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    • 专利摘要:
    HDPE. The present invention relates to a multimodal polyethylene polymer having an MFR2 of 0.05 to 10.0 g / 10 minutes, a density of 940 kg / m3 or greater, an elastic modulus of 900 MPa or greater and in which .
    公开号:BR112015028045B1
    申请号:R112015028045-5
    申请日:2014-05-09
    公开日:2021-01-19
    发明作者:Andrey Buryak；Christian Rein；Luc Monnissen；Geir Kristian Johnsen；Joy Cheng
    申请人:Borealis Ag；Abu Dhabi Polymers Company Limited (Borouge) L.L.C.；
    IPC主号:
    专利说明:

    [001] The present invention relates to a polyethylene polymer for injection molded articles, in particular for the production of lids and closures. The present invention also relates to a process for the production of said polymer, an injection molded article comprising said polymer and the use of said polymer for the production of an injection molded article, such as a cap or closure. The polyethylene of the invention is a multimodal high density polyethylene with a specific molecular weight distribution allowing the formation of injection molded articles with advantageous properties in terms of tensile strength and modulus of elasticity and in terms of the appearance of the article (appearance ). Background
    [002] Injection molding can be used to create a wide variety of articles including articles having relatively complex shapes and a range of sizes. Injection molding is, for example, suitable for the production of articles used as lids and closures for drinks and food applications, such as for bottles containing carbonated and non-carbonated drinks, or for non-food applications such as containers for cosmetic products and pharmaceutical products.
    [003] Injection molding is a molding process in which a polymer is melted and then loaded into a mold by means of injection. During the initial injection, high pressure is employed and the polymer melt is compressed. Thus, in the injection into the mold, the polymer melts initially expands or "relaxes" to fill the mold. The mold, however, is at a lower temperature than that of the polymer melt, and for that reason as the melt of the polymer cools, contraction tends to occur. To compensate for this effect, back pressure is applied. Accordingly, the polymer melt is further cooled to allow the molded article to be removed from the mold without causing deformation.
    [004] An important property of an injection molded article is tensile strength. It should be noted that the injection molded articles of the invention must not exhibit a brittle fracture and must therefore have a high resistance to stress breakage. An increase in tensile strength is, however, generally associated with a decrease in tensile strength, for example, in the modulus of elasticity. It should also be noted that injection molded articles are preferably rigid. This decrease in the modulus of elasticity is particularly marked for HDPE. Current inventors have looked for new HDPEs, developed, in particular, for the cover and beam market, which has improved tensile strength and modulus with high elasticity. To increase the refusal, however, these improvements should not be at the expense of the processability of the polymer or the appearance of any formed article. Processability must be maintained or even improved to meet customer needs. Injection molded articles are produced quickly and any reduction in processability can increase cycle times and consequently reduce the efficiency of the process.
    [005] Current inventors have found that if HDPEs have a certain ratio of molecular weight properties to the appropriate melt flow rates for injection molding, high tensile strength and tensile strength can be obtained. In particular, the present invention describes a multimodal HDPE polymer with adapted molecular weight that results in improved FNCT without reducing the modulus of elasticity. The FNCT is clearly improved during a selection of comparable grades of commercial polymer. In addition, the lids or closures produced using this polymer look better, specifically in terms of the lower raised ends and less angel hair.
    [006] When the cap or closure is formed in the injection molding process, there is usually a small defect in the injection point at the top of the cap. This defect is a slightly raised part at the top of the cover and is called a raised end. Although it is difficult to observe with the naked eye, the raised end can generally be felt at the top in most lids and closures. The polymers of the present invention allow this raised end to be minimized in size.
    [007] Images of an elevated end (figure 2) that is generally unacceptably extended, and a reduced “elevated end” (typically one that is less than 0.5 mm high - figure 1) which is the goal in the industry.
    [008] Furthermore, when the injection molding process is complete, another problem that can occur is the formation of angel hair. Angel hair is the polymer filament type fiber that forms at the top of the cap at the injection point as the cap is moved away from the injection molding nozzle in the continuous injection molding process. If the injection molding process and the polymer employed is not ideally suited for the injection molding process, the polymer melt can extend to form this hair-like fiber. The polymers of the invention also minimize the formation of such hair. Figure 3 shows the formation of angel hair in a cap. The hair of angels can have serious consequences for further manipulation of the cap, for example, the impression on it and its appearance.
    [009] The invention depends on the use of polymers which have a specific molecular weight distribution through a comparison in their values of Mz, Mn and Mw. Current inventors have found that a specific relationship of Mz, Mw and Mn gives rise to polymers with advantageous properties. For this reason in particular, the Mz / Mw ratio should be reduced compared to the Mw / Mn ratio. The relationship in claim 1 defines the polymers that have the back with less considerable high molecular weight. This does not prevent polymers having a relatively wide molecular weight distribution Mw / Mn however.
    [0010] Without wishing to be limited to theory, it may be that the problem of angel hair is exacerbated by the presence of chains with high molecular weight within the polymer. It may be that because the polymers of the invention have a lower back with high molecular weight less considerable than the polymers that offer benefits in terms of minimizing angel hair. Likewise, the inventors suggest that high levels of Mz / Mw may result in the formation of larger "high ends" in the caps. Polymers can therefore allow the formation of a lower “high end”.
    [0011] To avoid doubts, these raised ends are so small that cutting them is impractical. Likewise, caps are produced quickly in high numbers and the cost of even attempting a cutting process on a plurality of caps would be prohibitive.
    [0012] The advantageous properties of the HDPE of the invention can also be obtained without loss of processability. Again, the relationship between the high Mw and low Mw chains within the polymer of the invention means that the processability of the polymers of the invention is excellent.
    [0013] In EP-A-1940942, HDPE compositions are described mainly for blow molding applications. The compositions comprise a mixture of unimodal HDPE and a unimodal polymer with high Mw to thereby form a bimodal composition. The polymers do not satisfy the relationship in claim 1 however.
