention comprises or consists of one or more ethylene copolymers.
All features defined herein, which comprise features 1) to 3) defined above, refer to the ethylene polymer or polymeric ethylene composition. The addition of other components, such as additives normally used in the art, can modify one or more of the characteristics.
The MIF / MIP ratio provides a rheological measure of molecular weight distribution.
Another measure of molecular weight distribution is provided by the ratio Mw / Mn, where Mw is the average molar mass weight and Mn is the average number of molar mass, both measured by GPC (gel permeation chromatography) as explained In the examples.
Preferred values of Mw / Mn for the polyethylene composition of the present invention range from 20 to 30.
In addition, the polyethylene composition of the present invention preferably has at least one of the following additional characteristics.
Mw equal to or greater than 250000 g / mol, more preferably equal to or greater than 280000 g / mol, in particular equal to or greater than 300000 g / mol;
Long chain branching index (LCB) determined as described in the examples, equal to or greater than 0.70, more preferably equal to or greater than 0.72, in particular equal to or greater than 0.80;
- MIP: 0.05 - 0.5 g / 10 min .;
- MIF: 1-15 g / 10 min .;
- Content of comonomers equal to or less than 1% by weight, in particular from 0.05 to 1% by weight, with respect to the total weight of the composition.
The comonomer or comonomers present in ethylene copolymers are generally selected from olefins having the formula CH2 = CHR where R is an alkyl, linear or branched radical having 1 to 10 carbon atoms.
Specific examples are propylene, butene-1, pentene-1, 4-methylpentene-1, hexene-1, octene-1 and decene-1. A particularly preferred comonomer is hexene-1.
In particular, in a preferred embodiment, the present composition comprises:
A) from 30 to 50% by weight of a homopolymer or copolymer of ethylene (homopolymer is preferred) with a density equal to or greater than 0.960 g / cm<sup>3</sup> and an MIE melt flow rate at 190 ° C with a load of 2.16 kg, in accordance with ISO 1133, of 10-35 g / 10 min;
B) 50 to 7% by weight of an ethylene copolymer having an MIE value less than the MIE value of A), preferably less than 0.5 g / 10 min.
The amounts in percentages above are given with respect to the total weight of A) + B).
The total amount of comonomer in B) is preferably 0.1 to 2% by weight, based on the total weight of B).
As stated above, the present polyethylene composition can be advantageously used in the preparation of hollow blow molded articles, in particular large blow molded hollow articles such as open top drums (OTD). or industrial containers for bulk materials (IBC), thanks to their valuable mechanical properties.
In fact, it is preferably characterized by the following properties.
- FNCT equal to or greater than 10 hours, more preferably equal to or greater than 100 hours, in particular equal to or greater than 150 hours, measured at 4 MPa, 80 ° C;
- Impact of notch tension (-30 ° C) equal to or greater than 10 0 k J / m<sup>2</sup>;
- Critical shear speed for shark skin (190 ° C) equal to or greater than 250 s<sup>-1</sup>;
- Extrusion expansion ratio equal to or greater than 15%;
- Shrinkage at 1500 s<sup>_1</sup> (190 ° C) equal to or less than 17%.
Details of the test methods are provided in the examples.
In particular, the shark skin test (critical shear rate for shark skin) indicates the shear rate at which flow instabilities begin due to pressure fluctuations, therefore, melt processing conditions and consequently the extrusion performance, in which the irregularities in the surface of the extruded part become visible. The irregularities strongly reduce the brightness and smoothness of the surface, which decreases the quality of the extruded article to an unacceptable level.
As mentioned above, the polyethylene composition of the present invention can be melt processed at surprisingly high shear rate values, even without experiencing pressure fluctuations and flow instabilities.
While in principle there is no known necessary limitation on the type of polymerization processes and catalysts to be used, it was found that the polyethylene composition of the present invention can be prepared by a gas phase polymerization process in the presence of a catalyst Ziegler-Natta.
The Ziegler-Natta catalyst comprises the reaction product of an organometallic compound of group 1, 2 or 13 of the periodic table of elements with a transition metal compound of groups 4 to 10 of the periodic table of elements (new annotation). In particular, the transition metal compound can be selected from the compounds of Ti, V, Zr, Cr and Hf and is preferably supported on MgCl<sub>2</sub>.
Particularly preferred catalysts comprise the reaction product of the organometallic compound of group 1, 2 or 13 of the periodic table of elements, with a solid catalyst component comprising a Ti compound and an electron donor compound (ED) in English) supported in MgCl<sub>2</sub>.
Preferred organometallic compounds are organ-Al compounds.
Accordingly, in a preferred embodiment, the polyethylene composition of the present invention can be obtained by using a Ziegler-Natta polymerization catalyst, more preferably, a MgCl-supported ZieglerNatta catalyst<sub>2</sub>, even more preferably a Ziegler-Natta catalyst comprising the reaction product of:
a) a solid catalyst component comprising a Ti compound and an ED electron donor compound supported on MgC12,
b) an organ-Al compound; and optionally
c) an external electron donor compound EDext.
Preferably in component a) the ED / Ti molar ratio ranges from 1.5 to 3.5 and the Mg / Ti molar ratio is greater than 5.5, in particular from 6 to 80.
Suitable titanium compounds include tetrahalides or compounds of formula TiX<sub>n</sub> (OR<sup>1</sup>) 4-<sub>n</sub>, where 0 <n <3, X is halogen, preferably chlorine and R<sup>1</sup> It is a Ci-Cio hydrocarbon group. Titanium tetrachloride is the preferred compound.
The ED compound is generally selected from alcohol, ketones, amines, amides, nitriles, alkoxysilanes, aliphatic ethers and esters of aliphatic carboxylic acids.
Preferably the compound ED is selected from amides, esters and alkoxysilanes.
Excellent results have been obtained with the use of esters which are therefore particularly preferred as the ED compound. Specific examples of esters are alkyl esters of C1-C20 aliphatic carboxylic acids and in particular C1-C8 alkyl esters of aliphatic monocarboxylic acids such as ethyl acetate, methylformate, ethylformiate, methyl acetate, propylacetate, i-propylacetate, n-butylacetate, i- butylacetate In addition, aliphatic ethers and particularly C2-C20 aliphatic ethers, such as tetrahydrofuran (THF) or dioxane, are also preferred.
