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    • 专利摘要:
    POLYETHYLENE COMPOSITION FOR BLOW MOLDING WITH HIGH STRENGTH STRENGTH. The present invention relates to a polyethylene composition suitable for producing small articles by blow molding, in particular flexible and collapsible tubes, said composition having the following characteristics: 1) Density of more than 0.948 to 0.955 g/cm3; 2) IF/IFP ratio from 12 to 25; 3) IF from 25 to 40 g/10 min; 4) Mz from 1,000,000 to 2,000,000 g/mol; 5) long chain branching index (IRCL) equal to or greater than 0.55.
    公开号:BR112015031736B1
    申请号:R112015031736-7
    申请日:2014-06-19
    公开日:2021-07-06
    发明作者:Gerhardus Meier；Ulf Schüller；Diana Dotsch；Bernd Lothar Marczinke；Jens Wiesecke
    申请人:Basell Polyolefine Gmbh；
    IPC主号:
    专利说明:

    field of invention
    [001] The present invention relates to a polyethylene composition suitable for producing small articles by blow molding, especially flexible and collapsible tubes. Background of the invention
    [002] Some examples of prior art compositions used for said application are described in WO2009003627.
    [003] It has now been found that the proper selection of molecular weights of the composition makes it possible to obtain an especially high tensile crack strength and, at the same time, an extremely smooth and almost gel-free article surface.
    [004] Another important advantage of the polyethylene composition of the present invention is that it can be melt processed at unusually high shear rates. This means that it is possible to use high processing speeds and/or melt processing at low temperatures without encountering flow instabilities, which often produce unacceptable defects in the final article (eg shark skin or melt fracture), even in the absence of processing aids.
    [005] The present invention also relates to a multi-step polymerization process for preparing said polyethylene composition. Invention Summary
    [006] Thus, the present invention provides a polyethylene composition with the following characteristics: 1) density of more than 0.948 to 0.955 g/cm3, preferably 0.949 to 0.954 g/cm3, determined in accordance with ISO 1183 at 23°C ; 2) IF/IFP ratio from 12 to 25, in particular from 15 to 23, where IF is the melt index at 190°C under load of 21.60 kg and IFP is the melt index at 190°C under load of 5 kg, both determined in accordance with ISO 1133; 3) IF from 25 to 40 g/10 min, preferably from 30 to 35 g/10 min and in particular from 31 to 35 g/10 min; 4) Mz from 1,000,000 to 2,000,000 g/mol, in particular from 1,100,000 to 2,000,000 g/mol and preferably from 1,000,000 to 1,500,000 g/mol, in particular from 1,100,000 to 1,500 .000 g/mol, more preferably from 1,000,000 to 1,450,000 g/mol, in particular from 1,100,000 to 1,450,000 g/mol, more preferably from 1,000,000 to 1,400,000 g/mol and in particular from 1,100,000 to 1,400,000 g/mol; 5) long chain branching index (IRCL) equal to or greater than 0.55 and preferably equal to or greater than 0.60; where IRCL is the ratio between the root mean of the radius of gyration Rg measured by CPG-MALLS and the root mean of the radius of gyration of a linear PE with identical molecular weight. Preferably, in addition to the characteristics 1) to 5) mentioned above, the polyethylene composition of the invention also has: 6) eta (0.02) from 25,000 to 35,000 Pa.s, preferably from 28,000 to 33,000 Pa.s; where eta (0.02) is the complex shear viscosity at an angular velocity of 0.02 rad/s, measured by dynamic oscillatory shear in a two-plate rotary rheometer at a temperature of 190°C. Brief description of the drawings
    [007] These and other features, aspects and advantages of the present disclosure will be better understood by referring to the description and other features in the appendix and the figures in the following drawings, where:
    [008] Figure 1 is an illustrative configuration of a simplified process and flow diagram of two gas phase reactors connected in series and suitable for use in accordance with various configurations of ethylene polymerization processes disclosed herein to produce various configurations of compositions of ethylene described herein.
    [009] It is understood that the various configurations are not limited to the arrangements and instrumentality shown in the figures in the drawings. Brief description of the invention
    [0010] The term "polyethylene composition" is intended to include, as alternatives, both a single ethylene polymer and a composition of ethylene polymers, in particular a composition in which two or more components are ethylene polymers, preferably with different molecular weights, such composition being called “bimodal” or “multimodal” polymer in the relevant art.
    [0011] Typically, the polyethylene composition of the present invention consists of or comprises one or more ethylene copolymers.
    [0012] All features defined herein, including features 1) to 6) defined above, refer to said ethylene polymer or composition of ethylene polymers. The addition of other components, such as additives normally employed in the art, can modify one or more of the mentioned characteristics.
    [0013] The IF/IFP ratio provides a rheological metric of the molecular weight distribution.
    [0014] Another metric of the molecular weight distribution is that given by the ratio Mp/Mn, where Mp is the average molar mass weighted by weight and Mn is the average molar mass by number. Both can be measured by gel permeation chromatography (CPG) as explained in the examples.
    Preferred Mp/Mn values for the polyethylene composition of the present invention range from 15 to 30, more preferably from 20 to 30.
    [0016] Furthermore, the polyethylene composition of the present invention preferably has at least one of the following additional characteristics: - Mp equal to or less than 300,000 g/mol, more preferably equal to or less than 250,000 g/mol and particularly from 250,000 to 180,000 g/mol; - IFP: 1.0 to 2.5 g/10 min. more preferably from 1.5 to 2.5 g/10 min. - Comonomer content from 1 to 3%, preferably from 1.2 to 2.5% by weight relative to the total weight of the composition.
    [0017] The comonomer or comonomers present in ethylene copolymers are generally selected from olefins with the formula CH2=CHR, where R is a linear or branched alkyl radical with 1 to 10 carbon atoms.