    [0014] Current inventors have compared the polymer of the invention to a wide range of commercially available injection molding classes of comparable modulus to show that the relationship in claim 1 is not one that can be found in commercial polymers and is a which produces the advantageous properties highlighted above. Summary of the Invention
    [0015] Seen from one aspect the invention provides a multimodal polyethylene polymer having an MFR2 of 0.05 to 10.0 g / 10 minutes, a density of 940 kg / m3 or greater, an elastic modulus of 900 MPa or greater and where

    [0016] Preferably, the multimodal polyethylene polymer comprises a lower molecular weight homopolymer component in a high molecular weight copolymer component, for example, with a C3-12 alpha olefin comonomer.
    Thus, seen from another aspect, the invention provides a multimodal polyethylene polymer having a lower molecular weight homopolymer component in a high molecular weight copolymer component, for example, with a alpha olefin C3-12 and having an MFR2 of 0.05 to 10.0 g / 10 minutes, a density of 940 kg / m3 or greater, an elastic modulus of 900 MPa or greater and in which

    [0018] The polymer of the invention has a large Mw / Mn ratio and a small Mz / Mw ratio. This molecular distribution structure results in injection molded articles, and in particular lids and closures, which look good (for example, lower raised end and less angel hair).
    [0019] Seen from another aspect the invention provides a multimodal polyethylene polymer having an MFR2 of 0.05 to 10.0 g / 10 minutes, a density of 940 kg / m3 or greater, an elastic modulus of 900 MPa or greater, where

    Preferably, said multimodal polyethylene polymer comprises a lower molecular weight homopolymer component in a high molecular weight copolymer component, for example, with a C3-12 alpha olefin comonomer.
    Thus, seen from another aspect, the invention provides a multimodal polyethylene polymer having a lower molecular weight homopolymer component in a high molecular weight copolymer component, for example, with a alpha olefin C3-12 and having an MFR2 of 0.05 to 10.0 g / 10 minutes, a density of 940 kg / m3 or greater, an elastic modulus of 900 MPa or greater, where

    [0022] Seen from another aspect the invention provides an injection or compression molded article, such as a cap or closure comprising a polymer as defined herein before. Such lids or closures can weigh from 1 to 10 g. Furthermore, the lids or closures of the invention may have a raised end of less than 0.5 mm in height, such as, less than 0.25 mm in height.
    [0023] Seen from another aspect the invention provides the use of the polymer as defined hereinbefore in the production of a molded injection or compression article, such as a cap or closure.
    [0024] Seen from another aspect the invention provides a process for the preparation of a polyethylene as defined herein before comprising;
    [0025] polymerize ethylene and optionally at least one C3-10 alpha olefin co-monomer to form a low molecular weight component (A); and subsequently
    [0026] polymerize ethylene and optionally at least one C3-10 alpha olefin co-monomer in the presence of component (A) in order to form a high molecular weight component (B). The invention also comprises the compression or injection molding of the product of said process to form an article. Preferably, the multimodal polyethylene polymer produced in this process comprises a lower molecular weight homopolymer component in a high molecular weight copolymer component, for example, with a C3-12 alpha olefin comonomer. Definitions
    [0027] The term Mz refers to the average molecular weight of Z of the polymer. Mz is measured by establishing the thermodynamic balance where the molecules are distributed according to the molecular size. Mz is more sensitive than the other averages to the largest molecules present in the sample and, as a result, the values that have been reported in the present invention represent the polymers with a less considerable high molecular weight back. Detailed Description of the Invention
    [0028] It has been found that the high density polyethylene polymer according to the invention provides an improved material for compression or especially injection molding, in particular for cover and closure applications, which combines very good mechanical properties, for example, in terms of FNCT and modulus of elasticity with excellent processability and appearance, for example, in terms of high end and angel hair. Although the problems of angel hair and high extremities are not as critical when a cap is molded by compression, the improvements that have been observed in terms of FNCT and modulus of elasticity are important in caps molded by compression.
    [0029] The polymer of the invention is a multimodal high-density ethylene polymer and can be an ethylene homopolymer or an ethylene copolymer. By the ethylene copolymer is meant a polymer of the majority by weight from which it is derived from the ethylene monomer units. The comonomer contribution is preferably up to 10 mol%, more preferably up to 5 mol%. Ideally, however, there are many low levels of comonomer present in the polymers of the present invention, such as 0.1 to 2 mol%, for example, 0.1 to 1 mol%.
    [0030] The other copolymerizable monomer or monomers are preferably alpha olefin comonomers, C3-20, especially C310, particularly unsaturated comonomers alone or multiply ethylenically, in particular C3-10 alpha olefins, such as propene, but -1-ene, hex-1-ene, oct-1-ene, and 4-methyl-pent-1-ene. The use of hexene and butene is particularly preferred. Ideally, only one comonomer is present.
    [0031] It is preferred if the polymer of the invention is a copolymer and therefore comprises ethylene and at least one comonomer. Ideally, the comonomer is 1-butene.
    [0032] The polymer of the invention is multimodal and therefore comprises at least two components. The polymer of the invention preferably comprises
    [0033] (A) a first low molecular weight component of ethylene homo- or copolymer, and
    [0034] (B) a second high molecular weight of the ethylene homo- or copolymer component.
    [0035] It is generally preferred if the high molecular weight component has an Mw of at least 5,000 greater than the low molecular weight component, such as at least 10,000 more.
    [0036] The HDPE of the invention is multimodal. Generally, a polyethylene position comprising at least two polyethylene fractions, which were produced under different polymerization conditions resulting in different (average weight) molecular weights and molecular weight distributions for the fractions, is referred to as "multimodal". Thus, in this sense the compositions of the invention are multimodal polyethylenes. The prefix "multi" refers to the number of different polymer fractions in the composition it consists of. Thus, for example, a composition consisting of two fractions is only called "bimodal".
    [0037] The shape of the molecular weight distribution curve, that is, the appearance of the graph of the fraction of the polymer's weight as a function of its molecular weight, of such a multimodal polyethylene will show two or more maximums or at least be distinctly enlarged in comparison with the curves for the individual fractions.