In the solid catalyst component MgCl<sub>2</sub> it is the basic support, even if a smaller amount of additional carriers can be used. MgCl<sub>2</sub> it can be used as such or obtained from Mg compounds used as precursors that can be transformed into MgCl<sub>2</sub> by reaction with halogenated compounds. The use of MgCl is particularly preferred.<sub>2</sub> in the active form that is widely known in the patent literature as support for Ziegler-Natta catalysts. USP patents 4,298,718 and USP 4,495,338 were the first to describe the use of these compounds in Ziegler-Natta catalysts. From these patents it is known that magnesium dihalides in the active form used as support and co-support in catalyst components for the polymerization of olefins are characterized by X-ray spectrum in which the most intense diffraction line that appears in the ASTM card reference the spectrum of the non-active halide decreases its intensity and widens. In the X-ray spectrum of the actively preferred magnesium dihalides, the most intense line reduces its intensity and is replaced by a halo whose maximum intensity moves towards the lower angles with respect to the most intense line. Particularly suitable for the preparation of the polyethylene composition of the present invention are catalysts where the solid catalyst component a) is first obtained by contacting the titanium compound with the MgCl<sub>2</sub>, or a precursor Mg compound, optionally in the presence of an inert medium, whereby an intermediate product a ') containing a titanium compound supported on MgCl is prepared<sub>2</sub>, whose intermediate product a ') then comes into contact with the ED compound that is added to the reaction mixture alone or in a mixture with the other compounds where it represents the main component, optionally in the presence of an inert medium.
With the term main component it is intended that the compound ED be the main component in terms of molar amount, with respect to the other possible compounds except the inert solvents or diluents used to handle the contact mixture. The treated ED product can then be washed with the appropriate solvents to recover the final product. If necessary, treatment with the desired ED compound may be repeated one or more times.
As mentioned above, the MgCl precursor<sub>2 </sub>It can be used as an essential starting Mg compound. This can be selected, for example, from the Mg compound of formula MgR '<sub>2</sub> where the R groups<sup>1</sup> they may independently be optionally substituted C1-C20 hydrocarbon groups, OR groups, OCOR groups, chlorine, where R is an optionally substituted C1-C20 hydrocarbon group, with the obvious condition that the R 'groups are not simultaneously chlorine. Lewis adducts between MgCl are also suitable as precursors<sub>2</sub> and suitable Lewis bases. A particular and preferred class is constituted by MgCl adducts<sub>2</sub> (R'OH) m where the R groups are C1-C20 hydrocarbon groups, preferably C1-C10 alkyl groups and m is 0.1 to 6, preferably 0.5 to 3 and more preferably 0.5 to 2. Adducts of this type can generally be obtained by mixing alcohol and MgCl<sub>2</sub> in the presence of an inert hydrocarbon immiscible with the adduct, under stirring conditions at the melting temperature of the adduct (100130 ° C). Then, the emulsion is rapidly inactivated, which causes solidification of the adduct in the form of spherical particles. Representative methods for the preparation of these spherical adducts are reported, for example, in USP 4,469,648, USP 4,399,054 and W098 / 44009. Another useful method for spherulization is spray cooling described, for example, in USP 5,100,849 and 4,829,034.
Particularly interesting are the MgCl adducts<sub>2</sub>(EtOH) <sub>m</sub> in which m is 0.15 to 1.7 obtained by subjecting the adducts with a higher alcohol content to a thermal de-alcoholization process carried out in nitrogen flow at temperatures between 50 and 150 ° C until The alcohol content is reduced to the previous value. Such a process is described in EP 395083.
Desalcoholization can also be carried out by
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It is preferred that the desalcoholization reaction be carried out simultaneously with the reaction step that involves the use of a titanium compound. Therefore, these adducts react with the TiX compound<sub>n</sub>(OR<sup>1</sup>) 4-n (or possibly mixtures thereof) mentioned above which is preferably titanium tetrachloride. The reaction with the Ti compound can be carried out by suspending the adduct in T1CI4 (generally cold). The mixture is heated at temperatures ranging from 80 to 130 ° C and is maintained at this temperature for 0.5 to 2 hours. Treatment with the titanium compound can be carried out one or more times. Preferably repeated twice. It can also be carried out in the presence of an electron donor compound such as those mentioned above. At the end of the process the solid is recovered by separating the suspension through conventional methods (such as sedimentation and liquid removal, filtration, centrifugation) and can be subjected to solvent washes. While washings are typically carried out with inert hydrocarbon liquids, it is also possible to use more polar solvents (for example, having a higher dielectric constant) such as halogenated hydrocarbons.
As mentioned above, the intermediate product is then contacted with the ED compound under conditions capable of fixing in the solid an effective amount of donor. Due to the high versatility of this method, the amount of donor used can vary widely. By way of example, it can be used in a molar ratio with respect to the Ti content in the intermediate product ranging from 0.5 to 20 and preferably from 1 to 10. While not strictly necessary, contact is typically carried out in a liquid medium such as a liquid hydrocarbon. The temperature at which the contact takes place may vary depending on the nature of the reagents. It is generally in the range of -10 ° to 150 ° C and preferably 0<sup>or</sup> at 120 ° C. It is clear that temperatures that cause the decomposition or degradation of any specific reagents should be avoided even if they fall within the generally adequate range. Also, the treatment time may vary depending on other conditions such as the nature of the reagents, the temperature, the concentration, etc. As a general indication, this contact stage can last from 10 minutes to 10 hours, more frequently from 0.5 to 5 hours. If desired, to increase the final donor content, this step may be repeated one or more times. At the end of this stage the solid is recovered by separating the suspension through conventional methods (such as sedimentation and removal of the liquid, filtration, centrifugation) and can be subjected to solvent washes. While washing is typically carried out with inert hydrocarbon liquids, it is also possible to use more polar solvents (for example, having a higher dielectric constant) such as halogenated or oxygenated hydrocarbons.
As mentioned above, the solid catalyst component is converted into catalysts for the polymerization of olefins by their reaction, in accordance with known methods, with an organometallic component of group 1, 2 or 13 of the periodic table of elements, in particular with an alkyl-Al compound.
The alkyl-Al compound is preferably selected from trialkyl aluminum compounds such as, for example, triethylaluminum, triisobutylaluminum, tri-n-butyl aluminum, tri-n-hexyl aluminum, tri-n-octylaluminum.
It is also possible to use alkylaluminum halides, alkylaluminum hydrides or alkylaluminum sesquichlorides such as AlEtzCl and Al<sub>2</sub>Et3C13 optionally in admixture with the trialkylaluminum compounds.
The external electron donor compound ED<sub>former</sub>t optionally used to prepare the Ziegler-Natta catalysts may be the same or different from the ED used in the solid catalyst component a). It is preferably selected from the group consisting of ethers, esters, amines, ketones, nitriles, silanes and mixtures thereof. In particular, C2-C20 aliphatic ethers and in particular cyclic ethers, which preferably have 3 to 5 carbon atoms such as tetrahydrofuran and dioxane, can be advantageously selected.
Specific examples of the ZieglerNatta catalysts described above and the methods for their preparation are provided in W02004106388. However, the prior polymerization described therein of the solid catalyst component containing the Ti compound and the electron donor compound ED (solid catalyst component a)) is not comprised in the preferred embodiments in accordance with the present invention. In particular, the polyethylene composition of the present invention can be obtained by a process in which all polymerization steps are carried out in the presence of the catalyst.