    [0018] Specific examples are polypropylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-octene and 1-decene. A particularly preferred comonomer is 1-hexene.
    [0019] In particular, in a preferred configuration, the present composition comprises: A) 40 to 60% by weight of a homopolymer or copolymer (the homopolymer being preferred) of polyethylene with density equal to or greater than 0.960 g/cm3 and index of fluidity IF at 190°C under load of 2.16 kg, measured according to ISO 1133, from 20 to 120 g/10 min; B) 40 to 60% by weight of a polyethylene copolymer with IF less than the IF of A) and preferably less than 0.5 g/10 min.
    [0020] The percentages above are presented in relation to the total weight of A) + B).
    [0021] The amount of comonomer in B) is preferably 1.5 to 5% by weight relative to the total weight of B).
    [0022] As mentioned above, the present polyethylene composition can be used to advantage to produce small articles by blow molding, especially flexible and collapsible tubes.
    [0023] Indeed, it is preferably characterized by the following properties. - Tensile crack strength measured by FNCT 4 MPa/80°C > 35 h; - Expansion ratio > 175%; - Notch impact resistance at T = -30°C of 70 kJ/m2 or higher; - Absence of gels in substantial amounts.
    [0024] Test methods are detailed in the examples.
    [0025] In particular, the polyethylene composition of the invention is especially suitable for producing small blow molded articles in the blow molding process, initially by plasticizing the polyethylene molding composition in an extruder at temperatures from 180 to 250° C followed by extrusion through a die into a blow mold, in which the material is cooled.
    [0026] Preferred examples of small blow molds are those with a capacity of 250 to 5000 ml.
    [0027] As mentioned above, the polyethylene composition of the present invention can be melt processed at surprisingly high rates of shear without suffering pressure swings and flow instability.
    [0028] Therefore, another preferred feature of the polyethylene composition of the present invention is a CIS index of value from 1.5 to 3, preferably from 2 to 2.4, where the CIS index is the shear-induced crystallization index determined from according to the following relationship: CIS Index = (tstart,CIS at 1000 xt onset, quiescent)/(IF) where tstart,CIS at 1000, which is measured in seconds, is the time required for the start of crystallization at a rate of 1000 s-1 shear, t onset, quiescent, which is entered in seconds, is the crystallization onset time at a temperature of 125 °C without shear, determined in isothermal mode by differential scanning calorimetry (CDV).
    [0029] Although it is not known of the existence, in principle, of a 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 Ziegler-Natta catalyst.
    [0030] A Ziegler-Natta catalyst comprises the reaction product of an organometallic compound of groups 1, 2 or 13 of the Periodic Table of the Elements with a compound of a transition metal of groups 4 to 10 of the Periodic Table of the Elements (new notation). In particular, the transition metal compound can be selected from compounds of Ti, V, Zr, Cr and Hf and are preferably supported by MgCl2.
    [0031] Particularly preferred catalysts comprise the reaction product of said organometallic compound of groups 1, 2 or 13 of the Periodic Table of Elements, with a solid catalyst component comprising Ti supported by MgCl2.
    The preferred organometallic compounds are organoalumina compounds.
    [0033] Therefore, in a preferred configuration the polyethylene composition of the present invention can be obtained using a Ziegler-Natta polymerization catalyst supported by MgCl2 or, even more preferably, a Ziegler-Natta catalyst comprising the reaction product between: a) a solid catalyst component comprising a Ti compound and an electron donor (DE) compound supported by MgCl2; b) an organoaluminium compound; and optionally c) an external electron donor compound DEext.
    [0034] Preferably, in component a) the DE/Ti molar ratio ranges from 1.5 to 3.5 and the Mg/Ti molar ratio is greater than 5.5 and in particular from 6 to 80.
    Suitable titanium compounds are tetrahalides or compounds with the formula TiXn(OR1)4-n, where 0<n<3, X is halogen, preferably chlorine, and R1 is a C1-C10 hydrocarbon group. The preferred compound is titanium tetrachloride.
    [0036] The DE compound is generally selected from alcohols, ketones, amines, amides, nitriles, alkoxysilanes, aliphatic ethers and aliphatic carboxylic acid esters.
    [0037] Preferably, the DE compound is selected from amides, esters and alkoxysilanes.
    [0038] Excellent results have been obtained with the use of esters, which are therefore particularly preferred as the DE compound. Some specific examples of esters are C1-C20 aliphatic carboxylic acid alkylesters, in particular C1-C8 aliphatic monocarboxylic acid alkylesters like ethylacetate, methylformate, ethylformate, methylacetate, propylacetate, isopropylacetate, n-butylacetate and isobutylacetate. In addition to these, aliphatic ethers are also preferred, particularly C2-C20 aliphatic ethers such as tetrahydrofuran (THF) or dioxane.
    [0039] In said solid catalyst component, the basic support is MgCl2, but other carriers can be used in small amounts. MgCl2 can be used as such or obtained from Mg compounds used as precursors which can be transformed into MgCl2 by reaction with halogenating compounds. Particularly preferred is the use of MgCl2 in its active form, which is widely known in the patent literature as a support for Ziegler-Natta catalysts. USP 4,298,718 and USP 4,495,338 were the first to describe the use of these compounds in Ziegler-Natta catalysis. It is known from these patents that magnesium dihalides in active form used as support or co-support in catalyst components for polymerization of olefins are characterized by X-ray spectra in which the most intense diffraction line on the ASTM spectrum reference card for the spectrum of the inactive halide is wider and has a lower intensity. In the X-ray spectra of the preferred magnesium dihalides in active form, said more intense line has lower intensity and is replaced by a halo in which the maximum intensity is shifted to smaller angles relative to that of the more intense line.
