Composition of multimodal polypropylene for pipe applications

专利摘要:

公开号:ES2569078T9
申请号:ES13002102T
申请日:2013-04-22
公开日:2020-02-10
发明作者:Cristian Hedesiu；Kauno Alastalo
申请人:Abu Dhabi Polymers Co Ltd Borouge LLC；Borealis AG；
IPC主号:

专利说明:

[0001] Composition of multimodal polypropylene for pipe applications
[0002] Introduction
[0003] The present invention relates to polypropylene compositions with an equilibrium of advantageous properties with respect to mechanical properties, including impact and stiffness / flexibility properties, and with advantageous processing properties.
[0004] Polypropylene materials are frequently used for various pipe splicing applications, such as the transport of fluids, for example, water or natural gas, during which the fluid is pressurized and / or heated. In particular, polypropylene materials are used in plumbing and heating applications, such as internal pressure pipes for hot and cold water and fittings, floor and wall heating systems and radiator connections.
[0005] Thus, random propylene copolymers are especially suitable for pressure pipe applications for hot water and industrial pipes, since random copolymers have, among other properties, good impact resistance, stiffness, slip resistance and slow cracking. , and long-term pressure resistance.
[0006] State of the art
[0007] It is well known that increasing one of the impact properties or stiffness / flexibility sacrifices the other. In addition, propylene copolymer-based pipes for hot and cold water pressure applications are often colored, for example, green, gray, blue, and white, etc. Different pigments have different nucleation effects on random copolymers of propylene and the variation in the intensity of the effect from one color to another will result in dimensional variations due to differences in the contraction associated with nucleation. It is desirable to have a material that has contraction properties essentially independent of color.
[0008] Naturally, the processing capacity, such as the extrusion output frequency during the production of the pipes and a shorter cycling time during the injection molding of the fittings, must be industrially feasible, as well as the surface quality of the pipe and / or final fittings.
[0009] WO 00/68315 (EP 1183307) discloses a nucleated homopolymer and a heterophasic propylene copolymer and the use thereof in various applications primarily related to molding applications. The flow rates of the compositions do not allow pipe applications.
[0010] WO 99/24479 of Borealis discloses a nucleated propylene polymer, although the examples describe propylene homopolymers and heterophasic propylene copolymers. It is claimed that heterophasic propylene copolymers are "rigid" (examples 9 and 10, for example, a flexural modulus of approximately 1500 and 1600 MPa), so they are suitable for sewage pipe applications.
[0011] WO 2006/010414 discloses a propylene copolymer composition suitable for films and pipes. Said composition does not contain any random copolymer.
[0012] WO 2003/016553 refers to a composition that is used for films and fibers having flow rates (230 ° C, 2.16 kg) of 16 g / 10 min or higher. The compositions are produced by catalyst systems based on metallocene compounds.
[0013] EP 885926 refers to compositions that have a flow rate of 0.6 g / 10 min or higher that are suitable for uses that require transparency, resistance to bleaching under tension and good resistance to low temperature impact. All examples have an MFR2 of more than 1.0 g / 10 min, except for example 6 which has an MFR2 of 0.6 g / 10 min. The data in Table 1 shows that Example 6 has an ethylene unit content of 9.1% by weight at 13 mol%.
[0014] There is still a continuing need for new propylene copolymer compositions with an advantageous balance of mechanical properties that meet the increasing demands required for pipe applications, in particular for pressure pipe applications, more preferably, for pressure pipe applications. of hot water and cold water.
[0015] Objectives of the present invention
[0016] The present invention discloses a new multimodal polypropylene composition that is very suitable for pipe applications, preferably, for hot and cold water pressure pipe applications. The present invention further discloses an article, preferably, a pipe, which is, preferably, a pressure pipe, more preferably, a pressure pipe for hot and cold water applications, or an accessory for a pipe containing the multimodal polypropylene composition of the present invention.
[0017] Characteristics of the invention.
[0018] The present invention discloses a multimodal polypropylene composition suitable for pipe applications comprising
[0019] a multimodal propylene copolymer (U), at least, with a comonomer selected from alpha-olefins with 2 or 4 to 8 carbon atoms in a total amount of 4.0 to 10.0 mol%,
[0020] in which the multimodal polypropylene composition has a fluidity index MFR2 (2.16 kg, 230 ° C) of 0.05 to 1.00 g / 10 min, determined according to ISO 1133, a soluble fraction content cold in xylene (XCS) from 4.0 to 17.0% by weight, determined at 25 ° C according to ISO 16152, and
[0021] an IP polydispersity index of 2.5 to 4.0 Pa-1, determined by rheological measurements according to ISO 6721-1 and ISO 6721-10, as described below in the Determination Procedures section. The present invention further discloses an article, preferably, a pipe, which is, preferably, a pressure pipe, or an accessory for a pipe comprising the multimodal polypropylene composition of the present invention, such as defined above, including any preferred embodiment and subgroups thereof.
[0022] Definitions
[0023] A propylene copolymer herein means a polymer consisting essentially of propylene monomer units and comonomer units, whereby the comonomer units in the total amount are at least up to 0.1 mole%.
[0024] A random propylene copolymer indicates a copolymer of propylene monomer units and comonomer units, in which the comonomer units are randomly distributed in the polymer chain. The random copolymer does not contain an elastomeric polymer phase dispersed therein.
[0025] As is known to one skilled in the art, a random copolymer is different from heterophasic polypropylene which is a propylene copolymer comprising a propylene homopolymer matrix component (1) or a propylene random copolymer and a component (2) of the elastomeric propylene copolymer with one or more of ethylene and C4-C8 alpha-olefin copolymers, wherein the elastomeric (amorphous) elastomeric copolymer component (2) is dispersed in said propylene homopolymer matrix polymer (1) or a random copolymer of propylene.
[0026] Thus, a propylene homopolymer indicates a polymer consisting essentially of propylene monomer units. Due to the large-scale polymerization requirements, it may be possible for the propylene homopolymer to include smaller amounts of comonomer units, which are usually less than 0.1 molar, preferably less than 0.05 molar , most preferably, less than 0.01 mol% of the propylene homopolymer.
[0027] A nucleating agent herein indicates a compound or composition that is added for the purpose of increasing the crystallization rate within the solid polymer and leading to a greater degree of crystallinity (and, often, to a smaller crystal size ) of the solid polymer.
[0028] The pressure pipe for hot and cold water applications has a known meaning in the field of polypropylene pipe applications and implies for a skilled person generally accepted property requirements for the pipe to be used in such applications.
[0029] Typically, a propylene polymer comprising at least two fractions (components) of propylene polymer, which has been produced under different polymerization conditions resulting in different molecular weights (weight average) and / or different comonomer contents for the fractions, preferably produced by polymerization in multiple stages of polymerization with different polymerization conditions, reference is made as "multimodal". The "multi" prefix refers to the number of different polymer fractions of which the propylene polymer consists. As an example of a multimodal propylene polymer, a propylene polymer consisting of only two fractions is called "bimodal", while a propylene polymer consisting of three fractions is only called "trimodal."