In fact, it was found that by using the polymerization catalyst described above, the polyethylene composition of the present invention can be prepared in a process comprising the following steps, in any order:
a) polymerizing ethylene, optionally together with one or more comonomers, in a gas phase reactor in the presence of hydrogen;
b) copolymerizing ethylene with one or more comonomers in a gas phase reactor in the presence of a smaller amount of hydrogen than in step a);
where in at least one of the gas phase reactors the expanding polymer particles flow upward through the first polymerization zone (riser tube) under fluidization or rapid transport conditions, leave the riser tube and enter the second polymerization zone (downpipe) through which they flow down through the action of gravity, leave the downcomer and re-enter the riser, whereby a circulation of polymer is established between the two polymerization zones. In the first polymerization zone (riser tube), the fast fluidization conditions are established by supplying a gaseous mixture comprising one or more defined (ethylene and comonomers) at a speed greater than the transport speed of the polymer particles . The speed of the gas mixture is preferably between 0.5 and 15 m / s, more preferably between 0.8 and 5 m / s. The terms transport speed and rapid fluidization conditions are well known in the art; for a definition of these, see, for example, D. Geldart, Gas Fluidisation Technology, page 155 et seq., J. Wiley & Sons Ltd., 1986.
In the second polymerization zone (downpipe), the polymer particles flow through the action of gravity in a densified form, such that the density values of the solid (polymer mass per reactor volume) are reached, which they approach the apparent density of the polymer.
In another way, the polymer flows vertically down through the downcomer in a plug flow (compact flow mode), such that only small amounts of gas are entrained between the polymer particles.
The process allows to obtain from step a) an ethylene polymer with a molecular weight less than the ethylene copolymer obtained from step b).
Preferably, the polymerization of ethylene to produce a relatively low molecular weight ethylene polymer (step a) is performed upstream of the copolymerization of ethylene with a comonomer to produce a relatively high molecular weight ethylene copolymer (step b). For this purpose, in step a) a gas mixture comprising ethylene, hydrogen and an inert gas is introduced into a first gas phase reactor, preferably a fluid bed gas phase reactor. The polymerization is carried out in the presence of the Ziegler-Natta catalyst described above. Preferably, no comonomer is introduced into the first gas phase reactor and a highly crystalline ethylene homopolymer is obtained in step a). However, a minimum amount of comonomer can be introduced with the proviso that the degree of copolymerization in step a) is limited such that the density of the ethylene polymer obtained in step a) is not less than 0.960 g / cm<sup>3</sup>.
Hydrogen is introduced in an amount that depends on the specific catalyst used and, in any case, suitable for obtaining in step a) an ethylene polymer with an MIE melt flow rate of 10 to 35 g / 10 min. To obtain the above MIE range, in step a) the hydrogen / ethylene molar ratio is indicatively 0.5 to 2, the amount of ethylene monomer is 5 to 50% by volume, preferably of 5 to 30% by volume, based on the total volume of gas present in the polymerization reactor. The remaining portion of the feed mixture is represented by inert gases and one or more comonomers, if any. The inert gases that are necessary to dissipate the heat generated by the polymerization reaction are conveniently selected from nitrogen or saturated hydrocarbons, where propane is most preferred.
The operating temperature in the reactor of step a) is selected between 50 and 120 ° C, preferably between 65 and 100 ° C, while the operating pressure is between 0.5 and 10 MPa, preferably between 2.0 and 3.5 MPa
In a preferred embodiment, the ethylene polymer obtained in step a) represents from 3 0 to 50% by weight of the total ethylene polymer produced in the overall process, that is, in the first and second reactor connected in Serie.
The ethylene polymer from stage a) and the trapped gas are then subjected to a solid / gas separation stage to prevent the gas mixture from the first polymerization reactor from entering the stage b) reactor (second gas phase polymerization reactor). The gas mixture can be recycled back into the first polymerization reactor, while the separated ethylene polymer is introduced into the reactor of step b). A suitable point for introducing the polymer into the second reactor is in the connecting part between the drop tube and the rise tube, where the solid concentration is particularly low, such that the flow conditions are not adversely affected. .
The operating temperature in step b) is in the range of 65 to 95 ° C and the pressure is in the range of 1.5 to 4.0 MPa. The second gas phase reactor is intended to produce a relatively high molecular weight ethylene copolymer by copolymerizing ethylene with one or more comonomers. In addition, to extend the molecular weight distribution of the final ethylene polymer, the reactor in step b) can be conveniently operated by establishing different conditions of monomers and hydrogen concentration within the riser tube and the downstream tube.
For this purpose, in step b) it is possible to prevent the gaseous mixture containing the polymer particles and coming from the riser from entering all or part of the drop tube, in order to obtain two different gas composition zones. This can be achieved by introducing a gaseous and / or liquid mixture into the downcomer through a line placed at a suitable point of the downcomer, preferably at the top of it. The gaseous and / or liquid mixture must have a suitable composition, different from that of the gaseous mixture present in the riser. The flow of the gaseous and / or liquid mixture can be regulated in such a way that an upward flow of gas is generated that runs in the opposite direction to the flow of the polymer particles, particularly in its upper part, which acts as a barrier to the mixing. gas trapped between the polymer particles that come from the riser. In particular, it is advantageous to introduce a mixture with a low hydrogen content to produce the higher molecular weight polymer fraction in the downcomer. One or more comonomers can be introduced into the drop tube of step b), optionally together with ethylene, propane or other inert gases.
The hydrogen / ethylene molar ratio in the drop tube of step b) is between 0.005 and 0.2, the ethylene concentration is between 1 and 20%, preferably between 3 and 10% by volume , the comonomer concentration is between 0.2 and 1% by volume, based on the total volume of gas present in the downcomer. The rest is propane or similar inert gases. Since there is a very low hydrogen molar concentration in the drop tube, it is possible to join a relatively high amount of comonomer with the high molecular weight polyethylene fraction when carrying out the process of the present invention.
The polymer particles that come from the downcomer are reintroduced into the uptake tube of step b).
Since the polymer particles continue to react and no more comonomer is introduced into the riser tube, the concentration of the comonomer decreases at a range of 0.1 to 0.5% by volume, based on the total volume of gas present in the riser tube. In practice, the comonomer content is controlled to obtain the desired density of final polyethylene. In the riser tube of stage b) the hydrogen / ethylene molar ratio is in the range of 0.05 to 0.3, the concentration of ethylene is between 5 and 15% by volume based on the Total volume of gas present in the riser. The rest is propane or other inert gases.
More details about the polymerization process described above are provided in WO9412568.
The following examples are provided to illustrate, without limitation, the present invention.
Unless stated otherwise, the following test methods are used to determine the properties reported in the detailed description and in the examples.
Density
Determined in accordance with ISO 1183 at 23 ° C.