    [0038] For example, if a polymer is produced in a multi-step sequential process, using reactors coupled in series and using different conditions in each reactor, the polymer fractions produced in the different reactors will each have their own weight distribution molecular weight and weighted average molecular weight. When the molecular weight distribution curve of such a polymer is recorded, the individual curves of these fractions are superimposed on the molecular weight distribution curve for the total resulting polymer product, generally producing a curve with two or more distinct maximums.
    [0039] The polymer of the invention preferably has an MFR2 of 5 g / 10 minutes or less, preferably 4.5 g / 10 minutes or less, such as 3.5 g / 10 minutes or less, more preferably 2 , 8 g / 10 minutes or less, especially 2 g / 10 minutes or less, more especially 1.5 g / 10 minutes or less, such as, 1.1 g / 10 minutes or less, more especially of 1.0 g / 10 minutes or less. The polymer preferably has a minimum MFR2 of 0.1 g / 10 minutes, such as 0.3 g / 10 minutes.
    [0040] The polymer of the invention preferably has an MFR21 of 20 to 100 g / 10 minutes, such as, of 25 to 90 g / 10 minutes, more preferably, of 30 to 80 g / 10 minutes, more than preferably 30 to 60 g / 10 minutes.
    [0041] The polymer of the invention preferably has an MFR5 of 0.5 to 20 g / 10 minutes, such as 0.8 to 15 g / 10 minutes, preferably 1 to 10 g / 10 minutes.
    [0042] The density of the polymer is preferably 940 kg / m3 or greater. The polymers of the invention are, therefore, high density polyethylenes, HDPE. More preferably, the polymer has a density of 945 kg / m3 or greater, even more preferably it is 950 kg / m3 or greater, even more preferably it is 952 kg / m3 or greater, and more preferably, it is 954 kg / m3 or greater.
    [0043] In addition, the density of the polymer is preferably 970 kg / m3 or lower, and more preferably is 965 kg / m3 or lower. An ideal density range is 950 to 960 kg / m3.
    [0044] Preferably, the polymer of the invention has an elastic modulus of at least 900 kPa, more preferably of at least 910 kPa.
    [0045] The polymer preferably has a resistance to rupture by environmental stress measured as FNCT of 30 hours or more, more preferably of 40 hours or more, more preferably of 50 hours or more.
    [0046] In particular, the polymers of the invention also have an elastic modulus of at least 900 MPa and an FNCT of 50 hours or greater.
    [0047] It should be noted that the molecular weight and molecular distribution of the polymers of the invention are important. The polyethylene polymer preferably has a molecular weight distribution Mw / Mn, the weighted average molecular weight ratio Mw and the average numerical molecular weight Mn being 10 or greater, more preferably 12 or greater, even more, preferably 14 or higher.
    [0048] The polymer preferably has an Mw / Mn of 30 or below, more preferably of 25 or below.
    [0049] The weighted average molecular weight Mw of the polymer is preferably at least 50 kD, more preferably at least 80 kD, and more preferably at least 100 kD. Furthermore, the Mw of the composition preferably it is a maximum of 300 kD, more preferably 275 kD.
    [0050] The Mz / Mw ratio is preferably not more than 8.0, more preferably not more than 7.0, especially not more than 6.5. The Mz / Mw ratio is preferably at least 3.0, more preferably at least 3.5. The current value of Mz is preferably in the range of 400 kD to 700 kD, such as, from 450 kD to 600 kD.
    [0051] The value of Mw2 / MnMz is preferably at least 2.8, as well as at least 2.9, especially at least 3.0. This preference value does not exceed 5.0.
    [0052] The value of 0.29 (Mw / Mn) + 0.8 is preferably between 4.25 and 6.25 meaning the value Mz / Mw must be less than that.
    [0053] It is particularly preferred if Mz / Mw is at least 0.25 less, more preferably 0.5 less, especially 0.75 less, more preferably 1.0 less than 0.29 Mw / Mn + 0.8.
    [0054] In another modality, the value of the equation is preferably
    [0055] (1.05 Mz) / Mw <(0.29Mw / Mn) + 0.8
    [0056] (1.1 Mz) / Mw <(0.29 Mw / Mn) + 0.8
    [0057] (1.15 Mz) / Mw <(0.29 Mw / Mn) + 0.8; or even
    [0058] (1.2 Mz) / Mw <(0.29 Mw / Mn) + 0.8.
    [0059] These equations emphasize, for this reason, that the difference between the value Mz / Mw and (0.29 Mw / Mn) + 0.8 is significant.
    These molecular weight ratios in claim 1 define neither a high density polyethylene with a higher concentration of higher content of reduced molecular chains and a lower content of chains with high molecular weights. Although this affects the Mz value, the Mw / Mn value is independent. This weighting of the molecular weight distribution occurs in the results on the advantageous properties that were observed in the present application.
    [0061] As noted above, the polymers of the preferred invention comprise a low molecular weight component (A) and a high molecular weight component (B). The weight ratio of fraction (A) to fraction (B) in the composition is in the range of 30:70 to 70:30, more preferably from 35:65 to 65:35, more preferably from 40 : 60 to 60:40. In some modalities the ratio can be 45 to 55% by weight of the fraction (A) and 55 to 45% by weight of the fraction (B), as well as from 45 to 52% by weight of the fraction (A) and of 55 to 48% by weight of the fraction (B). It was found, however, that the best results are obtained when the HMW component is present in the same percentage or even predominates, for example, from 50 to 54% by weight of the HMW component (B) and from 50 to 46% in fraction weight (A).
    [0062] Fractions (A) and (B) may also be the copolymers of ethylene or homopolymers of ethylene, although preferably at least one of the fractions is an ethylene copolymer. Preferably, the polymer comprises an ethylene copolymer component and an ethylene copolymer.
    [0063] When one of the components is an ethylene homopolymer, that is, preferably, the component with the lowest weighted average molecular weight (Mw), that is, fraction (A). An ideal polymer is therefore a lower molecular weight homopolymer component (A) with a higher molecular weight component (B), ideally a lower molecular weight homopolymer component.