[0030] Thus, the term "different" means that the propylene polymer fractions differ from one another, at least, in one property, preferably, in the average molecular weight weight or comonomer content, or both, so more preferred, at a minimum, the weight average molecular weight.
[0031] The shape of the molecular weight distribution curve, that is, the appearance of the graph of the polymer weight fraction as a function of its molecular weight, of said multimodal propylene polymer is at least clearly widened compared to the curves for individual fractions.
[0032] It is known that the melt flow index (MFR) of a polymer is an indication of the weight average molecular weight (Mw) of the polymer, the higher the MFR, the lower the Mw of the polymer and, respectively, the lower the MFR , greater is the Mw of the polymer.
[0033] Detailed description of the invention
[0034] Surprisingly, it has been found that the multimodal polypropylene composition, according to the present invention, has an advantageous balance of properties between the mechanical properties according to the properties of the flexural modulus and impact resistance, as can be seen from the strength to the impact of Charpy type with notch at a cold temperature of 0 ° C and, preferably, also at room temperature. The balance between the flexural modulus and the impact resistance of Charpy type with low temperature notch provides sufficient flexibility and good impact properties to the multimodal polypropylene composition of the present invention, making it very suitable for pipe applications, so preferably, for pressure pipe applications, preferably hot and cold water pressure pipe applications. More preferably, the present multimodal polypropylene composition shows an advantageously possible creep resistance, as can be seen from the tensile stress. More preferably, the present multimodal polypropylene composition has an advantageous pressure resistance required for pressure pipe applications. The present multimodal polypropylene composition also preferably has an advantageous processing behavior in terms of extrusion of the pipes and / or cycling time of molded fittings. The final pipe or fittings obtained have a uniform contraction behavior and a good surface quality.
[0035] Therefore, the multimodal polypropylene composition of the present invention and the article, preferably, the pipe and / or fittings, are described below with generalizable embodiments and subgroups thereof preferred and with properties and ranges of properties. of the same preferred. "Generalizable" means herein that any of the embodiments, subgroups, properties and ranges of preferred properties of the multimodal polypropylene composition of the present invention can be combined with each other, and in any order.
[0036] Without being bound by any theory, it is believed that, at a minimum, the comonomer content and the cold soluble fraction (XCS) content of the multimodal polypropylene composition contribute to the advantageous balance of properties between the flexural and strength modulus properties to the impact, as well as the resistance to pressure, of the present invention.
[0037] Preferably, the multimodal polypropylene composition of the present invention comprises a multimodal propylene copolymer (U), comprising
[0038] (A) 75 to 98% by weight of a propylene random copolymer composition (X) having an MFR2 flow rate of 0.05 to 1.0 g / 10 min, or a comonomer unit content of 2 , 0 to 12.0% molar, or both; Y
[0039] (B) 2 to 25% by weight of a propylene copolymer (Y), in which the comonomer is selected, at least, from one of the group consisting of ethylene and C4-C8 alpha-olefins and, whereby , the propylene copolymer (Y) preferably has an MFR2 flow rate of 0.0001 to 0.1 g / 10 min, or a comonomer unit content of 9.0 to 40.0 mol%, or both.
[0040] Here, in the text below, the definitions of the components of the present invention may alternatively be abbreviated, in which case the letters (U), (X), (Y), (V), (W), etc. . They refer to the respective component. For example, "propylene random copolymer composition (X)" is also used shortly as "propylene copolymer composition (X)" or "copolymer composition (X)" and, similarly, the "copolymer of Multimodal propylene (U) "is shortened as" propylene copolymer (U) ".
[0041] Preferably, the propylene copolymer (X) and propylene copolymer (Y) composition are different with respect to the comonomer content and / or with respect to the MFR2 values, preferably, the propylene copolymer composition ( X) and propylene copolymer (Y) have, at least, different values of MFR2, more preferably, at least, a comonomer content and different values of MFR2.
[0042] The combination of the propylene copolymer (X) and propylene copolymer (Y) composition is advantageous for achieving the comonomer content and the cold xylene soluble fraction (XCS) content of the multimodal polypropylene composition of the present invention and, thus, contributes to the advantageous balance of properties between flexural modulus and impact properties, as well as pressure resistance, of the present invention.
[0043] The propylene copolymer composition (X) preferably comprises at least two propylene polymer components which have at least one different MFR2 or a different comonomer content and are selected from propylene homopolymer and propylene copolymer , provided that at least one of the two components is a random propylene copolymer, preferably, both propylene polymer components are random propylene copolymers.
[0044] Thus, preferably, the multimodal polymer composition of the present invention comprises the multimodal propylene copolymer (U) comprising the propylene copolymer composition (X), which comprises
[0045] 30 to 60% by weight of a first propylene (V) random homopolymer or copolymer having an MFR2 of 0.3 to 5.0 g / 10 min; Y
[0046] 40 to 70% by weight of a second homopolymer or random copolymer of propylene (W), having an MFR2 of 0.04 to 0.60 g / 10 min; provided that at least one of said first propylene (V) random homopolymer or copolymer and said second propylene (W) random homopolymer or copolymer is a random propylene copolymer.
[0047] The first propylene (V) random homopolymer or copolymer and the second propylene (W) random homopolymer or copolymer are different with respect to the comonomer content and / or with respect to the MFR2 values, and, preferably, the MFR2 of the first homopolymer or random copolymer of propylene (V) is greater than MFR2 of the second homopolymer or random copolymer of propylene (W), and optionally, and, preferably, the MFR2 of the second homopolymer or random copolymer of propylene (W) is higher than the MFR2 of propylene copolymer (Y).
[0048] At a minimum, said second propylene random homopolymer or copolymer (W) is preferably a random propylene copolymer.
[0049] More preferably, the multimodal polymer composition of the present invention comprises the multimodal propylene copolymer (U) comprising the propylene copolymer composition (X), which comprises
[0050] 30 to 60% by weight of the first random propylene copolymer (V) having an MFR2 of 0.3 to 5.0 g / 10 min, or a comonomer unit content of 1.0 to 6.0 molar% , or both; Y
[0051] 40 to 70% by weight of the second random propylene copolymer (W) having an MFR2 of 0.04 to 0.60 g / 10 min, or a comonomer unit content of 3.0 to 12.0% molar , or both.
[0052] The definitions of the preferred MFR properties and comonomer content for the first and second preferred propylene random copolymer component (V) and (W) are given below, however, the definitions for the MFR properties apply equally to the first and second propylene homopolymers (V) and (W), respectively.
[0053] The first random propylene copolymer (V) and the second random propylene copolymer (W) are different with respect to the comonomer content and / or with respect to the MFR2 values, preferably, the first random propylene copolymer (V ) and the second random propylene copolymer (W) have, at least, different MFR2 values, more preferably, at least, a comonomer content and different MFR2 values.
[0054] Each of the first random propylene copolymer (V), the second random propylene copolymer (W) and the propylene copolymer (Y) preferably have a different MFR2 and / or comonomer content, more preferably at least one different MFR2, more preferably, a different MFR2 and a different comonomer content.