Determination of molecular weight distribution
The determination of the molar mass distributions and the Mn, Mw and Mw / Mn averages derived from these was carried out by high temperature gel permeation chromatography using the method described in ISO 16014-1, 2, -4 , from 2003. The specifications in accordance with the aforementioned ISO standards are: Solvent 1,2,4trichlorobenzene (TCB), device temperature and 135 ° C solutions and as a concentration detector an IR-4 infrared detector from PolymerChar (Valencia, Paterna 46980, Spain), suitable for use with TCB. A WATERS Alliance 2000 equipped with the following SHODEX UT-G pre-column and SHODEX UT 806 M (3x) and SHODEX UT 807 (Showa Denko Europe GmbH, Konrad-Zuse-Platz 4, 81829 Muenchen, Germany) connected at Serie. The solvent was distilled under vacuum under 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 500μ1 and the polymer concentration was in the range of 0.01% <conc. <0.05% w / w The molecular weight calibration was established through the use of monodispersed polystyrene (PS) standards from Polymer Laboratories (currently Agilent Technologies, Herrenberger Str. 130, 71034 Boeblingen, Germany)) in the range of 580g / mol to 11600000g / mol and additionally with hexadecane. The calibration curve was then adapted to polyethylene (PE) by means of the universal calibration method (Benoit H., Rempp P. and Grubisic Z., & in J. Polymer Sci., Phys. Ed., 5, 753 ( 1967)). The Mark-Houwing parameters used here were for PS: k<sub>$</sub>= 0.000121 dl / g, a<sub>P</sub>s = 0.706 and for PE k<sub>P</sub>E = 0.000406 dl / g, «<sub>P</sub>e = 0.725, valid in TCB at 135 ° C. Data recording, calibration and calculation were carried out with the use of NTGPC_Control_V6.02.03 and NTGPC_V6.4.24 (HS GmbH, HauptstraEe 36, D-55437 Ober-Hilbersheim, Germany) respectively.
Shear-induced crystallization test
This method is used to determine the onset time of shear-induced crystallization (SIC) of the polymer. <sub>F</sub> tcomienzo, SIC · Samples are pressed by fusion at 210 ° C, 4 min. , under 200 bar in a laboratory press on thick Imm plates. The disk samples are cut with a diameter of 25mm. The samples are inserted into the oscillating plate shear rheometer. A Physica MCR 301 rotating rheometer from AntonPaar was used.
Then, the sample was melted within the test geometry at 190 ° C for 4 minutes, cooled with ~ 10K / min. at the test temperature, T = 125 ° C and it was warmed for 5 minutes. Consequently, a continuous shear was applied at a constant shear rate and the shear viscosity was controlled as a function of time. The experiment was repeated applying each time a different shear rate that varied from 0.05 to 0.5 s<sup>_1</sup>. The start time for SIC, t<sub>C</sub>omienzo, sic, was taken at the point where the viscosity had increased by 50% of its steady state value η to 125 ° C. The steady state value is the average continuous shear fusion viscosity measured at the specific temperature.
The logt graph<sub>C</sub>omienzo, sic vs. log shear rate provides a linear function (of type y = Ax + B) that is extrapolated at a shear rate of 1000 s<sup>_1</sup> (relevant to the process) to determine the value of t<sub>C</sub>omienzosic @ 1000.
The SIC index below is calculated in accordance with the following relationship:
SIC index = (start, SIC at 1000 xt start, rest) / (HLMI)
The tcomienzo, rest (in seconds) is the beginning of crystallization at a temperature of 125 ° C under resting conditions, that is, without shear, measured in isothermal mode in a differential scanning calorimetry apparatus, DSC, as explained then.
HLMI is the melt flow rate (g / lOmin.) Measured at T = 190 ° C with 21.6 kg load, in accordance with ISO 1133.
The same protocol is described in the following documents.
- I. Vittorias, Correlation among structure, processing and product properties, Würzburger Tage 2010, Wolfgang Kunze TA Instrumenta, Germany.
- Wo DL, Tanner RI (2010), The impact of blue organic and inorganic pigments on the crystallization and rheological properties of isotactic polypropylene, Rheol. Minutes 49, 75.
Derakhshandeh M., Hatzikiriakos SG, Flow-induced crystallization of high-density polyethylene: the effects of shear and uniaxial extension, Rheol. Minutes, 51, 315-327, 2012.
Isothermal DSC
The start, rest, the start time when no deformation is applied at 125 ° C, is determined by the method of iso-DSC (Isothermal differential scanning calorimetry). It is measured at 125 ° C on a TA Instruments Q2000 DSC device. The determination of tcomienzo, rest is done through the use of commercially available TA Universal Analysis 2000 software. Sample preparation and installation follows DIN EN ISO 11357-1: 2009 and ISO 11357-3: 1999.
melt flow rate
Determined in accordance with ISO 1133 at 190 ° C with the specified load.
long chain branching index (LCB)
The LCB index corresponds to the branching factor g ', measured for a molecular weight of 10<sup>6</sup> g / mol The branching factor g ', which allows the determination of long chain branching at a high Mw, was measured by gel permeation chromatography (GPC) coupled with laser light scattering (MALLS) ) as described below. The parameter g 'is the ratio of the average square radius of rotation of the linear polymer having the same molecular weight. Linear molecules show a g 'of 1, while values less than 1 indicate the presence of LCB. The values of g 'as a function of molar weight, M, were calculated from the equation:
g<sup>1</sup> (M) = <Rg<sup>2</sup>> sample, bl / <Rg<sup>2</sup>> ref. linear, M where <Rg<sup>2</sup>>, M is the root of the mean square radius of rotation for the molar weight fraction M.
The turning radius for each eluted fraction of GPC (as described above but with a flow rate of 0.6 ml / min. And a column packed with 30μτη particles) was measured by light scattering analysis at different angles . Therefore, from this configuration of MALLS it is possible to determine the molar weight M and <Rg<sup>2</sup>> Sample, M and define a g 'to a measured M = 10<sup>6</sup> g / mol <Rg<sup>2</sup>> ref. linear, m is calculated by the relationship established between the turning radius and the molecular weight for a linear polymer in solution (Zimm and Stockmayer WH 1949)) and is confirmed by measuring a linear PE reference with the same apparatus and methodology described.
The same protocol is described in the following documents.
Zimm BH, Stockmayer WH (1949) The dimensions of chain molecules containing branches and rings. J Chem Phys 17
Rubinstein M., Colby RH. (2003), Polymer Physics, Oxford University Press.
Comonomer Content
The comonomer content is determined by IR in accordance with ASTM D 6248 98, using a Bruker Tensor 27 FT-IR spectrometer, calibrated with a chemometric model to determine the ethyl or butyl side chains in PE for butene or hexane as comonomer, respectively.