    [0064] The low molecular weight fraction (A) preferably has an MFR2 of 10 g / 10 minutes or greater, more preferably of 50 g / 10 minutes or greater, and more preferably of 100 g / 10 minutes or greater.
    [0065] Furthermore, fraction (A) preferably has an MFR2 of 1000 g / 10 minutes or less, preferably 800 g / 10 minutes or less, and more preferably 600 g / 10 minutes or lower.
    [0066] The weighted average molecular weight Mw of the fraction (A) is preferably 10 kD or greater, more preferably it is 20 kD or greater. The Mw of the fraction (A) is preferably 90 kD or lower, more preferably 80 kD or lower, and most preferably it is 70 kD or lower.
    [0067] Preferably, fraction (A) is an ethylene homo- or copolymer with a density of at least 965 kg / m3.
    [0068] More preferably, fraction (A) is an ethylene homopolymer. If fraction (A) is a copolymer, the comonomer is preferably 1-butene. The comonomer content of the fraction (A), if it is a copolymer, is preferably very low, such as less than 0.2 mol%, preferably less than 0.1 mol%, especially less than 0.05 mol%. Another preferred option, for that reason, is for fraction (A) to be a homopolymer or a copolymer with a very low comonomer content, such as less than 0.2 mol%, preferably from less than 0.1 mol%, especially less than 0.05 mol%, The higher Mw fraction (B) is then preferably a copolymer.
    [0069] The high molecular weight fraction (B) preferably has an Mw of 60 kD or greater, more preferably of 100 kD or greater. In addition, fraction (B) preferably has an Mw of 500 kD or lower, more preferably 400 kD or lower.
    [0070] Preferably, fraction (B) is an ethylene homo- or copolymer with a density of less than 965 kg / m3.
    [0071] More preferably, fraction (B) is a copolymer. Preferred ethylene copolymers employ olefin alphas (e.g., C3-12 alpha olefins) as comonomers. Examples of suitable olefin alphas include but-1-ene, hex-1-ene and oct-1-ene, but-1-ene is an especially preferred comonomer.
    [0072] When the characteristics of the fractions (A) and / or (B) of the composition of the present invention are attached, these values are, in general, valid for cases in which they can be directly evaluated in the respective fraction, for example , when the fraction is separately produced or produced in the first stage of a multi-stage process. However, the composition can also be and, preferably, is produced in a multi-step process in which, for example, fractions (A) and (B) are produced in the subsequent steps. In such a case, the properties of the fractions produced in the second stage (or other stages) of the multi-stage process can be inferred from the polymers, which are separately produced in a single stage through the application of identical polymerization conditions (for example, example, identical temperature, partial pressures of reagents / diluents, suspension medium, reaction time) with respect to the multi-stage process step in which the fraction is produced, and using a catalyst in which no previously produced polymers are present . Alternatively, the properties of the fractions produced at a higher stage of the multi-stage process can also be calculated, for example, according to B. Hagstrom, Conference on Polymer Processing (The Polymer Processing Society). Extended Abstracts and Final Program. Gothenburg, 19-21 August 1997, 4:13.
    [0073] Thus, although not directly measurable in the products of the multistage process, the properties of the fractions produced in the higher stages of such a multistage process can be determined by applying one or both of the above methods . The knowledgeable person must be able to select the appropriate method.
    [0074] A multimodal polyethylene (for example, bimodal) as previously described here can be produced by mechanically mixing two or more polyethylenes (for example, modomodal polyethylenes) having maximums differently centered on their molecular weight distributions . The single-mode polyethylenes required for mixing may be commercially available or may be prepared using any conventional procedure known to one skilled in the art. Each of the polyethylenes employed in a mixture and / or the final polymer composition can have the properties described above for the low molecular weight component, high molecular weight component and the composition, respectively.
    [0075] The process of the invention preferably involves
    [0076] polymerize ethylene and optionally at least one C3-10 alpha olefin co-monomer to form a low molecular weight component (A); and subsequently
    [0077] polymerize ethylene and optionally at least one alpha olefin co-monomer C3-10 in the presence of component (A) in order to form a high molecular weight component (B).
    [0078] It is preferred if at least one component is produced in a gas phase reaction.
    [0079] Still preferred, one of the fractions (A) and (B) of the polyethylene composition, preferably the fraction (A), is produced in a reaction of the suspension, preferably in a full circuit reactor, and a of fractions (A) and (B), preferably fraction (B), is produced in a gas phase reaction.
    [0080] Preferably, the multimodal polyethylene composition can be produced by polymerization using the conditions that create a multimodal polymer product (for example, bimodal), for example, using a catalyst or mixture system with two or more different catalytic sites, each site obtained from its own catalytic site precursor, or employing a polymerization process of two or more stages, that is, multiple stages, with different process conditions in different stages or zones (for example, different temperatures , pressures, polymerization medium, hydrogen partial pressures, etc.).
    [0081] Preferably, the multimodal composition (for example, bi-modal) is produced by means of a multi-stage ethylene polymerization, for example, using a series of reactors, with optional addition of comonomer preferably in only the reactor (s) used for the production of the component with the highest / highest molecular weight or the differentiation of the comonomers used in each stage. A multi-step process is defined to be a polymerization process in which a polymer comprising two or more fractions is produced by producing each or at least two fractions of polymer in a separate reaction step, usually with different conditions of reaction in each step, in the presence of the reaction product from the previous step which comprises a polymerization catalyst. The polymerization reactions employed in each stage may involve the conventional reactions of copolymerization or homopolymerization of ethylene, for example, polymerizations of gas phase, suspension phase, liquid phase, using conventional reactors, for example, reactors of complete circuits , gas phase reactors, batch reactors, etc. (see, for example, WO 97/44371 and WO 96/18662).
    [0082] Polymer compositions produced in a multi-stage process are also referred to as "in situ" mixtures.
    [0083] Thus, it is preferred that the fractions (A) and (B) of the polyethylene position are produced in different stages of a multi-stage process.