[0055] Preferably, the MFR2 of the propylene copolymer composition (X) is greater than the MFR2 of the propylene copolymer (Y) and / or the comonomer content of the propylene copolymer composition (X) is less than the comonomer content of the propylene copolymer (Y). More preferably, the MFR2 of the propylene copolymer composition (X) is greater than the MFR2 of the propylene copolymer (Y) and the comonomer content of the propylene copolymer composition (X) is less than the comonomer content of the propylene copolymer (Y).
[0056] More preferably, the MFR2 of the first random propylene copolymer (V) is greater than the MFR2 of the second random propylene copolymer (W) and the MFR2 of the second random propylene copolymer (W) is greater than the MFR2 of the propylene copolymer ( Y); and / or the comonomer content of the first random propylene copolymer (V) is lower than the comonomer content of the second random propylene copolymer (W) and the comonomer content of the second random propylene copolymer (W) is less than the content of comonomer of the propylene copolymer (Y).
[0057] Even more preferably, the MFR2 of the first random propylene copolymer (V) is greater than the MFR2 of the second random propylene copolymer (W) and the MFR2 of the second random propylene copolymer (W) is greater than the MFR2 of the propylene copolymer (Y) and the comonomer content of the first random propylene copolymer (V) is lower than the comonomer content of the second random propylene copolymer (W), and the comonomer content of the second random propylene copolymer (W) is less than comonomer content of the propylene copolymer (Y).
[0058] The polymer composition (X) may contain a prepolymer fraction. In the presence of a prepolymer fraction, said fraction is calculated with respect to the amount (% by weight) of the propylene copolymer composition (X), more preferably, with respect to the amount (% by weight) of the first random copolymer of propylene (V). The prepolymer fraction can be a homopolymer or a copolymer of propylene.
[0059] The multimodal polypropylene composition optionally comprises a nucleating agent (Z).
[0060] Accordingly, the preferred nucleating agent (Z) can be incorporated into the multimodal polypropylene composition by adding part or all of the preferred nucleating agent (Z) separately (for example, by known composition techniques) to the copolymer of multimodal propylene (U). Alternatively, part or all of the preferred nucleating agent (Z) may be incorporated into the multimodal polypropylene composition by being present in any or all of the aforementioned polypropylene components of the multimodal propylene copolymer (U), in particular, in the copolymer composition (X), preferably, in the first propylene copolymer (V) and / or in the second random propylene copolymer (W), more preferably, both in the first and second copolymer of propylene (V) and (W); and / or in the propylene copolymer (Y), more preferably, in the first propylene copolymer (V) and in the second random propylene copolymer (W) of the propylene copolymer composition (X), as well as in the propylene copolymer (Y).
[0061] Accordingly, the multimodal polypropylene composition of the present invention preferably comprises the multimodal propylene copolymer (U), an optional and preferred nucleating agent (Z), and additional optional additives.
[0062] Even more preferably, said multimodal propylene copolymer (U) of the multimodal polypropylene composition consists of said propylene copolymer composition (X), said propylene copolymer (Y), said optional nucleating agent (Z), and preferred, and optional additional additives.
[0063] Even more preferably, said propylene copolymer composition (X) of said multimodal propylene copolymer (U) of the multimodal polypropylene composition consists of the first random propylene copolymer (V), the second random propylene copolymer (W) ), said optional, and preferred, nucleating agent (Z), and optional additional additives. Additionally, preferably, said propylene copolymer (Y) consists of the propylene copolymer (Y) and said optional nucleating agent (Z), and preferably, and optional additional additives.
[0064] The amount of the preferred nucleating agent (Z) in the multimodal polypropylene composition, when, preferably, is present, is 0.1 to 10,000 ppm by weight (means parts per million based on the total weight of the composition of multimodal polypropylene (100% by weight), preferably, based on the combined amount of multimodal propylene copolymer (U) and the nucleating agent (Z), also abbreviated herein as ppm). Said amount means the total sum of the amount of nucleating agent (Z) present in the multimodal polypropylene composition. That is, said amount may be the total amount resulting from the incorporation of the nucleating agent (Z) separately to the propylene copolymer (U) and / or resulting from any amount or amounts of the nucleating agent (Z) that is originally present in the propylene copolymer (U), that is, in the propylene copolymer composition (X), preferably, in the first random propylene copolymer (V) and / or in the second random propylene copolymer ( W), and / or in the propylene copolymer (Y), at the time of formation of the composition.
[0065] It is preferred that the nucleating agent (Z) be present in the multimodal polypropylene composition. It is believed that the nucleating agent (Z) contributes to the advantageous balance of properties between the flexural modulus and impact resistance properties, as well as the pressure resistance, of the present invention.
[0066] The multimodal propylene copolymer (U) may comprise one, two or more types, preferably one or two types, most preferably, one type of comonomer or comonomers.
[0067] The comonomers of said multimodal propylene copolymer (U) are preferably selected from C2 and C4 to C6 alpha-olefins. A particular preferred comonomer is ethylene.
[0068] The polypropylene composition of the present invention is, more preferably, a multimodal propylene copolymer (U), which is a propylene copolymer with ethylene comonomer.
[0069] Scheme 1 is a general flow chart illustrating the preferred production process for the production of the most preferred multimodal polypropylene composition of the present invention and the preferred polypropylene components thereof.
[0070]
[0071]
[0072]
[0073] The multimodal polypropylene polymer composition of the present invention can also be defined by defining a product obtained by a process, which has a known meaning in the patent sector.