Dilatation ratio
The expansion rate of the polymers studied is measured by using a capillary rheometer, Góttfert Rheotester2000 and Rheograph25, at T = 190 ° C, equipped with a commercial die 30/2/2/20 (total length 30 mm, length active = 2 mm, diameter = 2 mm, L / D = 2/2 and 20 ° entry angle) and an optical device (Góttfert laser diode) to measure the thickness of the extruded chain. The sample melts in the capillarity barrel at 190 ° C for 6 minutes and is extruded with a piston speed corresponding to a resulting shear rate in the die of 144 0 s<sup>_1</sup>. The extrudate is cut (by means of an automatic cutting device from Góttfert) at a distance of 150 mm from the die outlet, at the moment when the piston reaches a 96 mm position of the die inlet. The diameter of the extrudate is measured with a laser diode at a distance of 78 mm from the die outlet as a function of time. The maximum value corresponds to the Dextrudado · The proportion of expansion is determined from the calculation: SR = (Dextrudado<sup>-</sup> Dtroquel) 10 0 5 / Dtroquel where Dtroquel is the corresponding diameter at the die outlet, measured with the laser diode.
Shrink @ 1500 s<sup>-1</sup> (shrink lab test)
This method is applied to determine the shrinkage of the final polyethylene product after melt extrusion or otherwise, the stability capacity of one degree dimension. The method is recommended for homogeneous PE in granulated form. Powder samples can be measured only after stabilization and homogenization by fusion (typically in a laboratory plasticizer pulp crusher). However, in the latter case, a significant effect on the results can be expected, mainly due to the fact that the sample is more sensitive to degradation and air bubbles in the extrudate.
Samples in granulated form can be used directly and approximately 20 g of sample are needed to fill the capillarity barrel. The capillary rheometer used is a Góttfert Rheotester 2000, with a barrel of 15 mm in diameter and an applicable pressure range of 0-2000 bar, temperatures of 25-400 ° C, equipped with a 30/2/2/20 die , with a total length of 30mm, L / D = 2/2 and an entry angle of 20 °. The recommended test temperature for polyethylene is 210 ° C.
The piston speed is configured to have an apparent shear rate necessary at the die outlet. The test is performed at shear speeds of 50 s'<sup>1</sup>, 1000 S '<sup>1</sup>, 1500 s<sup>_1</sup> and 2500 S '<sup>1</sup>.
The extrudate is marked and each of the 40mm length pieces is perforated / stamped, while they are still in the molten state and allowed to cool to room temperature. At least 3 parts of 4 0 mm must be marked in this way. A metal clamping tool is used to stamp the extrudates after the die exit on the parts to be measured, with a length of
<td>4 0 mm</td><td>(initial length for</td><td>each part,</td><td>Li,<sub>0</sub>)</td><td>and typically</td>
<td>10 mm</td><td>Wide.</td><td></td><td></td><td></td>
<td></td><td colspan="2">The entire extrudate is cut</td><td>and</td><td>leave on the</td>
<td>table</td><td>laboratory for</td><td colspan="2">crystallize and</td><td>chill to</td>
room temperature for at least 15 minutes. The parts are cut at the marks and their length is measured. The resulting length, Li, in mm is recorded for each part and is averaged for 4 parts.
Shrinkage = x 1 QCP / o = X1 OCP / o
Ά A) and Shrinkage
Average shrinkage ~,
The procedure is carried out for each shear rate applied and the shrinkage measurement for each shear rate is repeated at least twice.
Remark: Shrinkage deviations are expected along the length of the extrudate, that is, due to the variable cooling time after the die is exited for each part and combined (the perforated part left by the die last will be less exposed time at room temperature and it will stretch due to the weight of the extrudate).
Critical shear speed for shark skin (shark skin test)
The shark skin test is a method to quantify flow instabilities and surface defects that occur during extrusion of polymer blends. Specifically, the commercial shark skin option is used with the Rheotester2000 capillary rheometer from Góttfert. The shark skin option is a 30x3x0.3mm cutting die with three pressure transducers distributed along the die (at the entrance of the die, in the middle and before the exit of the die). Pressure is recorded and analyzed (Fourier transformation) through the use of commercially available software Góttfert WebRheo.
The polymer is extruded at 190 ° C with the application of the following shear speeds in this specific order: 100-150-200-250-300-350-400-450-500 s'<sup>1</sup>. The extrudate is then visually inspected for surface defects. The critical shear rate for shark skin instability is the applied shear rate at which shark skin instability occurs for the first time (high frequency pressure oscillations and visually detectable periodic surface deformations).
The same protocol is described in the following documents.
- Palza H., Ñaue IFC, Wilhelm M., Filipe S., Becker A., Sunder J., Göttfert Α., Οη-Line Detection of Polymer Melt Flow Instabilities in a Capillary Rheometer, KGK. Kautschuk, Gummi, Kunststoffe, 2010, vol. 63, nolO, pp. 456-461.
Susana Filipe, Lakovos Vittorias, Manfred Wilhelm,
Experimental Correlation between Mechanical Non-Linearity in LAOS Flow and Capillary Flow Instabilities for Linear and Branched Commercial Polyethylenes, Macromol. Mat. and Eng., Volume 293, Topic 1, pages 57-65, 2008.
- Góttfert, A .; Sunder, J., AIP Conference Proceedings, Volume 1027, pages 1195-1197 (2008).
Notch tension impact test
The tensile impact force is determined with the use of ISO 8256: 2004 with type 1 double notch samples in accordance with method A. The test samples (4 x 10 x 80 mm) are cut to form a molded sheet by compression that was prepared in accordance with the requirements of ISO 1872-2 (average cooling rate of 15 K / min. and a high pressure during the cooling phase). Notches are made on both sides of the test samples with a 45 ° V notch. The depth is 2 ± 0.1 mm and the radius of curvature over the slope of the notch is 1.0 + 0.05 mm. The free length between the handles is 30 + 2 mm. Before measurement, all test samples are conditioned at a constant temperature of 30 ° C for a period of 2 to 3 hours. The procedure for voltage impact force measurements, including energy correction following method A is described in ISO 8256.
Tensile strength resistance to environmental degradation for creep test (FNCT)
The tensile strength resistance to environmental degradation of polymer samples is determined in accordance with the international standard ISO 16770 (FNCT) in aqueous surfactant solution. A 10 mm thick sheet molded by compression was prepared from the polymer sample. The bars with a square cross section (10x10x100 mm) are cut by using a razor blade on all four sides perpendicular to the tension direction. A notching device described in M. Fleissner in Kunststoffe 77 (1987), page 45 is used for the notch marked with a depth of 1.6 mm. The applied load is calculated from the tensile force divided by the initial ligament area. The ligament area is the remaining area = total cross-sectional area of the sample minus the area of the notch. For the FNCT sample: 10x10 mm<sup>2</sup> - 4 times of trapezoidal notch area = 46.24 mm<sup>2</sup> (the remaining cross section for the crack interruption / propagation process). The test sample is loaded with a standard condition suggested by ISO 16770 with a constant load of 4 MPa at 80 ° C in an aqueous solution of 2% non-ionic surfactant (by weight) ARKOPAL N100. The time until the test sample is broken is detected.