    [0084] Preferably, the multistep process comprises at least one gas phase step in which, preferably, fraction (B) is produced.
    [0085] Still preferred, the fraction (B) is produced in a subsequent step in the presence of the fraction (A) that was produced in a previous step.
    [0086] It is previously known to produce olefin polymers, multimodal, in particular, bimodal, such as multimodal polyethylene, in a multi-stage process comprising two or more reactors connected in series. As an example of this prior art, mention may be made of EP 517 868, which is incorporated herein by reference in its entirety, including all of its preferred embodiments as described here, as a preferred multi-stage process for the production of the composition of polyethylene according to the invention.
    [0087] Preferably, the main stages of polymerization of the multi-stage process for the production of the composition according to the invention are, as described in EP 517 868, that is, the production of fractions (A) and (B ) is performed as a combination of suspension polymerization for fraction (A) / gas phase polymerization for fraction (B). The suspension polymerization is preferably carried out in a so-called full-circuit reactor. Still preferred, the polymerization step of the suspension precedes the gas phase step.
    [0088] Optionally and advantageously, the main polymerization steps can be preceded by a prepolymerization, in which case up to 20% by weight, preferably from 1 to 10% by weight, more preferably from 1 to 5% by weight. weight, of the total composition are produced. The prepolymer is preferably an ethylene homopolymer (High Density PE). In prepolymerization, preferably, the entire catalyst is loaded into a full-circuit reactor and prepolymerization is carried out as a polymerization of the suspension. Such prepolymerization leads to less fine particles being produced in the reactors that follow and to a more homogeneous product being obtained at the end.
    [0089] Polymerization catalysts include transition metal coordination catalysts, such as Ziegler-Natta (ZN), metallocenes, non-metallocenes, Cr catalysts, etc. The catalyst can be supported, for example, with conventional supports including silica, supports containing Al and supports based on magnesium dichloride. Preferably, the catalyst is a ZN catalyst, more preferably, the catalyst is ZN catalyst supported by silica.
    [0090] The Ziegler-Natta catalyst also preferably comprises a group 4 metal compound (numbering group according to the new IUPAC system), preferably titanium, magnesium dichloride and aluminum.
    [0091] The catalyst can be commercially available or produced according to or analogous to the literature. Reference is made to WO 2004055068 and WO 2004055069 by Borealis, EP 0 688 794 and EP 0 810 235 for the preparation of the preferred catalyst usable in the invention. The content of these documents in their entirety is incorporated herein by reference, in particular with regard to the general and all preferred modalities of the catalysts described here, as well as the methods for producing the catalysts. Particularly preferred Ziegler-Natta catalysts are described in EP 0 810 235.
    [0092] The resulting final product consists of an intimate mixture of the polymers of the two or more reactors, the different molecular weight distribution curves of these polymers, at the same time, forming a molecular weight distribution curve having a wide maximum or two or maximum, that is, the final product is a mixture of bimodal or multimodal polymer.
    [0093] It is preferred that the base resin, that is, the totality of all polymeric components, of the composition according to the Invention is a mixture of bimodal polyethylene consisting of fractions (A) and (B), optionally also comprising a small fraction of prepolymerization in the amount as described above. It is also preferred that this bimodal polymer mixture was produced by means of polymerization as described above under different polymerization conditions in the two or more polymerization reactors connected in series. Because of the flexibility with regard to the reaction conditions thus obtained, it is more preferred that the polymerization be carried out in a combination of the full circuit reactor / one of the gas phase reactor.
    [0094] Preferably, the polymerization conditions in the preferred two-step method are so chosen that the comparatively low molecular weight polymer, having no comonomer content is produced in one step, preferably the first step, because of a high content of chain transfer agent (hydrogen gas), since the high molecular weight polymer having a comonomer content is produced in another step, preferably the second step. The order of these steps can, however, be reversed.
    [0095] In the preferred mode of polymerization in a full circuit reactor followed by a gas phase reactor, the polymerization temperature in the full circuit reactor is preferably 85 to 115 ° C, more preferably is 90 to 105 ° C, more preferably 92 to 100 ° C, and the temperature in the gas phase reactor is preferably 70 to 105 ° C, more preferably 75 to 100 ° C , and most preferably it is 82 to 97 ° C.
    [0096] A chain transfer agent, preferably hydrogen, is added as needed to the reactors, and preferably 100 to 800 moles of H2 / k moles of ethylene are added to the reactor when the LMW fraction is produced in this reactor, and 50 to 500 moles of H2 / k moles of ethylene are added to the gas phase reactor when this reactor is producing the HMW fraction.
    [0097] In the production of the composition of the present invention, preferably, a composition step is applied, in which the composition of the base resin, that is, the mixture, which is characteristically obtained as a reactor base resin powder, is extruded in an extruder and then pelletized to the polymer pellets in a manner known in the art.
    [0098] The polyethylene composition may also contain minor amounts of additives, such as pigments, nucleating agents, antistatic agents, fillers, antioxidants, etc., in general, in amounts of up to 10% by weight, preferably up to 5% by weight.
    [0099] Optionally, additives or other components of the polymer can be added to the composition during the composition step in the amount as described above. Preferably, the composition of the invention obtained from the reactor is composed in the extruder, at the same time, with the additives in a manner known in the art.
    The polyethylene polymer of the invention can also be combined with other components of the polymer, such as, other polymers of the invention, with other HDPEs or with other polymers, such as LLDPE or LDPE. Meanwhile, articles of the invention, such as caps and closures, are preferably at least 90% by weight of the polymer of the invention, such as at least 95% by weight. In one embodiment, the articles essentially consist of the polymer of the invention. The term essentially consists of what the polymer of the invention means is the only "non-additive" polyolefin present. It should be noted, however, that such a polymer may contain standard polymer additives, some of which, could be supported on a polyolefin (a so-called master batch as is well known in the art). The term essentially consists of not excluding the presence of such a sustained additive. applications
    [00101] However, the present invention also relates to an injection or compression-shaped article, preferably a cap or closure, comprising a polyethylene composition as described above and the use of such a polyethylene composition for the production of a injection or compression molded article, preferably a cap or closure. Preferably, injection molded articles are produced.