[0074] Accordingly, also, alternatively to the above preferred subgroups, the multimodal polypropylene composition comprises a multimodal propylene copolymer (U) containing at least one comonomer selected from alpha-olefins having 2 or 4 to 8 carbon atoms in a total amount of 4.0 to 10.0% molar
[0075] in which the multimodal polypropylene composition has a fluidity index MFR2 (2.16 kg, 230 ° C) of 0.05 to 1.00 g / 10 min, determined according to ISO 1133, a soluble fraction content in cold xylene (XCS) from 4.0 to 17.0% by weight, determined at 25 ° C according to ISO 16152, in which the multimodal polypropylene composition is obtainable by a multistage process, in which propylene and at least one comonomer selected from alpha-olefins with 2 or 4 to 8 carbon atoms is polymerized in the presence of (I) a solid catalyst component comprising a magnesium halide, a titanium halide and a donor internal electron; Y
[0076] (II) a cocatalyst comprising an aluminum alkyl and, optionally, an external electron donor; and (III) an optional nucleating agent (Z), preferably, a polymeric nucleating agent (Z), preferably, the nucleating agent (Z) is present and is preferably a polymer of a vinyl compound of formula 1 as defined below, more preferably, a vinylcyclohexane polymer and / or 3-methyl-1-butene, even more preferably, a vinylcyclohexane polymer; the multistage process comprising the stages of
[0077] (A) continuously polymerize propylene, optionally, a comonomer selected from the ethylene group and, at least, a C4-C8 alpha-olefin, in a first polymerization stage by introducing streams of propylene, hydrogen and, optionally, said comonomer in the first polymerization stage at a temperature of 60 to 100 ° C and a pressure of 40 to 65 bar to produce a first propylene polymer (V), in which the first propylene polymer (V) has an index of fluidity MFR2 (2.16 kg, 230 ° C; ISO 1133) from 0.3 to 5.0 g / 10 min;
[0078] (B) extracting from the first stage of polymerization a stream comprising the first propylene polymer (V) and transferring said stream to a second stage of polymerization;
[0079] (C) polymerize propylene in the presence of said first propylene polymer (V) in the second polymerization stage at a temperature of 65 to 90 ° C and a pressure of 19 to 25 bar by introducing streams of propylene, hydrogen and, optionally, at least one comonomer, to produce a copolymer composition (X) of said first propylene polymer (V) and a second propylene polymer (W); provided that at least one of said first and second polymers (V) and (W) is a random copolymer of propylene;
[0080] said copolymer composition (X) comprising
[0081] from 30 to 60% by weight of said first propylene polymer (V) and from 40 to 70% by weight of said second propylene polymer (W) with respect to the copolymer composition (X),
[0082] wherein the copolymer composition (X) has an MFR2 flow rate of 0.05 to 1.0 g / 10 min which is lower than the MFR2 of said first polymer (V);
[0083] (D) extracting a stream comprising the copolymer composition (X) of the second polymerization stage and transferring said stream to a third polymerization stage;
[0084] (E) polymerize propylene and at least one comonomer in the presence of the copolymer composition (X) in the third polymerization stage at a temperature of 65 to 90 ° C and a pressure of 10 to 100 bar by introducing streams of propylene, hydrogen and at least one comonomer, to produce the multimodal propylene copolymer (U) comprising the copolymer composition (X) and an additional component of propylene copolymer (Y), in which the propylene copolymer multimodal (U) has an MFR2 flow rate of 0.05 to 1.00 g / 10 min;
[0085] wherein the multimodal propylene copolymer (U) comprises 75 to 98% by weight, preferably 85 to 95% by weight of said copolymer composition (X) and 2 to 25% by weight, so preferably, 5 to 15% by weight of said propylene copolymer (Y); Y
[0086] wherein the comonomer content of the propylene copolymer (Y) is 9.0 to 40 mol%;
[0087] (F) continuously extracting a stream comprising the multimodal propylene copolymer (U) from the third polymerization stage and, optionally, mixing the multimodal propylene copolymer (U) with additives; Y
[0088] (G) Extrude the multimodal propylene copolymer (U) into granules.
[0089] More preferably, the multimodal polypropylene composition of the present invention is obtainable by the multistage process as defined above, which comprises an additional stage (AA) preceding stage (A), in which
[0090] (AA) polymerizing a vinyl compound of the formula (1) as defined above or preferably, preferably, vinylcyclohexane (VCH) in the presence of a catalyst system comprising the solid catalyst component (I) to obtain a modified catalyst system which is the reaction mixture comprising the solid catalyst component (I) and the polymer produced from the vinyl compound of formula (1), preferably, and in which, the weight ratio (g) of the Polymer of the vinyl compound of the formula (1) with respect to the solid catalyst component (I) is up to 5 (5: 1), preferably up to 3 (3: 1), most preferably, it is from 0.5 (1: 2) to 2 (2: 1), and the modified catalyst system obtained is introduced in the polymerization stage (A) of the multistage process for the production of the multimodal propylene copolymer (U).
[0091] Preferably, the multimodal polypropylene composition, more preferably, the multimodal propylene copolymer (U) has the following properties. It should be understood that the subgroups and / or intervals of the preferred properties shown below can be combined in any order:
[0092] a) MFR
[0093] The multimodal polypropylene composition, more preferably, the propylene copolymer (U), according to The present invention has a flow rate of MFR2 (2.16 kg, 2302C) of 0.05 to 1.00 g / 10 min, preferably 0.10 to 0.70 g / 10 min, so more preferably, from 0.15 to 0.50 g / 10 min, and most preferably, from 0.18 to 0.40 g / 10 min, determined according to ISO 1133.
[0094] b) XCS content
[0095] In addition, the multimodal polypropylene composition, more preferably, the propylene copolymer (U), according to the present invention, has a fraction of cold xylene soluble (XCS) fraction of 4.0 to 17.0% in weight, preferably, from 5.0 to 15.0% by weight, and most preferably, from 6.0 to 13.5% by weight, based on the weight of the multimodal propylene random copolymer, determined at 25 ° C according to ISO 16152.
[0096] c) XCU Content
[0097] In addition, the multimodal polypropylene composition, more preferably, the propylene copolymer (U), according to the present invention, preferably has a cold insoluble fraction (XCU) content of 83.0 to 96, 0% by weight, more preferably, from 85.0 to 95.0% by weight, and most preferably, from 86.5 to 94.0% by weight, based on the weight of the random propylene copolymer multimodal, determined at 25 ° C according to ISO 16152.
[0098] d) Polydispersity index
[0099] The multimodal polypropylene composition, more preferably, the propylene copolymer (U), according to the present invention, has a polydispersity index (PI) of 2.5 to 4.0 P a, preferably 2, 9 to 3.9 Pa-1, and most preferably, from 3.1 to 3.8 Pa-1, determined by rheological measurements as described below in the examples section.
[0100] e) Crystallization temperature
[0101] In addition, the multimodal polypropylene composition, more preferably, the propylene copolymer (U), according to the present invention, preferably has a crystallization temperature Tc of at least 110 ° C, more preferably at least 112 ° C, and most preferably at least 114 ° C, determined according to ISO 11357-1, 11357-2, and 11357-3. In general, the crystallization temperature Tc is not higher than 130 ° C.
[0102] f) Charpy type impact resistance with notch at 0 ° C
[0103] The multimodal polypropylene composition, more preferably, the propylene copolymer (U), according to the present invention, preferably has a notched Charpy impact resistance (NIS) at least 0 ° C, 4.0 kJ / m2, more preferably, at least, 5.0 kJ / m2, even more preferably, at least, 6.0 kJ / m2, even more preferably, at least , 7.0 kJ / m2 and, most preferably, at least 8.0 kJ / m2, determined according to ISO 179 / 1eA: 2000 using injection molded samples with notches. In general, the impact resistance of the notched Charpy type (NIS) at 0 ° C is not more than 40 kJ / m2.
[0104] g) Charpy type impact resistance with notch at 23 ° C
[0105] The multimodal polypropylene composition, more preferably, the propylene copolymer (U), according to the present invention, preferably has a notched Charpy impact resistance (NIS) at a minimum of 23 ° C, 30 kJ / m2, more preferably, at least, 40 kJ / m2, and most preferably, at least 50 kJ / m2, determined according to ISO 179 / 1eA: 2000 using samples molded by injection with notches. In general, the notched Charpy impact resistance (NIS) at 23 ° C is not more than 130 kJ / m2.