Charpy aFM
The fracture resistance is determined using an internal method on test bars measuring 10 x 10 x 80 mm that were cut from a compression molded sheet with a thickness of 10 mm. Six of these test bars are drilled in the center by using a razor blade in the aforementioned drilling device for FNCT. The depth of the notch is 1.6 mm. The measurement is carried out substantially in accordance with the Charpy measurement method in accordance with ISO 179-1, with modified test samples and a modified impact geometry (distance between the supports). All test samples are conditioned at the measurement temperature of 0 ° C for a period of 2 to 3 hours. The test sample below is placed without delay on the support of a pendulum impact tester in accordance with ISO 179-1. The distance between the supports is 60 mm. The fall of the hammer 2 J is triggered with a fall angle set at 160 °, a pendulum length of 225mm and an impact speed of 2.93 m / s. The fracture resistance value is expressed in kJ / m<sup>2</sup> and is given by the ratio of the impact energy consumed and the initial transverse area in the notch, aFM. Here only values for a complete fracture and hinge fracture can be used as the basis for a common meaning (see suggestion for ISO 179-1).
Examples 1, 2 and comparative examples 1 and 2 Process configuration
In Examples 1 and 2 the process of the invention was carried out under continuous conditions in a plant comprising two gas phase reactors connected in series as shown in Figure 1.
Comparative example 1 was carried out in the same plant also under continuous conditions.
Example 1
The solid catalyst component was prepared as described in example 13 of W02004106388. The molar ratio of AcOEt / Ti was 8.
Polymerization
7 g / h of the solid catalyst component prepared as described above was introduced, with the use of 5 kg / h of liquid propane, in a prior contact apparatus, in which a mixture of triisobutylaluminum (TIBA) was also administered and diethyl aluminum chloride (DEAC) as well as tetrahydrofuran (THF). The weight ratio between TIBA and DEAC was 7: 1. The weight ratio between alkyl aluminum and the solid catalyst component was 10: 1. The weight ratio between alkyl aluminum and THF was 70. The previous contact step was carried out with stirring at 50 ° C with a total residence time of 70 minutes.
The catalyst enters the first gas phase polymerization reactor of Figure 1 via line 10. In the first reactor, ethylene was polymerized with the use of H2 as a molecular weight regulator in the presence of propane as an inert diluent. . 35 kg / h of ethylene and 62 g / h of hydrogen were introduced into the first reactor via line 9. No comonomer was introduced into the first reactor.
The polymerization was carried out at a temperature of 75 ° C and a pressure of 2.5 MPa. The polymer obtained in the first reactor was discharged discontinuously by means of line 11, separated from the gas in the gas / solid separator 12 and reintroduced into the second gas phase reactor by means of line 14.
The polymer produced in the first reactor had an MIE melt index of approximately 25 g / 10 min. and a density of 0.966 kg / dm<sup>3</sup>.
The second reactor was operated under polymerization conditions of approximately 80 ° C and a pressure of 2.5 MPa. 14 kg / h of ethylene and 0.75 kg / h of 1-hexene were introduced into the downstream tube 33 of the second reactor via line 46. 5 kg / h of propane, 28.5 kg / h of ethylene and 3.1 g / h of hydrogen were introduced via line 45 into the recycling system.
To extend the molecular weight distribution of the final ethylene polymer, the second reactor was operated by establishing different conditions of monomers and hydrogen concentration within the riser 32 and the downstream tube 33. This is achieved by introducing by means of of line 52, 330 kg / h of liquid stream (liquid barrier) at the top of the downpipe 33. The liquid stream has a different composition than the gas mixture present in the riser tube. The different concentrations of monomers and hydrogen within the riser tube, the downstream tube of the second reactor and the liquid barrier composition are indicated in Table 1. The liquid stream of the line 52 comes from the condensation stage in the condenser 49, under operating conditions of 52 ° C and 2.5 MPa, where a part of the recycle stream is cooled and partially condensed. As shown in the figure, a separation vessel and a pump are placed in order downstream of the condenser 49. The final polymer was discharged discontinuously via line 54.
The polymerization process in the second reactor produced polyethylene fractions of a relatively high molecular weight. Table 1 specifies the properties of the final product. It can be seen that the melt index of the final product decreases compared to the ethylene resin produced in the first reactor, which shows the formation of high molecular weight fractions in the second reactor.
The first reactor produced about 44.5% by weight (% by weight divided) of the total amount of the final polyethylene resin produced by the first and second reactor. At the same time, the polymer obtained has a relatively wide molecular weight distribution as seen by an MIF / MIP ratio equal to 23.7.
Example 2
The process of the invention was carried out with the same configuration and the same polymerization catalyst as in Example 1. Also, the process conditions and consequently the properties of the polymer obtained from the first reactor were the same.
The second reactor was operated under polymerization conditions of approximately 80 ° C and a pressure of 2.5 MPa. 14 kg / h of ethylene and 0.86 kg / h of 1-hexene were introduced into the drop tube of the second reactor via line 46. 5 kg / h of propane, 27.4 kg / h of ethylene and 3.6 g / h of hydrogen were introduced via line 45 into the recycling system.
To extend the molecular weight distribution of the final ethylene polymer, the second reactor was operated by establishing different conditions of monomers and hydrogen concentration within the riser 32 and the downstream tube 33. Again 330 kg / h barrier Liquid were introduced via line 52. The gas compositions of the riser tube, the downstream tube and the liquid barrier are indicated in Table 1. The liquid stream of line 52 comes from the condensation stage in condenser 49, under operating conditions of 51 ° C and 2.5 MPa, where a part of the recycle stream is cooled and partially condensed.
The first reactor produced about 45% by weight (% by weight divided) of the total amount of the final polyethylene resin produced by the first and second reactor. At the same time, the polymer obtained has a relatively wide molecular weight distribution as seen by an MIF / MIP ratio equal to 22.5.
Comparative Example 1
The polymerization was carried out by using the same configuration of examples 1 and 2, but the polymerization catalyst was the same as that used in example 6 of W02005019280.
8 g / h of the solid catalyst component prepared as described above was introduced, with the use of 5 kg / h of liquid propane, in a prior contact apparatus, in which triethylaluminum (TEA) was also administered as well as tetrahydrofuran ( THF). The weight ratio between alkyl aluminum and the solid catalyst component was
5: 1. The weight ratio between alkyl aluminum and THF was 44. The prior contact step was carried out with stirring at 50 ° C with a total residence time of 70 minutes.
The catalyst enters the first gas phase polymerization reactor of Figure 1 via line 10. In the first reactor ethylene was polymerized with the use of H<sub>2</sub> as a molecular weight regulator in the presence of propane as an inert diluent. 40 kg / h of ethylene and 75 g / h of hydrogen were introduced into the first reactor via line 9. No comonomer was introduced into the first reactor.
The polymerization was carried out at a temperature of 80 ° C and a pressure of 2.4 MPa. The polymer obtained in the first reactor was discharged discontinuously by means of line 11, separated from the gas in the gas / solid separator 12 and reintroduced into the second gas phase reactor by means of line 14.