    [0040] Particularly suitable for preparing the polyethylene composition of the present invention are catalysts in which the solid catalyst component a) is obtained by first placing the titanium compound in contact with MgCl2 or with a precursor Mg compound, optionally in the presence of an inert medium, thus producing the intermediate product a') which contains a titanium compound supported by MgCl2; then, the intermediate product a') is brought into contact with the DE compound which is added to the reaction mixture alone or mixed with other compounds among which it constitutes the main component, optionally in the presence of an inert medium.
    [0041] By the term "major component", we mean that the DE compound needs to be the major component in terms of molar quantity relative to other possible components, excluding inert solvents or diluents used to handle the contact mixture. The DE treated product can then be subjected to washes with appropriate solvents to recover the final product. If necessary, treatment with the desired DE compound can be repeated one or more times.
    [0042] As mentioned earlier, a MgCl2 precursor can be used as the essential Mg starting compound. It can be selected, for example, among Mg compounds with the formula MgR'2, where the R' groups can be, independently, substituted or unsubstituted C1-C20 hydrocarbon groups, OR groups, OCOR groups and chlorine, in which R are substituted or unsubstituted C1-C20 hydrocarbon groups, of course under the condition that the R' groups cannot both be chlorine. Also suitable as precursors are Lewis base adducts between MgCl2 and appropriate Lewis bases. A particular and preferred class is MgCl2 (R''OH)m adducts in which the R" groups are C1-C20 hydrocarbon groups, preferably C1-C10 alkyl groups, and m is from 0.1 to 6, preferably from 0 .5 to 3 and more preferably from 0.5 to 2. Adducts of this type can generally be obtained by mixing alcohol and magnesium chloride in the presence of an inert hydrocarbon immiscible with the adduct, operating under stirring conditions at the temperature of melting the adduct (100-130°C) The emulsion is then rapidly cooled, causing the adduct to solidify in the form of spherical particles Representative methods for preparing such spherical adducts are described, for example, in US patents 4,469. 648 and 4,399,054, as well as in WO98/44009. Another usable method for spherulization is spray cooling described in, for example, USP 5,100,849 and 4,829,034.
    [0043] Of particular interest are MgCh*(EtOH)m adducts in which m is 0.15 to 1.7 obtained by exposing adducts with higher alcohol content to a thermal dealcoholization process carried out under nitrogen flow at temperatures from 50 to 150°C until the alcohol content is reduced to the value indicated above. Such a process is described in EP 395083.
    [0044] Dealcoholization can also be carried out chemically by placing the adduct in contact with compounds capable of reacting with the alcohol groups.
    [0045] Generally, such dealcoholized adducts are also characterized by porosity (measured by the mercury method) due to pores with a radius of 0.1 μm between 0.15 and 2.5 cm3/g, preferably from 0.25 to 1, 5 cm3/g.
    [0046] It is preferred that the dealcoholization reaction is carried out at the same time as the reaction step which involves the use of a titanium compound. For this, the adducts are governed with the compound TiXn(OR1)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 TiCl4 (usually cold). The mixture is heated to temperatures of 80 to 130°C and kept at this temperature for 0.5 to 2 hours. Treatment with the titanium compound can be carried out one or more times. Preferably, it should be repeated twice. It can also be carried out in the presence of an electron-donating compound such as those mentioned above. At the end of the process, the solid is recovered by separating the suspension using conventional methods, such as decanting and removing the liquid, filtering and centrifuging, in addition to submitting it to washing with solvents. Although washings are generally carried out with liquid inert hydrocarbons, it is also possible to use more polar solvents (which have, for example, a higher dielectric constant), such as halogenated hydrocarbons.
    [0047] As mentioned above, the intermediate product is then placed with the DE compound under conditions capable of fixing an effective amount of donor to the solid. As this method is highly versatile, the amount of donor can vary widely. As in the example, it can be used in molar proportion to the Ti content in the intermediate product between 0.5 and 20 and preferably between 1 and 10. Although not strictly necessary, the contact is usually carried out in a medium liquid as a liquid hydrocarbon. The temperature at which contact occurs can vary depending on the nature of the reactants. Generally, it is in the range -10° to 150°C, preferably 0° to 120°C. Of course, temperatures that cause the decomposition or degradation of any of the specific reagents should be avoided even if they fall within the generally acceptable range. Furthermore, the treatment time may vary depending on other conditions such as the nature, temperature and concentration of the reagents, among other parameters. As a general guideline, this contact step can last from 10 minutes to 10 hours, with more often from 0.5 to 5 hours. If desired, this step can be repeated one or more times in order to increase the final donor content. At the end of this step, the solid is recovered by separating the suspension using conventional methods, such as decanting and removing the liquid, filtering and centrifuging, in addition to submitting it to washing with solvents. Although washings are generally carried out with inert liquid hydrocarbons, it is also possible to use more polar solvents (which have, for example, a higher dielectric constant), such as halogenated or oxygenated hydrocarbons.
    [0048] As mentioned above, said solid catalyst component is converted into catalysts for polymerization of olefins by reacting according to known methods with organometallic compounds of groups 1, 2 or 13 of the Periodic Table of Elements, and in particular with an alkylaluminum compound .
    The alkylaluminum compound is preferably chosen from trialkylaluminum compounds such as, for example, triethylaluminum, triisobutylaluminum, tri-n-butylaluminum, tri-n-hexylaluminum, tri-n-octylaluminum. It is also possible to use alkylaluminum halides, alkylaluminum hydrides or alkylaluminum sesquichlorides, such as AlEt2Cl and Al2Et3Cl3 possibly in admixture with said trialkylaluminated compounds.