[0106] h) Flexural modulus
[0107] The multimodal polypropylene composition, more preferably, the propylene copolymer (U), according to the present invention, preferably has a flexural modulus of at least 700 MPa, more preferably at least 750 MPa, more preferably, at least, 800 MPa, more preferably, at least, 830 MPa, determined according to ISO 178 at a test speed of 2 mm / min and a force of 100 N in test samples having a dimension of 80 x 10 x 4.0 mm3 (length x width x thickness) prepared by injection molding according to EN ISO 1873-2. The upper limit of the flexural modulus usually does not exceed 1400 MPa, and is preferably 1200 MPa or less. The polypropylene composition most preferably has a flexural modulus of 830 to 1100 MPa.
[0108] i) Tensile tension at the creep point
[0109] The multimodal polypropylene composition, more preferably, the propylene copolymer (U), according to the present invention, preferably has a tensile stress at the creep point of at least 20 MPa, more preferably at least 22 MPa, and most preferably at least 24 MPa, determined according to ISO 527-2: 1996 using injection molded test samples of type 1A prepared according to ISO 527- 2: 1996. In general, the tensile stress at the creep point is not more than 40 MPa.
[0110] j) Content of comonomer
[0111] Said at least one comonomer of the multimodal propylene copolymer (U), according to the present invention, is selected from alpha-olefins with 2 or 4 to 8 carbon atoms in a total amount of 3.5 to 12.0 mol% , preferably, from 4.0 to 10.0 molar%, more preferably, from 4.5 to 9.0 molar%, most preferably, from 5.0 to 9.0 molar%, in based on the total content of monomer units in the multimodal propylene copolymer (U).
[0112] k) Relationship between the crystallization temperature Tc and the comonomer content
[0113] The multimodal polypropylene composition, more preferably, the propylene copolymer (U), according to The present invention preferably has the following relationship between the crystallization temperature Tc and the comonomer content: Tc x comonomer content of the multimodal propylene copolymer (U) is at least 400 ° C mole%, more preferably, at least 450 ° C molar%, and most preferably, at least 480 ° C molar%, and not exceeding 1500 ° C molar%.
[0114] ^l ) Content of the copolymer composition (X) of the multimodal propylene copolymer (U)
[0115] The amount of the preferred propylene copolymer composition (X) in the multimodal propylene copolymer (U) is 75 to 98%, preferably 85 to 95% by weight, more preferably 88 to 95 % in weigh.
[0116] m) Content of the propylene copolymer (Y) of the multimodal propylene copolymer (U)
[0117] In addition, the amount of the preferred propylene copolymer (Y) in the multimodal propylene copolymer (U) is from 2 to 25%, preferably, from 5 to 15% by weight, more preferably, from 5 to 12% in weigh.
[0118] In addition, the multimodal propylene copolymer (U) has, more preferably, the following properties and / or ranges of properties:
[0119]
[0120] n) MFR2m division ratio between MFR2x
[0121] Preferably, the ratio of the division of MFR2, or between MFR2, x, according to the present invention, is 0.4 to 0.95, preferably 0.5 to 0.90, and in the manner more preferred, from 0.6 to 0.85.
[0122] o) C2tx division ratio between C2tu
[0123] Preferably, the ratio of the comonomer content division of the copolymer composition (X), C2, x, between the comonomer content of the multimodal propylene copolymer (U), C2m, according to the present invention, is 0 , 50 to 0.96, preferably, from 0.55 to 0.95, and most preferably, from 0.60 to 0.90.
[0124] p) Preferred copolymer composition (X) of the multimodal propylene copolymer (U)
[0125]
[0126] i. MFR 2 of the copolymer composition (X)
[0127] The copolymer composition (X), according to the present invention, has a flow rate of MFR2 (2.16 kg, 230 ° C) of 0.05 to 1.0 g / 10 min, preferably 0.1 at 0.9 g / 10 min, determined according to ISO 1133.
[0128] ii. Contents of the first propylene homopolymer or copolymer (V) of the copolymer composition (X) The amount of the first preferred propylene homopolymer or copolymer, preferably, random propylene copolymer (V) in the copolymer composition (X), according to the present invention, it is from 30 to 60% by weight, preferably, from 33 to 55% by weight, and most preferably, from 40 to 53% by weight.
[0129] ii. Contents of the second propylene homopolymer or copolymer (W) of the copolymer composition (X)
[0130] The amount of the second preferred propylene homopolymer or copolymer, preferably, random propylene copolymer (W) in the copolymer composition (X), according to the present invention, is 40 to 70% by weight, preferably, of the 45 to 67% by weight, and most preferably, 47 to 60% by weight.
[0131] iv. XCS content of the copolymer composition (X)
[0132] In addition, the copolymer composition (X), according to the present invention, preferably has a cold xylene soluble fraction (XCS) content of 3.0 to 20.0% by weight, preferably, from 4.0 to 15.0% by weight, and most preferably, from 4 to 7% by weight, with respect to the weight of the copolymer composition (X), determined at 25 ° C according to ISO 16152 .
[0133] v. Comonomer content of the copolymer composition (X)
[0134] The comonomer of the copolymer composition (X), according to the present invention, is selected, at least, from one of the group consisting of ethylene and alpha-olefins with 4 to 8 carbon atoms in a total amount of 2.0 to 12.0% molar, preferably, 2.5 to 10.0% molar and, most preferably, 4.0 to 6.0 molar%, based on the total content of monomer units in the composition of copolymer (X).
[0135] saw. MFR2x division ratio between MFR2iv
[0136] Preferably, the ratio of the MFR2 value division of the propylene copolymer composition (X) by the MFR2 value of the first random propylene copolymer (V), according to the present invention, is 0.20 to 0 , 80, preferably, from 0.25 to 0.75, and most preferably, from 0.30 to 0.70.
[0137] vii. Ratio of the division of the C2 ^ comonomer content between the C2tx comonomer content Preferably, the ratio of the comonomer content division of the first propylene copolymer (V), C2: v, between the comonomer content of the composition of propylene copolymer (X), C2tx, according to the present invention, is from 0.50 to 0.98, preferably from 0.60 to 0.98, and most preferably from 0.70 to 0.98.
[0138]
[0139] q) First preferred propylene copolymer homopolymer (V) of the propylene copolymer composition (X) of multimodal propylene copolymer (U)
[0140] i. MFR 2
[0141] The first propylene homopolymer or copolymer, preferably, the random propylene copolymer, (V), according to the present invention, has a flow rate of MFR2 (2.16 kg, 230 ° C) of 0.3 to 5, 0 g / 10 min, preferably 0.3 to 3.0 g / 10 min, and most preferably 0.35 to 2.8 g / 10 min, determined according to ISO 1133.
[0142] ii. XCS content
[0143] In addition, the first propylene homopolymer or copolymer, preferably, the random propylene copolymer, (V), according to the present invention has a cold xylene soluble fraction (XCS) content of 1.0 to 20.0 % by weight, preferably, from 2.0 to 15.0% by weight, and most preferably, from 3.0 to 10.0% by weight, based on the weight of the propylene copolymer composition (X), determined at 25 ° C according to ISO 16152.
[0144] Ii. Comonomer content
[0145] The comonomer of the first preferred propylene (V) random copolymer, according to the present invention, is selected, at least, from one of the group consisting of ethylene and alpha-olefins having 4 to 8 carbon atoms in a total amount of 0, 1 to 6.0 molar%, preferably 0.5 to 5.0 molar%, and most preferably 2.0 to 5.0 molar%, based on the total content of monomer units in the first random copolymer of propylene (V).