    [00102] The injection molding of the composition described above can be carried out using any conventional injection molding equipment. A typical injection molding process can be carried out at a temperature of 190 to 275 ° C.
    [00103] However, the present invention also relates to a compression-shaped article, preferably a cap or closure article, comprising a polyethylene polymer as described above and the use of such a polyethylene polymer for the production of an article Compression-shaped, preferably a lid or closure.
    [00104] Preferably, the composition of the invention is used for the production of an article from the lids or closures.
    [00105] As noted above, the caps and locks of the present invention are advantageous not only because of their high FNCT and the properties of the modulus of elasticity, but also because we minimize the formation of angel hair and high ends. It is, therefore, preferred if any injection molding process does not result in the formation of angel hair.
    [00106] It is also preferred if the caps comprising the polymer of the invention have a raised end of less than 0.5 mm in height, such as 250 microns or less, in height, for example, 200 microns or less, such as 100 microns or less. Ideally, the raised end is so small that the human being cannot feel it at the top of the lid or closure.
    [00107] The lids and closures of the invention are of conventional size designed, for that reason, for the bottles and so on. They can be approximately 2 to 8 cm in outer diameter (measured through the solid top of the cap) depending on the bottle and supplied with a screw. The height of the lid could be from 0.8 to 3 cm.
    [00108] The lids and closures can be provided with tear strips from which the lid separates at the first opening as is well known in the art. The lids can also be supplied with linings.
    [00109] It should be noted that any parameter mentioned above is measured according to the detailed test determined below. In any parameter where a more limited and broader modality is described, that modality is described in connection with the more limited and broader modalities of other parameters.
    [00110] The invention should now be described with reference to the figures and the non-limiting examples that follow.
    [00111] Figure 1 shows a cover with a small acceptable end.
    [00112] Figure 2 shows a "high end" cover.
    [00113] Figure 3 shows the presence of angel hair in a cap.
    [00114] Figure 4 shows the relationship between the plot Mz / Mw and Mw / Mn of the line of the equation of the invention.
    [00115] Figure 5 shows FNCT vs modulus of elasticity of the polymers of the invention and those of the prior art. Test Methods: Fusion Flow Rate
    [00116] The melt flow rate (MFR) is determined according to ISO 1133 and is indicated in g / 10 minutes. MFR is an indication of the melt viscosity of the polymer. The MFR is determined at 190 ° C for PE. The load under which the melt flow rate is determined is generally indicated as a subscript, for example, MFR2 is measured under 2.16 kg of load (condition D), MFR5 is measured under 5 kg of load (condition T) or MFR21 is measured under 21.6 kg of load (condition G).
    [00117] The amount of FRR (flow rate ratio) is an indication of the molecular weight distribution and indicates the ratio of flow rates in different loads. In this way, the FRR21 / 2 indicates the value of MFR21 / MFR2. Density
    [00118] The density of the polymer was measured according to ISO 1183 / 1872-2B.
    [00119] For the purpose of this invention the density of the mixture can be calculated from the densities of the components according to:

    [00120] where pb is the density of the mixture,
    [00121] wi is the fraction of the weight of component “i” in the mixture and
    [00122] pi is the density of component “i”.
    [00123] Quantification of the microstructure by means of NMR spectroscopy.
    [00124] Quantitative nuclear magnetic resonance (NMR) spectroscopy was used to quantify the comonomer content of the polymers.
    [00125] The quantitative NMR spectra C13 {1H} recorded in the molten state using a NMR spectrometer Bruker Advance III 500 running at 500.13 and 125.76 MHz for 1H and C13 respectively. All spectra were recorded using an optimized C13 with rotation in the magic angle (MAS) at 7 mm probe head at 150 ° C using nitrogen gas for all tires. Approximately 200 mg of the material was stored in a MAS zirconia rotor with 7 mm outside diameter and centrifuged at 4 kHz. Standard single-pulse excitation was employed using transient NOE for short 3-second recycling delays {pollard04, klimke06} and the RS-HEPT dissociation scheme {fil-lip05, griffin07}. A total of 1024 (1k) transients were acquired by spectrum. This stage was chosen due to its high sensitivity to low comonomer contents.
    [00126] The quantitative C13 {1H} NMR spectra were processed, integrated and the quantitative properties determined using automation programs for spectral analysis on demand. All chemical shifts are internally referenced to the volume of the methylene signal (δ +) at 30.00 ppm {randall89}.
    [00127] The characteristic signs corresponding to the incorporation of 1-butene were observed (randall89) and all levels calculated with respect to all other monomers present in the polymer.