    [0050] The external electron donor compound DEext that can be used to prepare said Ziegler-Natta catalysts can be the same or different from the DE used in the solid catalyst component a). Preferably, the compound is selected from the group formed by ethers, esters, amines, ketones, nitriles, silanes and mixtures thereof. In particular, it can be advantageously selected from C2-C20 aliphatic ethers and, in particular, from cyclic ethers which preferably have 3 to 5 carbon atoms, such as tetrahydrofuran and dioxane.
    [0051] Some specific examples of the aforementioned Ziegler-Natta catalysts and methods for their preparation are provided by WO2004106388.
    [0052] The catalyst can be prepolymerized according to known techniques by producing reduced amounts of polyolefin, preferably polypropylene or polyethylene. Prepolymerization can be carried out before adding the DE electron donor compound, which subjects the intermediate product a') to prepolymerization. As an alternative, the solid catalyst component a) can be subjected to prepolymerization.
    [0053] The amount of prepolymer produced can be up to 500 g per g of intermediate product a') or component a). Preferably, the amount is from 0.5 to 20 g per g of intermediate product a').
    [0054] Prepolymerization is carried out using a reliable cocatalyst such as an organoaluminium compound, which can also be used in combination with an external electron donor compound as discussed above.
    [0055] It can be carried out at temperatures from 0 to 80°C, preferably from 5 to 70°C, in liquid or gas phase.
    Catalysts in which the intermediate product a') is subjected to prepolymerization as described above are particularly preferred.
    [0057] It was found that the use of the polymerization catalyst described above allows to prepare the polyethylene composition of the present invention in a process comprising the following steps, in any order between them: a) polymerization of ethylene, optionally together with a or more comonomers, in a gas-phase reactor in the presence of hydrogen; b) copolymerization of ethylene with one or more comonomers in another gas phase reactor in the presence of hydrogen in an amount smaller than that used in step a);
    [0058] where in at least one of said gas phase reactors the growing polymer particles flow upwards passing through a first polymerization zone ("riser") under conditions of rapid fluidization or transport, leave said "riser" and they enter a second polymerization zone ("downcomer") in which they flow downwards under the action of gravity, leave the "downcomer" and are reintroduced into the "riser", thus establishing a polymer circulation between the two mentioned polymerization zones .
    [0059] In the first polymerization zone ("riser"), conditions of rapid fluidization are maintained by feeding a gaseous mixture containing one or more olefins (ethylene and comonomers) at a speed greater than the transport speed of the polymer particles. The velocity of said gas mixture is preferably comprised between 0.5 and 15 m/s and more preferably between 0.8 and 5 m/s. The terms "transport speed" and "rapid fluidization conditions" are well known in the art. For definitions thereof, see, e.g., "D. Geldart, Gas Fluidization Technology, page 155 et seq., J. Wiley & Sons Ltd., 1986".
    [0060] In the second polymerization zone ("downcomer"), the polymer particles flow under gravity in a dense form, so that the solid reaches high density values (polymer mass per reactor volume), which approximate of the polymer mass density.
    [0061] In other words, the polymer flows vertically down the downcomer in buffer flow (dense flow mode), so that only small amounts of gas are intermingled between the polymer particles.
    [0062] This process allows to obtain in step a) an ethylene polymer with lower molecular weight than the ethylene copolymer obtained in step b).
    [0063] Preferably, the 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 to produce a relatively high molecular weight ethylene copolymer (step a) B). For this purpose, in step a) a first gas-phase reactor, which is preferably a fluidized-bed gas-phase reactor, is introduced into a mixture comprising ethylene, hydrogen and an inert gas. 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 high crystallinity ethylene homopolymer is obtained in step a). However, a minimal amount of comonomer can be introduced, provided 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.
    [0064] Hydrogen is introduced in an amount that depends on the specific catalyst used and, in all cases, suitable to obtain in step a) an ethylene polymer with melt index IF of 20 to 120 g/10 min. To obtain an IF in the above range, the molar ratio between hydrogen and ethylene in step a) should be, indicatively, from 1.5 to 3, the amount of ethylene monomer used from 6 to 20% by volume, preferably from 10 to 15% 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 aces and one or more comonomers, if any. The inert gases, which are needed to dissipate the heat generated by the polymerization reaction, are conveniently selected from nitrogen and saturated hydrocarbons, with propane being most preferred.
    [0065] The operating temperature of the reactor in step a) is selected between 50 and 120°C, preferably 65 and 100°C, while the operating pressure is between 0.5 and 10 MPa and preferably between 2.0 and 3 .5 MPa.
    [0066] In a preferred configuration, the ethylene polymer obtained in step a) represents 40 to 60% by total weight of ethylene polymer produced in the process as a whole, i.e., in the first and second reactors connected in series .
    [0067] The ethylene polymer originating from step a) and the gas intermingled therein go through a gas and solid separation step to prevent the gas mixture originating from the first polymerization reactor from entering the reactor of step b) (second reactor) of gas phase polymerization). Said gas mixture can be recycled back to the first polymerization reactor, while the separated ethylene polymer is introduced into the reactor of step b). A suitable point of introduction into the polymer in the second reactor is the portion connecting the "downcomer" and the "riser", where the solids concentration is especially low so that the flow conditions are not harmed.
    [0068] The operating temperature of step b) is in the range of 65 to 95°C and the pressure in the range of 1.5 to 4.0 MPa. The second gas phase reactor is designed to produce a relatively high molecular weight ethylene copolymer by copolymerizing ethylene with one or more comonomers. Furthermore, to further extend the molecular weight distribution of the final ethylene polymer, the reactor in step b) can be conveniently operated by setting different monomer and hydrogen concentration conditions inside the riser and downcomer .