[0146] r) Second preferred propylene homopolymer or copolymer, preferably, random propylene copolymer, (W), of the propylene copolymer composition (X) of multimodal propylene copolymer (U) i. MFR 2
[0147] The second propylene homopolymer or copolymer, preferably, the random propylene copolymer, (W), according to the present invention, has a melt flow index MFR2 (2.16 kg, 230 ° C) of 0.04 to 0, 60 g / 10 min, preferably 0.06 to 0.30 g / 10 min, and most preferably 0.10 to 0.25 g / 10 min, determined according to ISO 1133.
[0148] ii. Comonomer content
[0149] The comonomer of the second preferred propylene (W) random copolymer, according to the present invention, is selected, at least, from one of the group consisting of ethylene and alpha-olefins with 4 to 8 carbon atoms in a total amount of 3, 0 to 12.0% molar, preferably, 3.5 to 10.0% molar, and most preferably, 4.0 to 7.0 molar%, based on the total content of monomer units in the second random copolymer of propylene (W).
[0150] s) Preferred propylene copolymer (Y) of multimodal propylene copolymer (U)
[0151] i. MFR 2
[0152] The propylene copolymer, (Y), according to the present invention, has a flow rate of MFR2 (2.16 kg, 230 ° C) of 0.0001 to 0.10 g / 10 min, preferably 0.001 to 0.08 g / 10 min, and most preferably, from 0.005 to 0.07 g / 10 min, determined according to ISO 1133.
[0153] ii. Comonomer content
[0154] The comonomer of the propylene copolymer (Y), according to the present invention, is selected, at least, from one of the group consisting of ethylene and alpha-olefins with 4 to 8 carbon atoms in a total amount of 9 to 40 mol% , preferably, from 10 to 40 molar%, preferably, from 12 to 40 molar%, more preferably, from 12 to 38 molar%, and most preferably, from 12 to 30 molar%, in based on the total content of monomer units in the propylene copolymer (Y).
[0155] The shrinkage of the polypropylene composition after forming the composition in an article, preferably, a pipe or a pipe fitting, is preferably not more than 6%, more preferably, not more than 5% , most preferably, not more than 4%.
[0156] Optional and preferred nucleating agent (Z)
[0157] As mentioned above, the nucleating agent (Z) is preferably present in the polypropylene composition of the present invention and is preferably selected from
[0158] - polymeric nucleating agents,
[0159] - salts of monocarboxylic acids and polycarboxylic acids, for example, sodium benzoate;
[0160] - sorbitol compounds, for example, sorbitol or xylitol diacetals, for example 1.3: 2,4 bis (3,4-dimethylbenzylidene) sorbitol (CAS No. 135861-56-2, for example, Millad 3988, Milliken supplier );
[0161] - nonitol-based nucleating agents, for example, 1,2,3-trideoxy-4,6: 5,7-bis-O - ((4-propylphenyl) methylene) nonitol (CAS No. 882073-43-0, for example, MilladNX8000, Milliken provider):
[0162] - phosphorus-based compounds, for example monophenyl, bisphenyl or tetraphenyl phosphates, for example 2,2'-methylene bis- (4,6 di-tert-butylphenyl) sodium phosphate (CAS No. 85209-91-2, for example, NA-11, provider Adeka Corporation) or Hidroxibis (2,4,8,10-tetra-tert) -butyl-6-hydroxy-12-H-dibenzo (d, g) (1,3,2) dioxaphosphocin 6-oxidate) aluminum (CAS No. 151841-65-5, for example, ADK STAB NA-21, supplier Adeka Corporation), or
[0163] - talcum powder,
[0164] - or any mixture thereof.
[0165] More preferably, the nucleating agent (Z) is different from beta-nucleating agents, which are well known in the art.
[0166] It is preferred that said nucleating agent (Z) is a polymeric nucleating agent, preferably, a polymerized vinyl compound, more preferably, a polymeric nucleating agent obtainable by polymerization of vinylcycloalkane monomers or vinyl alkylene monomers.
[0167] The polymeric nucleating agent (Z) is, more preferably, a polymer of a vinyl compound, according to the following formula
[0168] CH2 = CH-CH1R2 (1)
[0169] wherein R1 and R2 together form a saturated, unsaturated or aromatic, 5 or 6-membered ring, optionally containing substituents, or independently representing, an alkyl group comprising 1 to 4 carbon atoms, by which, in case R1 and R2 form an aromatic ring, the hydrogen atom of the group -CHR1R2 is not present.
[0170] Even more preferably, the nucleating agent (Z) is selected from: vinylcycloalkane polymer, preferably, vinylcyclohexane polymer (VCH), vinylcyclopentane polymer, 3-methyl-1-butene polymer and vinyl polymer 2-methyl cyclohexane. The most preferred nucleating agent (Z) is a vinylcyclohexane (VCH) polymer.
[0171] As mentioned above, in a preferred embodiment, the nucleating agent (Z) is a polymeric nucleating agent, more preferably, a vinyl compound polymer according to formula (1), as defined above. , even more preferably, a vinylcyclohexane polymer (VCH). The amount of nucleating agent (Z) is preferably not more than 10,000 ppm, more preferably, not more than 6,000 ppm, even more preferably not more than 5,000 ppm, based on the total weight of the multimodal polypropylene composition (100% by weight), preferably, based on the combined weight of the multimodal propylene copolymer (U) and the nucleating agent (Z).
[0172] The amount of the nucleating agent (Z) is, even more preferably, not more than 500 ppm, preferably, it is 0.025 to 200 ppm, and more preferably, it is 0.1 to 200 ppm, so more preferably, it is from 0.3 to 200 ppm, most preferably, it is from 0.3 to 100 ppm, based on the total weight of the multimodal polypropylene composition (100% by weight), preferably, in based on the combined weight of the multimodal propylene copolymer (U) and the nucleating agent (Z).
[0173] In the preferred embodiment, the nucleating agent (Z) is a polymeric nucleating agent, most preferably, a vinyl compound polymer according to formula (1), as defined above, even more preferably , a vinylcyclohexane (VCH) polymer, as defined above, and the amount of said nucleating agent (Z) is not more than 500 ppm, more preferably, it is from 0.025 to 200 ppm, and more preferably, it is 0.1 to 200 ppm, more preferably, it is 0.3 to 200 ppm, most preferably, it is 0.3 to 100 ppm, based on the total weight of the polypropylene composition multimodal (100% by weight), preferably, based on the combined weight of the multimodal propylene copolymer (U) and the nucleating agent (Z).