The polymer produced in the first reactor had an MIE melt index of approximately 100 g / 10 min. and a density of 0.968 kg / dm<sup>3</sup>.
The second reactor was operated under polymerization conditions of approximately 80 ° C and a pressure of 2.1 MPa. 12 kg / h of ethylene and 1.5 kg / h of 1-hexene were introduced into the downpipe 33 of the second reactor via line 46. 5 kg / h of propane, 26.5 kg / h of ethylene and 1.2 g / h of hydrogen were introduced via line 45 into the recycling system.
To extend the molecular weight distribution of the final ethylene polymer, the second reactor was operated by establishing different conditions of monomers and hydrogen concentration within the riser 32 and the downstream tube 33. This is achieved by introducing by means of of line 52, 200 kg / h of liquid stream (liquid barrier) at the top of the downpipe 33. The liquid stream has a different composition than the gas mixture present in the riser tube. The different concentrations of monomers and hydrogen within the riser tube, the downstream tube of the second reactor and the liquid barrier composition are indicated in Table 1. The liquid stream of line 52 comes from the condensation stage in condenser 49, under operating conditions of 53 ° C and 2.1 MPa, where a part of the recycle stream is cooled and partially condensed. As shown in the figure, a separation vessel and a pump are placed in order downstream of the condenser 49. The final polymer was discharged discontinuously via line 54.
The polymerization process in the second reactor produced polyethylene fractions of a molecular weight specified to be relatively high. In table 1 properties of the final product. It can be seen that the melt index of the final product decreases compared to the ethylene resin produced in the first reactor, which shows the formation of high molecular weight fractions in the second reactor.
The first reactor produced about 50% by weight (% by weight divided) of the total amount of the final polyethylene resin produced by the first and second reactor. At the same time, the polymer obtained has a relatively wide molecular weight distribution as seen by an MIF / MIP ratio equal to 38.8.
Comparative Example 2
The polymer of this comparative example is a prior art polyethylene composition prepared with a Cr catalyst, in a single gas phase reactor.
Table 1
<td></td><td>Example one</td><td>Example two</td><td>Comp. one</td><td>Comp. two</td>
<td>Funcionament condition</td><td></td><td></td><td></td><td></td>
<td>of the first reactor</td><td></td><td></td><td></td><td></td>
<td>Molar ratio of H2 / C2H4</td><td> 1,9</td><td> 1,9</td><td> 1,7</td><td></td>
<td>c<sub>2</sub>h<sub>4</sub>%</td><td> 12,1</td><td> 12,4</td><td> 14</td><td></td>
<td>Division (% by weight)</td><td> 44,5</td><td> 45</td><td> 50</td><td></td>
<td></td><td></td><td></td><td></td><td></td>
<td>Operating conditions of the second reactor</td><td></td><td></td><td></td><td></td>
<td>Molar ratio of H2 / C2H4 riser tube</td><td> 0,157</td><td> 0,203</td><td> 0,038</td><td></td>
<td>C<sub>2</sub>H<sub>4</sub>% ascent tube</td><td> 11,3</td><td> 11,4</td><td> 15</td><td></td>
<td>C<sub>6</sub>H12 riser tube</td><td> 0,56</td><td> 0,65</td><td> 1,2</td><td></td>
<td>Molar ratio of H2 / C2H4 tube come down</td><td> 0,069</td><td> 0,086</td><td> 0,04</td><td></td>
<td>C<sub>2</sub>IÍ4% down tube</td><td> 2,6</td><td> 2,8</td><td> 5,4</td><td></td>
<td>C<sub>6</sub>H12 down tube</td><td> 0,60</td><td> 0,71</td><td> 2,2</td><td></td>
<td>Molar ratio of H2 / C2H4 barrier</td><td> 0,013</td><td> 0,015</td><td> 0,01</td><td></td>
<td>C<sub>2</sub>H<sub>4</sub>% barrier</td><td> 6,8</td><td> 7,1</td><td> 6,5</td><td></td>
<td>C<sub>6</sub>Hi2 barrier</td><td> 0,93</td><td> 1,17</td><td> 2,7</td><td></td>
<td></td><td></td><td></td><td></td><td></td>
<td>Properties of the final polymer</td><td></td><td></td><td></td><td></td>
<td>MIP [5 kg] (g / 10 min.)</td><td> 0,2</td><td> 0,29</td><td> 0,21</td><td> 0,31</td>
<td>MIF [21.6 kg] (g / 10 min.)</td><td> 4,8</td><td> 6,5</td><td> 8,15</td><td> 6,25</td>
<td>MIF / MIP</td><td> 23,7</td><td> 22,5</td><td> 38,8</td><td> 20,16</td>
<td>Density (kg / dm<sup>3</sup>)</td><td> 0,9509</td><td> 0,9496</td><td> 0,9487</td><td> 0,947</td>
<td>Mw [g / mol]</td><td>3.5E + 5</td><td>3.8E + 5</td><td>3.6E + 5</td><td>3.9E + 5</td>
<td>Mz [g / mol]</td><td>2, OE + 6</td><td>8.3E + 6</td><td>5.0E + 6</td><td>3.5E + 6</td>
<td>Mw / Mn</td><td> 25</td><td> 27</td><td> 52</td><td> 25</td>
<td>LCB</td><td> 0,89</td><td> 0,84</td><td> 0,69</td><td> 0,99</td>
<td>IR comonomer content [%</td><td> 1 0,7%</td><td> 0,7%</td><td> 1,6</td><td> 1,6</td>
<td>in weigh]</td><td>± 0.1 (C<sub>6</sub>H<sub>12</sub>)</td><td>± 0.1 (C<sub>S</sub>H<sub>12</sub>)</td><td>(C<sub>6</sub>H<sub>12</sub>)</td><td>(C<sub>6</sub>Hi<sub>2</sub>)</td>
<td>SIC index</td><td> 3,8</td><td> 3,3</td><td> 1,9</td><td> 6,1</td>
<td>Proportion of dilatation (%)</td><td> 179</td><td> 171</td><td> 120</td><td> 210</td>
<td>Shrink @ 1500 s<sup>_1</sup>, T = 190 ° C [%]</td><td> 15</td><td> 12</td><td> -</td><td> 23</td>
<td>Critical shear rate for shark skin, T = 190 ° C, [1 / s]</td><td> 300</td><td> 300</td><td> -</td><td> 200</td>
<td>Notch tension impact test, T = -30 ° C [kJ / m<sup>2</sup>]</td><td> 164</td><td> 155</td><td> 93</td><td> 145</td>
<td>FNCT 4 MPa / 80 ° C (hours) *</td><td> 329</td><td> 20</td><td> >2000</td><td> 4</td>
<td>Charpy aFM, T = 0 ° C [kJ / m<sup>2</sup>]</td><td> -</td><td> -</td><td> 8,9</td><td></td>
Notes: C2H4 = ethylene; C<sub>6</sub>Hi<sub>2</sub> = hexene; * 2% Arkopal N100 aqueous solution
It is noted that in relation to this date, the best method known by the applicant to implement said invention is that which is clear from the present description of the invention.