    [00128] The characteristic signals resulting from the isolated incorporation of 1-butene, that is, the EEBEE comonomer sequences, were observed. The isolated incorporation of 1-butene was quantified using the total signal at 39.84 ppm determined at B2 sites, being responsible for the number of sites reported per comonomer:
    [00129] B = I B2
    [00130] Without other indicative signs of other comonomer sequences, that is, the consecutive comonomer incorporation, observed that the total comonomer content of 1-butene was calculated based solely on the quantity of the isolated 1-butene sequences:
    [00131] Btotal = B
    [00132] The relative ethylene content was quantified using the total volume of the methylene signals (δ +) at 30.00 ppm:
    [00133] E = (1/2) * Iδ +
    [00134] The total ethylene comonomer content was calculated based on the volume of the methylene signals and is responsible for the ethylene units present in other terminal groups or observed comonomer sequences:
    [00135] Etotal = E + (5/2) * B
    [00136] The total mole fraction of 1-butene in the polymer was then calculated as:
    [00137] fB = (Btotal / (Etotal + Btotal)
    [00138] The total incorporation of 1-butene comonomer in the mole percentage was calculated from the mole fraction in the usual way:
    [00139] B [mol%] = 100 * fB
    [00140] The total incorporation of 1-butene comonomer in weight percent was calculated from the mole fraction in the standard way:
    [00141] B [% by weight] = 100 * (fB * 56.11) / ((fB * 56.11) + (fH * 84.11) + ((1- (fB + fH)) * 28, 05))
    [00142] klimke06
    [00143] Klimke, K, Parkinson, M, Piel, C, Kaminsky, W, Spiess, H, W, Wilhelm, M, Macromol, Chem, Phys, 2006; 207: 382,
    [00144] pollard04
    [00145] Pollard, M, Klimke, K, Graf, R, Spiess, H, W, Wilhelm, M, Sperber, O, Piel, C, Kaminsky, W, Macromolecules 2004; 37: 813,
    [00146] filip05
    [00147] Filip, X, Tripon, C, Filip, C, J, Mag, Resn, 2005, 176, 239
    [00148] griffin07
    [00149] Griffin, J, M, Tripon, C, Samoson, A, Filip, C, and Brown, S, P, Mag, Res, in Chem, 2007 45, S1, S198
    [00150] rrandall89
    [00151] J, Randall, Macromol, Sci, Rev, Macromol, Chem, Phys, 1989, C29, 201. Molecular weight Molecular weight averages, molecular weight distribution (Mn, Mw, Mz MWD)
    [00152] The molecular weight averages (Mz, Mw and Mn), the Molecular Weight Distribution (MWD) and its amplitude, described by the polydispersity index, PDI = Mw / Mn (where Mn is the average numerical molecular weight and Mw is the weighted average molecular weight) were determined by means of Gel Permeation Chromatography (GPC) according to ISO 16014-1: 2003, ISO 16014-2: 2003, ISO 160144: 2003 and ASTM D 6474-12 using the formulas that follow:

    [00153] For a constant elution volume interval ΔVi, where Ai, and Mi are the area of the chromatographic peak slice and the molecular weight of the polyolefin (MW), respectively associated with the elution volume, Vi, where N is equal to the number of data points obtained from the chromatogram between the limits of integration.
    [00154] A high temperature GPC instrument, equipped with either an infrared (IR) detector (IR4 or IR5 from PolymerChar (Valencia, Spain) or differential refractometer (IR) from Agilent Technologies, equipped with 3 x Agilent-PLgel Olexis and 1 columns x Agilent-PLgel Olexis Guard was used, as the 1,2,4-trichlorobenzene (TCB) solvent with mobile phase stabilized with 250 mg / L of 2,6-Di tert butyl-4-methyl-phenol) was used. The chromatographic system was operated at 160 ° C and at a constant flow rate of 1 mL / minute. 200 μL of the sample solution was injected for analysis. Data collection was performed using either Agilent Cirrus software version 3.3 or PolymerChar GPC-IR control software.
    [00155] The column set was calibrated using universal calibration (according to ISO 16014-2: 2003) with 19 MWD limited polystyrene (PS) standards in the range of 0.5 kg / mol to 11 500 kg / mol. The PS standards were dissolved at room temperature for several hours. The conversion of the molecular weight of the polystyrene peak into molecular weights of polyolefin is performed using the Mark Houwink equation and the following Mark Houwink constants:
    [00156] KPS = 19 x 10-3 mL / g, αPS = 0.655
    [00157] KPE = 39 x 10-3 mL / g, αPE = 0.725
    [00158] KPP = 19 x 10-3 mL / g, αPP = 0.725
    [00159] A third order of polynomial adjustment was employed to adjust the calibration data.
    [00160] All samples were prepared in the concentration range of 0.5 -1 mg / ml and dissolved at 160 ° C for 2.5 hours for PP or 3 hours for PE under gentle continuous agitation. Spiral Flow
    [00161] The Spiral Test is performed using an Engel ES330 / 65 cc90 injection molding device with a 1000 bar pressure and spiral mold;
    [00162] screw diameter: 35 mm
    [00163] maximum piston displacement: 150 cm3
    [00164] tool shape: oval shape; provided by Axxicon; 2 mm thickness, width: 5 mm
    [00165] temperature in the pre-chamber and matrix: 220 ° C
    [00166] temperature in zone 2 / zone 3 / zone 4 / zone 5: 220 ° C / 230 ° C / 225 ° C / 200 ° C,
    [00167] injection cycle: injection time including maintenance: 15 seconds
    [00168] cooling time: 15 seconds
    [00169] injection pressure: Results from the predetermined length of the test material,
    [00170] pressure on permanence = injection pressure
    [00171] screw speed: 30 rpm
    [00172] system pressure: 160 bar
    [00173] measurement path: Measurement stroke must be defined so the screw stops 20 mm before the final position at the end of the maintenance pressure,
    [00174] tool temperature: 40 ° C.