    [0069] For this purpose, in step b) the gas mixture that intermingles the polymer particles originating from the riser can be totally or partially prevented from entering the downcomer, so as to produce two zones with different gas composition. This can be accomplished by introducing a gaseous or liquid mixture into the downcomer via an inlet positioned at an appropriate point on the downcomer, preferably at the top of the downcomer. Said gaseous and/or liquid mixture must have an appropriate composition and different from that of the gaseous mixture present in the riser. The flow of said gaseous and/or liquid mixture can be regulated so as to generate an upward and countercurrent flow to the flow of polymer particles, especially at the top of it, which acts as a barrier for the gaseous mixture intermingled between polymer particles originating from the "riser". In particular, it is advantageous to introduce a mixture with relatively low hydrogen content to produce the relatively higher molecular weight polymer fraction found in the downcomer. One or more comonomers can be introduced into the "downcomer" in step b), optionally together with ethylene, propane or other gases.
    [0070] The molar ratio of hydrogen and ethylene in the "downcomer" in step b) is comprised between 0.05 and 0.3, the concentration of ethylene is comprised between 1 to 20%, preferably from 3 to 10% by volume and the comonomer concentration is comprised between 0.5 and 2% by volume based on the total volume of gas present in said "downcomer". The rest consists of propane and similar inert gases. As the molar concentration of hydrogen in the downcomer is very low, carrying out the process of the present invention allows to bind a relatively high amount of comonomer to the high molecular weight polyethylene fraction.
    [0071] Polymer particles coming out of the downcomer are reintroduced into the riser in step b).
    [0072] As the polymer particles keep arriving and the riser no longer receives comonomer, the concentration of said comonomer drops to a range of 0.1 to 1% or volume based on the total volume of gas present in said riser ". In practice, the comonomer content is controlled in order to obtain the desired density of the final polyethylene. In the "riser" of step b), the molar ratio of hydrogen and ethylene is comprised between 0.1 and 0.6 and the concentration of ethylene is comprised between 5 to 15% by volume based on the total volume of gas present in said "riser". The rest consists of propane and other inert gases.
    [0073] WO9412568 provides further details on the polymerization process described above.
    [0074] In addition to polyethylene, the polyethylene composition of the invention may also comprise other additives. Such additives can be, for example, thermostabilizers, antioxidants, UV absorbers, photostabilizers, metal deactivators, peroxide decomposing compounds, basic costabilizers in amounts of up to 10% by weight, preferably up to 5% by weight, in addition to a decomposition agent. fillers, reinforcing materials, plasticizers, lubricants, emulsifiers, pigments, optical brighteners, flame retardants, antistatic blowing agents or combinations of the compounds in total amounts of up to 50% by weight based on the total weight of the mixture.
    [0075] The following examples are presented to illustrate the present invention without limiting it. EXAMPLES
    [0076] Unless otherwise indicated, the following test methods are used to determine the properties described in the detailed description and examples. Density
    [0077] Determined in accordance with ISO 1183 at 23°C. Determination of molecular weight distribution
    [0078] The determination of the molar mass distributions and the mean values of Mn, Mp, Mz and Mp/Mn derived therefrom was performed by high temperature gel permeation chromatography using the method described in ISO 16014-1, 2 and 4, 2003 edition. According to the referred ISO standards, the details are as follows: Solvent 1,2,4-trichlorobenzene (TCB), apparatus and solutions at a temperature of 135°C and, as a polymerization detector, an infrared detector PolymerChar (Valencia, Paterna 46980, Spain) IR-4 suitable for use with TCB. A WATERS Alliance 2000 was used with a SHODEX UT-G guard column and connected SHODEX UT 806 M (3x) and SHODEX UT 807 (Showa Denko Europe GmbH, Konrad-Zuse-Platz 4, 81829 Muenchen, Germany) separation columns in series. The solvent was vacuum distilled under nitrogen and stabilized with 2,6-di-tert-butyl-4-methylphenol 0.025% by weight. The flow rate used was 1 ml/min, the injection 500 μl and the polymer concentration in the range of 0.01% < conc. < 0.05% w/w. Molecular weight calibration was established using polystyrene monodispersed (PS) standards from Polymer Laboratories (currently Agilent Technologies, Herrenberger Str. 130, 71034 Boeblingen, Germany)) in the range of 580 g/mol to 11600000g/mol and additionally , hexadecane. Then, the calibration curve was 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 for this were: for PS, kPS= 0.000121 dl/g, αPS=0.706; for PE with kPE=0.000406 dl/g, αPE=0.725, valid for TCB at 135°C. Recording, calibration and calculations were performed using NTGPC_Control_V6.02.03 and NTGPC_V6.4.24 (hs GmbH, Hauptstraβe 36, D-55437 Ober-Hilbersheim, Germany) respectively. Shear-induced crystallization test
    [0079] This method is used to determine the onset time of polymer shear-induced crystallization (CIS) or tinnitus, CIS. The samples are melted at 200 °C and pressed for 4 minutes at 200 bar in a laboratory press to form 1 mm thick plates. Then, 25 mm specimen discs are cut out and these specimens are introduced into a rotating two-plate rheometer. A rotary rheometer Physica MCR 301, produced by AntonPaar, was used.
    [0080] Then, the sample was melted inside the test geometry at 190°C for 4 minutes, cooled to ~10 K/min until reaching the test temperature of T = 125 °C and annealed for 5 minutes. Consequently, a constant rate shear was applied and the shear viscosity was monitored as a function of time. The experiment was repeated, applying each time a different shear rate between 0.05 and 0.5 s-1. The CIS onset time (tstart,CIS) is considered to be the point at which the viscosity increases by 50% of its equilibrium value n at 125 °C. The equilibrium value is the average of the melt viscosity under constant shear measured at the specific temperature.