[0174] The nucleating agent (Z) can be introduced into the multimodal propylene copolymer (U), for example, during the polymerization process of the multimodal propylene copolymer (U), preferably, during the polymerization process of the composition of propylene copolymer (X), that is, during the polymerization process of the first and second propylene components (V) and (W) thereof, and, preferably, during the polymerization process of the propylene copolymer (Y ). Alternatively, the nucleating agent (Z) may be incorporated into the multimodal propylene copolymer (U) in the form of a masterbatch (MB) together with, for example, a carrier polymer. It is preferred that the nucleating agent (Z) be introduced into the multimodal propylene copolymer (U) during the polymerization process of the multimodal propylene copolymer (U). The nucleating agent (Z) is more preferably introduced into the multimodal propylene copolymer (U) by a first polymerization of the vinyl compound defined above according to the formula (1), as defined above, of even more preferably, of vinylcyclohexane (VCH), in the presence of a catalyst system comprising a catalyst component solid, preferably, a solid catalyst component of Ziegler Natta, a cocatalyst and an optional external donor, and the reaction mixture obtained from the polymer of the vinyl compound according to formula (1), as defined above, of even more preferably, of the vinylcyclohexane polymer (VCH), and the catalyst system is then used to produce the multimodal propylene copolymer (U).
[0175] Said reaction mixture obtained is referred to herein below, interchangeably, as a modified catalyst system.
[0176] Additional additives optional
[0177] In addition, in addition to the nucleating agent (Z), the propylene composition of the present invention may additionally contain additives suitable for pipe applications, preferably conventional additives for pipe applications, including, but not limited to, nucleating agents. additional, clarifying, brightening, acid and antioxidant scavengers, as well as slip agents, inorganic fillers and UV light stabilizers. Each additive can be used, for example, in conventional amounts, with the total amount of additives present in the propylene composition, preferably, as defined below. Such additives are, in general, commercially available and are described, for example, in "Plastic Additives Handbook", "fifth edition, 2001 by Hans Zweifel.
[0178] The total amount of optional additional additives is preferably between 0.0001 and 10% by weight, preferably between 0.0001 and 5.0% by weight, preferably between 0.0001 and 2.5% by weight, more preferably, between 0.0001 and 1.5% by weight, even more preferably, between 0.0001 and 1.0% by weight , based on the total weight of the polypropylene composition (100% by weight). In case the nucleating agent (Z) and / or any additive or optional additives are added in an optional stock mixture, then the carrier material, for example, carrier polymer, of the additive, is calculated with respect to the quantity (total ) of the additive or additives, based on the total weight of the polypropylene composition (100% by weight), preferably, based on the combined weight of the multimodal propylene copolymer (U) and the nucleating agent (Z). It is especially preferred that the polypropylene composition, according to the present invention, consists of the multimodal propylene copolymer (U), the nucleating agent (Z) and optional additional additives, all as defined above.
[0179] Catalyst
[0180] The multimodal propylene copolymer (U) can be produced by polymerization in the presence of any conventional coordination catalyst system, including Ziegler-Natta, chromium and single site (such as, a metallocene catalyst), preferably, in the presence of a Ziegler-Natta catalyst system. Said Ziegler-Natta catalyst system usually comprises a solid catalyst component, preferably, a solid transition metal component, and a cocatalyst, and, optionally, an external donor. The solid catalyst component most preferably comprises a magnesium halide, a titanium halide and an internal electron donor. Such catalysts are well known in the art.
[0181] It is preferred that the nucleating agent (Z) be introduced into the multimodal propylene copolymer (U) during the polymerization process of the multimodal propylene copolymer (U).
[0182] More preferably, a vinyl compound of the formula (1) is polymerized, as defined above or preferably, preferably, of vinylcyclohexane (VCH), in the presence of a catalyst system comprising the solid catalyst component , preferably, a solid catalyst component of Ziegler Natta, to obtain a modified catalyst system which is the reaction mixture comprising the solid catalyst component and the polymer produced from the vinyl compound of formula (1). In the modified catalyst system obtained, the weight ratio (g) of the polymer of the vinyl compound of the formula (1) with respect to the solid catalyst component is preferably up to 5 (5: 1), preferably Preferred, up to 3 (3: 1), most preferably, is 0.5 (1: 2) to 2 (2: 1). The modified catalyst system obtained is then used for the polymerization of the multimodal propylene copolymer (U) of the present invention. The general preparation of the modified catalyst system of the present invention and the polypropylene nucleated with a vinyl compound (1) is disclosed, for example, in EP 1028984.
[0183] As for the Ziegler Natta solid catalyst component used for the modification, said catalyst component preferably comprises a transition metal component and a magnesium halide. These compounds may be supported on a particulate support, such as inorganic oxide, such as silica or alumina, or, usually, magnesium halide to form on said solid support. Some examples of said solid catalyst components are disclosed, among others, in WO 87/07620, WO 92/21705, WO 93/11165, WO 93/11166, WO 93/19100, 97/36939, WO 98/12234, WO 99/33842.
[0184] A catalyst of the Ziegler-Natta type commonly used in the present invention for the polymerization of Propylene is stereospecific, comprising a high-performance Ziegler-Natta catalyst as essential components, Mg, Ti, Al and Cl. This type of catalysts usually comprises, in addition to a solid transition metal component (such as Ti), a cocatalyst or cocatalysts, as well as a donor or external donors as a stereoregulation agent.
[0185] These compounds may be supported on a particulate support, such as inorganic oxide, such as silica or alumina, or, usually, magnesium halide can form the solid support. It is also possible that the solid catalysts are self-supported, that is, the catalysts are not supported on an external support, but are prepared by an emulsion-solidification process.
[0186] The solid catalyst components for the polymerization of the multimodal propylene copolymer (U) usually comprise, in addition to the magnesium halide and the transition metal compound, an electron donor (internal electron donor).
[0187] Suitable electron donors are, among others, esters of carboxylic acids, such as phthalates, citraconates and succinates. Silicon compounds containing oxygen or nitrogen can also be used. Some examples of suitable compounds are shown in WO 92/19659, WO 92/19653, WO 92/19658, US 4347160, US 4382019, US 4435550, US 4465782, US 4473660, US 4530912 and US 4560671.
[0188] The cocatalyst used in combination with the transition metal compound usually comprises an alkyl aluminum compound. The alkyl aluminum compound is preferably trialkyl aluminum, such as trimethyl aluminum, triethyl aluminum, tri-isobutyl aluminum or tri-n-octyl aluminum. However, it can also be an alkyl aluminum halide, such as diethyl aluminum chloride, dimethyl aluminum chloride and ethyl aluminum sesquichloride. Triethyl aluminum is an especially preferred alkyl aluminum compound. The alkyl aluminum is preferably introduced to achieve a desired proportion of aluminum with respect to titanium. Suitable proportions depend on the catalyst and are in the range of 30 to 1000 mol / mol, such as 50 to 600 mol / mol.
[0189] In addition, said solid catalyst components are preferably used in combination with known external electron donors, including, but not limited to, ethers, ketones, amines, alcohols, phenols, phosphines and silanes, for example organosilane compounds. containing Si-OCOR, Si-OR or Si-NR2 bonds, which have silicon as the central atom, and R is an alkyl, alkenyl, aryl, arylalkyl or cycloalkyl group having 1-20 carbon atoms; and known cocatalysts, which preferably comprise an alkyl aluminum compound, as is known in the art, to produce the multimodal propylene copolymer (U). Especially preferred external donors include alkoxysilanes bearing alkyl substituents, such as methylcyclohexyldimethoxysilane and dicyclopentyldimethoxysilane.