    [00175] The extent of the spiral flow can be determined immediately after the injection operation. Traction Properties
    [00176] The tensile properties were measured in the injection molded samples according to ISO 527-2. Specimen type Multi-purpose bar 1A, 4 mm thick. The modulus of elasticity was measured at a speed of 1 mm / minute. Sample preparation was done acc ISO 1872-2 Resistance to Breaking by Environmental Stress
    [00177] The resistance to rupture by environmental stress (ESCR) can be measured according to the creep test method with total notch (FNCT) according to ISO / DIS 16770 at 50 ° C with a notch depth of 1 mm and the specimen dimensions of 6 mm x 6 mm x 90 mm. The solvent used was 2% by weight Arcopal N110 in deionized water. The compression modeled samples were used (ISO 1872-2), cooling rate in the compression model: 15 K / minute. The fracture time (tf) was measured at 4 different stress levels (a) between 5-7 MPa. A log plot (tf) vs. log (a) was equipped with a straight line and an equation of the form log (tf) = A log (a) + B. The value of the FNCT at the stress of 6 MPa is then calculated based on the linear interpolation using the equation. Breaking Resistance by Environmental Stress
    [00178] The resistance to rupture by environmental stress (ESCR) was determined according to ASTM 1693, condition B at 50 ° C, and using 10% of Igepal co-630. Experimental Synthesis of the polymers of the invention: Preparation of the catalyst Complex preparation:
    [00179] 87 kg of toluene were added to the reactor. And then 45.5 kg of Bomag A in heptane were also added to the reactor, 161 kg of 99.8% 2-ethyl-1-hexanol were then introduced into the reactor at a flow rate of 24-40 kg / hour. The molar ratio between BOMAG-A and 2-ethyl-1-hexanol was 1: 1.83. Preparation of the solid catalyst component:
    [00180] 275 kg of silica (ES747JR from Crossfield, having an average particle size of 20 mm) activated at 600 ° C in nitrogen was loaded into a catalyst preparation reactor. Then, 411 kg of 20% EADC (2.0 mmol / g silica) diluted in 555 liters of pentane were added to the reactor at room temperature for one hour. The temperature was then raised to 35 ° C at the same time as the stirring of the treated silica for one hour. The silica was dried at 50 ° C for 8.5 hours. Then 655 kg of the complex prepared as described above (2 mmol Mg / g silica) was added at 23 ° C for ten minutes. 86 kg of pentane was added to the reactor at 22 ° C for ten minutes. The suspension was stirred for 8 hours at 50 ° C. Finally, 52 kg of TiCl4 was added over 0.5 hours at 45 ° C. The suspension was stirred at 40 ° C for five hours. The catalyst was then dried by nitrogen purification.
    [00181] The polymers of the invention were prepared as summarized in table 1 in a Borstar process using the above catalyst and the TEAL cocatalyst: Table 1


    [00182] The results are shown in tables 2 to 8. Table 2

    Injection molding of screw caps:
    [00183] Injection molding of the screw caps (type: short neck PE PCO1881) was done on an Engel speed of 180, melting temperature ~ 225 ° C, injection speed: relative 180 mm / s, absolute of 173 cm3 / s; injection time 0.35 s, back pressure 1 bar, The mold was equipped with a hot runner system, mold temperature: 10 ° C.
    [00184] The properties of the cover are reported in table 6. Table 6

    [00185] The polymers of the invention have been compared to a wide range of commercially available lids / closures qualities sold by various producers. Table 7


    [00186] It can be seen that all tested assertions failed to satisfy the equation forming the cap of claim 1. The polymers of the Invention therefore have a higher FNCT without losing the modulus of elasticity.
    权利要求:
    Claims (11)
    [0001]
    1. Multimodal polyethylene polymer, characterized by the fact that it has 45 to 52% by weight of a lower molecular weight homopolymer component (LMW) and 48 to 55% by weight of an ethylene copolymer component high molecular weight (HMW) with the 1-butene comonomer, and has a melt flow rate (MFR2) of 0.05 to 10.0 g / 10 minutes, a density of 940 kg / m3 or more, a weight average molecular Z of the polymer (Mz) from 400 to 700kD, an elastic modulus of 900 MPa or more, and in which
    [0002]
    2. Multimodal polyethylene polymer, according to king-vindication 1, characterized by the fact that
    [0003]
    3. Multimodal polyethylene polymer, according to claim 1 or 2, characterized by the fact that it has an MFR2 of 0.1 to 2 g / 10 minutes.
    [0004]
    4. Multimodal polyethylene polymer according to any one of claims 1 to 3, characterized in that it has 0.1 to 1 mol% of comonomer.
    [0005]
    5. Multimodal polyethylene polymer according to any one of claims 1 to 4, characterized in that it has an FNCT of more than 50 hours.
    [0006]
    6. Multimodal polyethylene polymer according to any one of claims 1 to 5, characterized in that it has an elastic modulus of 910 MPa or more.
    [0007]
    7. Multimodal polyethylene polymer according to any one of claims 1 to 6, characterized in that it has a density of 950 to 960 kg / m3.
    [0008]
    8. Multimodal polyethylene polymer according to any one of claims 1 to 7, characterized by the fact that Mz is in the range of 450 kD to 600 kD.
    [0009]
    9. Injection or compression molded article such as lid or closure, characterized in that it comprises a polymer, as defined in any one of claims 1 to 8.
    [0010]
    10. Article according to claim 9, characterized by the fact that it is a lid having an elevated end of less than 0.5 mm or is free from an elevated end.
    [0011]
    11. Use of the polymer, as defined in any one of claims 1 to 8, characterized by the fact that it is in the production of an injection or compression molded article such as a cap or closure.
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    同族专利:
    公开号 | 公开日
    US20160083488A1|2016-03-24|
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    PE20160102A1|2016-02-25|
    AU2014264567B2|2017-08-03|
    MA38644B1|2018-11-30|
    RU2015149952A3|2018-03-12|
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    RU2674695C2|2018-12-12|
    ES2636850T3|2017-10-09|
    CN105408412B|2017-11-17|
    AP2015008887A0|2015-11-30|
    CL2015003240A1|2016-06-10|
    TN2015000489A1|2017-04-06|
    RU2015149952A|2017-06-15|
    CN105408412A|2016-03-16|
    EP2994506B1|2017-07-05|
    US9441062B2|2016-09-13|
    SG11201509210UA|2015-12-30|
    BR112015028045A2|2017-07-25|
    PH12015502552B1|2016-02-22|
    EP2994506B2|2020-07-01|
    AU2014264567A1|2015-11-19|
    ES2636850T5|2021-02-17|
    PL2994506T5|2020-09-07|
    PL2994506T3|2017-11-30|
    WO2014180989A1|2014-11-13|
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    法律状态:
    2018-02-27| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|
    2019-12-24| B06U| Preliminary requirement: requests with searches performed by other patent offices: procedure suspended [chapter 6.21 patent gazette]|
    2020-11-24| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|
    2021-01-19| 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 09/05/2014, OBSERVADAS AS CONDICOES LEGAIS. |
    优先权:
    申请号 | 申请日 | 专利标题
    EP13167191.9|2013-05-09|
    EP13167191|2013-05-09|
    PCT/EP2014/059579|WO2014180989A1|2013-05-09|2014-05-09|Hdpe|
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