    [0081] The log tstart,CIS vs. log shear rate presents a linear function (of the type y = Ax + B), whose extrapolation revealed a shear rate of 1000 s-1 (relevant to the process) to determine the start value,CIS at 1000.
    [0082] The CIS index is then calculated according to the following relationship:

    [0083] The tstart, quiescent (in seconds) corresponds to the start of crystallization at a temperature of 125 °C under quiescent conditions, i.e., without shear measured in isothermal mode in a differential scanning calorimetry (DVC) apparatus as explained Next.
    [0084] The IF is the melt index (g/10 min) measured at T = 190 °C under a load of 21.6 kg according to ISO 1133.
    [0085] The same protocol is described in the following documents. - I. Vittorias, Correlation among structure, processing and product properties, Würzburger Tage 2010, Wolfgang Kunze TA Instruments, Germany. - Wo DL, Tanner RI (2010), The impact of blue organic and inorganic pigments on the crystallization and rheological properties of isotactic polypropylene, Rheol. Acta 49, 75. Derakhshandeh M., Hatzikiriakos S.G., Flow-induced crystallization of high-density polyethylene: the effects of shear and uniaxial extension, Rheol. Minutes, 51, 315-327, 2012. Isothermal CDV
    [0086] The tstart, quiescent, that is, the onset time when no deformation is applied at 125 °C, was determined by the isothermal differential scanning calorimetry (CDV) method. The value was measured at 125 °C on a TA Instruments Q2000 CDV apparatus. The start, quiescent was determined by the commercially available TA Universal Analysis 2000 software. Sample preparation and configuration followed DIN EN ISO 11357-1:2009 and ISO 11357-3:1999. Complex shear viscosity
    [0087] Measured at the angular frequency of 0.02 rad/s and 190°C as follows.
    [0088] The samples are cast and pressed for 4 minutes at 200πC and 200 bar on 1 mm thick plates. 25 mm sample discs were stamped and inserted into the rheometer preheated to 190 πC. This measurement can be performed by any commercially available rotary rheometer. In this case, Anton Paar MCR 300 with two-plate geometry was used. A so-called frequency scan is performed after 4 minutes of sample annealing at the temperature measured at T = 190 πC under a constant stress amplitude of 5%, and the response of the material to stress was measured and analyzed in the range of excitation frequencies w of 670 to 0.02 rad/sec. A standardized basic software was used to calculate the rheological properties, i.e., the storage modulus G', the loss modulus G'', the phase delay δ (=arctan(G"/G')) and a complex viscosity η* as a function of the applied frequency, that is, η* (
    . The value of the latter for the applied frequency w of 0.02 rad/s is (0.02). fluidity index
    [0089] Determined in accordance with ISO 1133 at 190°C with the specified load. Long Chain Branching Index (IRCL)
    [0090] The RCL index corresponds to the branching factor g' measured for a molecular weight of 106 g/mol. The branching factor g', which allows the determination of long-chain branches when the Mp is high, was measured by gel permeation chromatography (CPG) coupled with multi-angle laser scattering (MALLS, "Multi-Angle Laser-Light Scattering" ), as described below. Parameter g' is the relationship between the measured root mean square of the radius of swivel and the mean of a linear polymer of the same molecular weight. Linear molecules have g' of 1, while values less than 1 indicate the presence of RCL. The g' values as a function of molecular weight M are calculated by the following equation:
    where <Rg2>,M is the root mean square of the radius of gyration for the molecular weight fraction M.
    [0091] The turning radius for each eluted fraction of the CPG (as described above, but with a flow rate of 0.6 ml/min and column filled with 30 μm particles) is measured by analyzing the light scattering at various angles . Therefore, this MALLS setting allows you to determine the molecular weight M and <Rg2>sample,M and define a g’ for M = 106 g/mol as measured. The <Rg2> ref. linear,M is calculated by the relationship established between the gyroradius and the molecular weight of linear polymers in solution (Zimm and Stockmayer WH 1949)) and confirmed by measuring a linear PE reference with the same apparatus and the same methodology described above .
    [0092] The same protocol is described in the following documents.