Contents2
1 sheet
Sheet 1
84 members in 10 offices
Priority claims15
| Document | Office | Kind | Date |
|---|---|---|---|
| 12189392 | European Patent Office (EPO) | A | |
| 12189392 | European Patent Office (EPO) | A | |
| 121893929 | European Patent Office (EPO) | – | |
| 12194530 | European Patent Office (EPO) | A | |
| 12194530 | European Patent Office (EPO) | A | |
| 121945307 | European Patent Office (EPO) | – | |
| 201261730925 | United States of America | P | |
| 201261730925 | United States of America | P | |
| 61730925 | United States of America | – | |
| 2013072000 | European Patent Office (EPO) | W | |
| 2013072000 | European Patent Office (EPO) | W | |
| EP20120189392 | – | – | – |
| EP20120194530 | – | – | – |
| US201261730925P | – | – | – |
| WO2013EP72000 | – | – | – |
Members84
| Document | Office | Kind | |
|---|---|---|---|
| EP2722347A1 | European Patent Office (EPO) | A1 | |
| CA2887044A1 | Canada | A1 | |
| CA2887332A1 | Canada | A1 | |
| CA2887336A1 | Canada | A1 | |
| WO2014064059A1 | World Intellectual Property Organization (WIPO) | A1 | |
| WO2014064060A1 | World Intellectual Property Organization (WIPO) | A1 | |
| WO2014064061A1 | World Intellectual Property Organization (WIPO) | A1 | |
| WO2014064062A1 | World Intellectual Property Organization (WIPO) | A1 | |
| EP2738211A1 | European Patent Office (EPO) | A1 | |
| EP2738212A1 | European Patent Office (EPO) | A1 | |
| EP2738213A1 | European Patent Office (EPO) | A1 | |
| KR20150067271A | Republic of Korea | A | |
| KR20150068438A | Republic of Korea | A | |
| KR20150068439A | Republic of Korea | A | |
| CN104755549A | China | A | |
| EP2909263A1 | European Patent Office (EPO) | A1 | |
| EP2909264A1 | European Patent Office (EPO) | A1 | |
| EP2909265A1 | European Patent Office (EPO) | A1 | |
| US2015267010A1 | United States of America | A1 | |
| US2015274866A1 | United States of America | A1 | |
| US2015274947A1 | United States of America | A1 | |
| JP2015532347A | Japan | A | |
| JP2015532348A | Japan | A | |
| JP2015532349A | Japan | A | |
| MX2015004906A | Mexico | A | |
| MX2015004830A | Mexico | A | |
| MX2015004825A | Mexico | A | |
| CN105264006A | China | A | |
| US9353206B2 | United States of America | B2 | |
| US2016237265A1 | United States of America | A1 | |
| US9428623B2 | United States of America | B2 | |
| US9458312B2 | United States of America | B2 | |
| JP6001186B2 | Japan | B2 | |
| JP6001187B2 | Japan | B2 | |
| US2016326354A1 | United States of America | A1 | |
| JP2016196648A | Japan | A | |
| JP2016196649A | Japan | A | |
| RU2015116946A | Russian Federation | A | |
| RU2015117245A | Russian Federation | A | |
| RU2015117278A | Russian Federation | A | |
| CN106170512A | China | A | |
| US9512308B2 | United States of America | B2 | |
| EP3109276A1 | European Patent Office (EPO) | A1 | |
| EP3109277A1 | European Patent Office (EPO) | A1 | |
| EP3109278A1 | European Patent Office (EPO) | A1 | |
| RU2607625C2 | Russian Federation | C2 | |
| JP6062056B2 | Japan | B2 | |
| JP2017036433A | Japan | A | |
| US9580583B2 | United States of America | B2 | |
| KR20170033918A | Republic of Korea | A | |
| CN105264006B | China | B | |
| CA2887044C | Canada | C | |
| CA2887332C | Canada | C | |
| CA2887336C | Canada | C | |
| US2017121512A1 | United States of America | A1 | |
| CN104755549B | China | B | |
| KR101732831B1 | Republic of Korea | B1 | |
| KR20170058460A | Republic of Korea | A | |
| RU2621045C2 | Russian Federation | C2 | |
| RU2621807C2 | Russian Federation | C2 | |
| BR112015008932A2 | Brazil | A2 | |
| BR112015008956A2 | Brazil | A2 | |
| BR112015008963A2 | Brazil | A2 | |
| US9738777B2 | United States of America | B2 | |
| JP6262289B2 | Japan | B2 | |
| JP2018111821A | Japan | A | |
| JP2018204022A | Japan | A | |
| KR101950622B1 | Republic of Korea | B1 | |
| JP6495495B2 | Japan | B2 | |
| MX364863B | Mexico | B | |
| MX366406BThis record | Mexico | B | |
| MX366407B | Mexico | B | |
| KR102008590B1 | Republic of Korea | B1 | |
| EP2909263B1 | European Patent Office (EPO) | B1 | |
| EP2909264B1 | European Patent Office (EPO) | B1 | |
| EP2909265B1 | European Patent Office (EPO) | B1 | |
| BR112015008932B1 | Brazil | B1 | |
| CN106170512B | China | B | |
| BR112015008956B1 | Brazil | B1 | |
| BR112015008963B1 | Brazil | B1 | |
| BR122021008743B1 | Brazil | B1 | |
| EP3109276B1 | European Patent Office (EPO) | B1 | |
| EP3109277B1 | European Patent Office (EPO) | B1 | |
| EP3109278B1 | European Patent Office (EPO) | B1 |
1 legal event, as the office reported them to INPADOC
Events
| Event | Code | |
|---|---|---|
| Grant or registrationFG | FG |
Numbers
- Publication
- 366406
- Publication, DOCDB
- 366406
- Publication, EPODOC
- MX366406
- Application
- 20150004906
- Application, DOCDB
- 2015004906
- Application, EPODOC
- MX20150004906
Titles2
- Spanish
- COMPOSICION DE POLIETILENO QUE TIENE UNA PROPORCION ALTA DE DILATACION.
- English
- COMPOSITION OF POLYETHYLENE THAT HAS A HIGH PROPORTION OF DILATATION.
Classification
- CPC, 23
- C08L23/0815
- C08L23/08
- C08L2205/025
- C08L2308/00
- B29C49/04
- B29C48/022
- B29C48/92
- C08J2323/08
- C08L23/06
- C08L2314/02
- B29C49/0005
- B29C49/00
- C08F2/34
- C08F210/16
- C08J5/00
- C08J2323/06
- C08J2423/08
- B29B15/00
- B29K2023/06
- B29L2031/7154
- B29L2031/7172
- C08J2423/06
- C08L2207/07
- IPC, 3
- C08L23 08
- B29C49 00
- B29C48 92