    [0093] Zimm BH, Stockmayer WH (1949) The dimensions of chain molecules containing branches and rings. J Chem Phys 17
    [0094] Rubinstein M., Colby RH. (2003), Polymer Physics, Oxford University Press Comonomer content
    [0095] Comonomer content is determined by infrared according to ASTM D 6248 98 using a Bruker Tensor 27 Fourier transform infrared spectrometer calibrated according to a chemometric model to determine ethyl or butyl side chains in PE with butene or hexene as comonomer, respectively. The result was compared with the estimated comonomer content derived from the mass balance of the polymerization process and the results were consistent. expansion ratio
    [0096] The expansion ratio of the studied polymers was measured by a Gottfert Rheotester2000 and Rheograph25 capillary rheometer at T = 190°C equipped with a commercial matrix 30/2/2/20 (total length 30 mm, active length 2 mm, diameter 2 mm, L/D=2/2 and 20° entry angle) and an optical device (Gottfert laser diode) to measure the thickness of the extruded strip. The sample is melted in a capillary tube at 190°C for 6 minutes and extruded at a piston speed corresponding to a final die shear rate of 1440 s-1. The extruded product is cut (by an automatic cutter also produced by Gottfert ) at a distance of 150 mm from the die output when the piston reaches a position 96 mm from the device inlet. The diameter of the extruded product as a function of time is measured by the laser diode at a distance of 78 mm from the outlet. The maximum value corresponds to Dextruded. The expansion ratio is determined by the formula: SR = (Dextruded-Dmatrix)100%/Dmatrix
    [0097] where Dmatrix is the corresponding diameter at the output of the matrix measured by the laser diode. Notch impact resistance test
    [0098] The notch impact strength was determined according to ISO 8256:2004 using type 1 specimens with two grooves according to method A. The test specimens (4 x 10 x 80 mm) were cut from a compression molded sheet in accordance with the requirements of ISO 1872-2 (average cooling rate 15 K/min and high pressure during the cooling phase). Test samples were grooved on both sides with a 45° V-groove. The depth was 2 ± 0.1 mm and the radius of curvature at the tip of the groove 1.0 ± 0.05 mm. The free distance between the presses was 30 ± 2 mm. Prior to measurement, all test samples were conditioned at a constant temperature of -30°C for a period of 2-3 hours. The procedure for measuring the tensile strength to impact, including energy correction after method A, is described in ISO 8256. Stress cracking strength measured by the notch crack crack strength test (FNCT)
    [0099] The tensile crack strength of polymer samples is measured according to the international standard ISO 16770 (FNCT) in aqueous surfactant solution. A 10mm thick compression molded sheet was prepared from the polymer sample. Bars with square cross section (10x10x100 mm) were grooved by a stylet on four sides perpendicular to the tension direction. A furrower device described in M. Fleissner in Kunststoffe 77 (1987), pp. 45 is used to create sharp grooves 1.6mm deep. The applied load is calculated from the tensile strength divided by the initial bonding area. The bonding area is the remaining area (area = total cross section minus the groove area). For FNCT samples: 10x10 mm2 - 4 x trapezoid groove area = 46.24 mm2 (crossover area remaining for process failure and crack propagation). Test samples are loaded under standard conditions suggested in ISO 16770 under a constant load of 4 MPa at 80°C in a 2% (by weight) aqueous solution of ARKOPAL N100 surfactant. The time to rupture of the test sample was measured. Charpy's aCN
    [00100] Determination of fracture strength by an internal method on test bars measuring 10 x 10 x 80 mm sawn from a 10 mm thick compression molded sheet. Six test bars like these were grooved in the center with a razor blade from the previously mentioned grooving device for the FNCT test. The groove depth is 1.6 mm. The measurement is basically carried out according to the Charpy measurement method and according to the ISO 179-1 standard using modified test samples and modified impact geometry (distance between supports). All samples used in the test were conditioned at the measuring temperature of -30°C for a period of 2 to 3 hours. Then, a test sample was immediately placed on the stand of a pendulum impact tester in accordance with ISO 179-1. The distance between the supports is 60 mm. The 2 J hammer drop is triggered and the drop angle set to 160°, the pendulum length to 225 mm and the impact velocity to 2.93 m/s. The fracture strength value is expressed in kJ/m2 and given by the quotient of the impact energy consumed and the initial cross-sectional area at the level of the groove. Only values for complete fractures of bending fractures can be used here as a basis for a common meaning (see suggestion in ISO 179-1). Example 1 and Comparative Examples 1 and 2 Preparation of the process
    [00101] In Example 1, the process of the invention was carried out under continuous conditions in a plant that had two connected gas phase reactors, as shown in Figure 1. Example 1
    [00102] The solid catalyst component was prepared as described in Example 15 of WO2004106388. Polymerization
    [00103] 18 g/h of the prepolymerized solid catalyst component as described above were introduced using 5 kg/h of liquid propane into a pre-contact apparatus in which triethylaluminum (TEA) had been introduced. The weight ratio of aluminum alkyl to solid catalyst component was 3:1. The pre-contact step was carried out under stirring at 50°C, with a total residence time of 120 minutes.
    [00104] The catalyst entered the first gas phase polymerization reactor 1 of Fig. 1 through line 10. In the first reactor, ethylene was polymerized using H2 as molecular weight regulator in the presence of propane as inert diluent. 40 kg/h of ethylene and 130 g/h of hydrogen were introduced into the first reactor through line 9. No comonomer was introduced into the first reactor.
    [00105] The polymerization was carried out under a temperature of 80°C and a pressure of 2.9 MPa. The polymer obtained in the first reactor was withdrawn in a non-continuous way through line 11, separated from the gas in the gas and solid separator 12 and reintroduced in the second gas phase reactor through line 14.
    [00106] The polymer produced in the first reactor had a melt index (IF) of about 80 g/10 min and density of 0.968 kg/dm3.
    [00107] The second reactor was operated under polymerization conditions of about 84°C and pressure of 2.5 MPa. 10 kg/h of ethylene, 0.5 g/h of hydrogen and 1.8 kg/h of 1-hexene were introduced into the downcomer 33 of the second reactor via line 46. 5 kg/h of propane, 31 kg/h h of ethylene and 5 g/h of hydrogen were introduced through line 45 into the recycling system.
    [00108] To extend the molecular weight distribution of the final ethylene polymer, the second reactor was operated by establishing different conditions of concentrations of monomers and hydrogen inside the riser 32 and the downcomer 33. This is achieved by introducing - through line 52 to 330 kg/h of a liquid flow (liquid barrier) in the upper part of the "downcomer" 33. Said liquid flow must have a different composition from that of the gas mixture present in the "riser". Said different concentrations of monomers and hydrogen inside the riser, in the downcomer of the second reactor and in the composition of the liquid barrier are indicated in Table 1. The liquid flow of line 52 originates from the condensation step in the condenser 49 under working conditions at 48°C and 2.5 MPa, in which part of the recycled stream is cooled and partially condensed. As shown in the figure, a separator vessel and pump are positioned in the order shown downstream of condenser 49. The final polymer was continuously discharged via line 54.
    [00109] The polymerization process in the second reactor produced polyethylene fractions of relatively high molecular weight. Table 1 specifies the properties of the final product. It can be observed that the melt flow index of the final product is lower than that of the ethylene resin produced in the first reactor, demonstrating that the formation of high molecular weight fractions in the second reactor.
    [00110] The first reactor produced about 48% by weight (% division) of the total amount of the final polyethylene resin produced in the first and second reactor. At the same time, the polymer obtained is endowed with a relatively broad molecular weight distribution, as indicated by its IF/IFP ratio of 19. Comparative Example 1
    [00111] The polymer of the comparative example is a Ziegler-Natta polyethylene composition, commercially available under the trade name Hostalen GF 4750 (Basell). Comparative Example 2
    [00112] The polymer of the comparative example is a Ziegler-Natta polyethylene composition, commercially available under the trade name Lupolen 5021DX (Basell). Table 1

    Remarks: C2H4 = ethylene; C4H8 = butene; C6H12 = hexene; *2% aqueous solution of Arkopal N100
    权利要求:
    Claims (12)
    [0001]
    1. Polyethylene composition, characterized by the fact that it has the following characteristics: a) density of more than 0.948 to 0.955 g/cm3, determined in accordance with ISO 1183 at 23°C; b) IF/IFP ratio from 12 to 25, where IF is the melt index at 190°C under a load of 21.60 kg and IFP is the melt index at 190°C under a load of 5 kg, both determined accordingly with ISO 1133; c) IF from 25 to 40 g/10 min; 4) Mz from 1,000,000 to 1,500,000 g/mol; d) long chain branching index (IRCL) equal to or greater than 0.55; where IRCL is the ratio between the root mean square of the radius of gyration Rg measured by CPG-MALLS and the root mean of the radius of gyration of a linear PE with the same molecular weight. e) IFP: 1.5 to 2.5 g/10 min.
    [0002]
    2. Polyethylene composition according to claim 1, characterized in that it also has: f) eta (0.02) from 25,000 to 35,000 Pa.s; where eta (0.02) is the complex shear viscosity at an angular frequency of 0.02 rad/s, measured with dynamic oscillatory shear in a two-plate rotary rheometer at a temperature of 190°C.
    [0003]
    3. Polyethylene composition according to claim 1 or 2, characterized in that it comprises one or more ethylene copolymers.
    [0004]
    4. Polyethylene composition according to claim 3, characterized in that it has a comonomer content of 1 to 3%.
    [0005]
    5. Polyethylene composition according to any one of claims 1 to 3, characterized in that it can be obtained using a Ziegler-Natta polymerization catalyst.
    [0006]
    6. Polyethylene composition according to claim 5, characterized in that the Ziegler-Natta polymerization catalyst comprises the product of the reaction between: a) a solid catalyst component comprising a titanium compound supported on MgCl2, wherein the said component is obtained by placing the titanium compound in contact with MgCl2 or with a precursor magnesium compound, optionally in the presence of an inert medium, thus obtaining an intermediate product a') and then subjecting it to ') pre-polymerization and contact with an electron donor compound; b) an organoaluminium compound; and optionally c) an external electron donor compound.
    [0007]
    7. Polyethylene composition according to claim 1, characterized in that it has at least one of the following additional characteristics: - Mp equal to or less than 300,000 g/mol; - Mp/Mn from 15 to 30; - CIS index from 1.5 to 3; where the CIS index is the shear-induced crystallization index determined according to the following relationship:
    [0008]
    8. Polyethylene composition according to claim 1, characterized in that it also 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 melt index IF at 190°C under a load of 2.16 kg, measured in accordance with ISO 1133, from 20 to 120 g/10 min; B) 40 to 60% by weight of an ethylene copolymer with an IF value less than the IF value of A).
    [0009]
    9. Manufactured articles, characterized in that they comprise the composition as defined in claim 1.
    [0010]
    10. Manufactured articles according to claim 9, characterized in that they are in the form of blow molded articles with a capacity of 250 to 5000 ml.
    [0011]
    11. Process for preparing the polyethylene composition as defined in claim 1, characterized in that all polymerization steps are carried out in the presence of a Ziegler-Natta polymerization catalyst supported on MgCl2.
    [0012]
    12. Process according to claim 11, characterized in that it comprises the following steps, in any order between them: a) polymerization of ethylene, optionally together with one or more comonomers, in a gas phase reactor in the presence of hydrogen; b) copolymerization of ethylene with one or more comonomers in another gas phase reactor in the presence of hydrogen in an amount smaller than in step a); wherein, in at least one of said gas phase reactors, the growing polymer particles flow upward past a first polymerization zone under conditions of rapid fluidization or transport, leave said "riser" and enter a second zone of polymerization in which they flow downwards under gravity, leave the second polymerization zone and are reintroduced into the first polymerization zone, thus establishing a polymer circulation between said two polymerization zones.
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    KR20160032114A|2016-03-23|
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    RU2016101002A|2017-07-28|
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    WO2014206854A1|2014-12-31|
    US20160152747A1|2016-06-02|
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    法律状态:
    2019-12-17| B06U| Preliminary requirement: requests with searches performed by other patent offices: procedure suspended [chapter 6.21 patent gazette]|
    2020-12-29| B06A| Patent application procedure suspended [chapter 6.1 patent gazette]|
    2021-05-25| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|
    2021-07-06| 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 19/06/2014, OBSERVADAS AS CONDICOES LEGAIS. |
    优先权:
    申请号 | 申请日 | 专利标题
    EP13173535.9|2013-06-25|
    EP20130173535|EP2818509A1|2013-06-25|2013-06-25|Polyethylene composition for blow molding having high stress cracking resistance|
    PCT/EP2014/062927|WO2014206854A1|2013-06-25|2014-06-19|Polyethylene composition for blow molding having high stress cracking resistance|
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