[0190] When the nucleating agent (Z) is introduced into the multimodal propylene copolymer (U) during the polymerization process of the multimodal propylene copolymer (U), the amount of nucleating agent (Z) present in the multimodal propylene copolymer ( U) is preferably not more than 500 ppm, more preferably, it is 0.025 to 200 ppm, even more preferably, it is 1 to 100 ppm, and most preferably, it is 5 to 100 ppm, based on the total weight of the propylene composition (100% by weight), preferably, based on the combined weight of the multimodal propylene copolymer (U) and the nucleating agent (Z). General procedure
[0191] The multimodal polypropylene (U) composition of the present invention is preferably produced in a continuous multistage process in a conventional manner. It should be understood that as soon as the present inventors have discovered the advantageous balance of properties that gives rise to the multimodal polypropylene (U) composition, for industrial scale production it is within the capabilities of a person skilled in the art to adjust the parameters and process controls to obtain the properties of the multimodal polypropylene composition (U). The process preferably comprises at least three polymerization steps.
[0192] It should be understood that the process may contain additional polymerization steps, preferably, included in the first polymerization stage. It may contain additional polymerization stages, such as a prepolymerization stage. In addition, any of the three polymerization steps may comprise two or more polymerization sub-stages to give rise to the polymer reaction mixture of that stage. In the most preferred embodiment, the process consists of three polymerization stages each comprising a single polymerization stage, while the first polymerization stage may additionally include a prepolymerization stage.
[0193] Accordingly, the present invention further discloses a multistage process for producing the multimodal polypropylene composition, as defined above or in the claims, wherein the propylene and at least one comonomer selected from alpha- olefins with 2 or 4 to 8 carbon atoms polymerize in the presence of
[0194] (I) a solid catalyst component comprising a magnesium halide, a titanium halide and an internal electron donor; Y
[0195] (II) a cocatalyst comprising an aluminum alkyl and, optionally, an external electron donor; and (III) an optional nucleating agent (Z), preferably, in the presence of a nucleating agent (Z) as defined above or subsequently;
[0196] the multistage process comprising the stages of
[0197] (A) continuously polymerize propylene, optionally, a comonomer selected from the ethylene group and, at least, a C4-C8 alpha-olefin, in a first polymerization stage by introducing streams of propylene, hydrogen and, optionally, said comonomer, in the first polymerization stage at a temperature of 60 to 100 ° C and a pressure of 40 to 65 bar to produce a first propylene polymer (V), in which the first propylene polymer (V) has a MFR2 flow rate (2.16 kg, 230 ° C; ISO 1133) from 0.3 to 5.0 g / 10 min;
[0198] (B) extracting from the first stage of polymerization a stream comprising the first propylene polymer (V) and transferring said stream to a second stage of polymerization;
[0199] (C) polymerize propylene in the presence of said first propylene polymer (V) in the second polymerization stage at a temperature of 65 to 90 ° C and a pressure of 19 to 25 bar by introducing streams of propylene, hydrogen and, optionally, at least one comonomer, to produce a copolymer composition (X) of said first propylene polymer (V) and a second propylene polymer (W); provided that at least one of said first and second polymers (V) and (W) is a random copolymer of propylene;
[0200] said copolymer composition (X) comprising
[0201] from 30 to 60% by weight of said first propylene polymer (V) and from 40 to 70% by weight of said second propylene polymer (W) with respect to the copolymer composition (X),
[0202] wherein the copolymer composition (X) has an MFR2 flow rate of 0.05 to 1.0 g / 10 min which is lower than the MFR2 of said first polymer (V);
[0203] (
[0204] D) extracting a stream comprising the copolymer composition (X) of the second polymerization stage and transferring said stream to a third polymerization stage;
[0205] (E) polymerize propylene and at least one comonomer in the presence of the copolymer composition (X) in the third polymerization stage at a temperature of 65 to 90 ° C and a pressure of 10 to 100 bar by introducing streams of propylene, hydrogen and at least one comonomer, to produce the multimodal propylene copolymer (U) comprising the copolymer composition (X) and an additional component of propylene copolymer (Y), in which the propylene copolymer multimodal (U) has an MFR2 flow rate of 0.05 to 1.00 g / 10 min;
[0206] wherein the multimodal propylene copolymer (U) comprises 75 to 98% by weight, preferably 85 to 95% by weight of said copolymer composition (X) and 2 to 25% by weight, so preferably, 5 to 15% by weight of said propylene copolymer (Y); Y
[0207] wherein the comonomer content of the propylene copolymer (Y) is 9.0 to 40 mol%;
[0208] (F) continuously extracting a stream comprising the multimodal propylene copolymer (U) from the third polymerization stage and, optionally, mixing the multimodal propylene copolymer (U) with additives; Y
[0209] (G) Extrude the multimodal propylene copolymer (U) into granules.
[0210] At a minimum, the second propylene polymer (W) is preferably a random copolymer of propylene.
[0211] In the preferred multi-stage process of the present invention, propylene and at least one comonomer selected from alpha-olefins having 2 or 4 to 8 carbon atoms are polymerized in the presence of
[0212] (I) a solid catalyst component comprising a magnesium halide, a titanium halide and an internal electron donor; Y
[0213] (II) a cocatalyst comprising an aluminum alkyl and, optionally, an external electron donor; and (III) an optional nucleating agent (Z), preferably, in the presence of a nucleating agent (Z) as defined above or subsequently;
[0214] the multistage process comprising the stages of
[0215] (A) continuously polymerize propylene, a comonomer selected from the ethylene group and at least one C4-C8 alpha-olefin, in a first polymerization stage by introducing streams of propylene, hydrogen and said comonomer in the first polymerization step at a temperature of 60 to 100 ° C and a pressure of 40 to 65 bar to produce a first propylene polymer (V), in which the first random propylene copolymer (V) has a flow rate of MFR2 ( 2.16 kg, 230 ° C; ISO 1133) from 0.3 to 5.0 g / 10 min;
[0216] (B) extracting from the first stage of polymerization a stream comprising the first random propylene copolymer (V) and transferring said stream to a second stage of polymerization;
[0217] (C) polymerize propylene in the presence of said first random propylene copolymer (V) in the second polymerization stage at a temperature of 65 to 90 ° C and a pressure of 19 to 25 bar by introducing streams of propylene, hydrogen and at least one comonomer, to produce a copolymer composition (X) of said first random propylene copolymer (V) and a second random propylene copolymer (W);
[0218] said copolymer composition (X) comprising
[0219] from 30 to 60% by weight of said first random propylene copolymer (V) and from 40 to 70% by weight of said second random propylene copolymer (W) with respect to the copolymer composition (X),
[0220] wherein the copolymer composition (X) has an MFR2 flow rate of 0.05 to 1.0 g / 10 min which is lower than the MFR2 of said first polymer (V);
[0221] (D) extracting a stream comprising the copolymer composition (X) of the second polymerization stage and transferring said stream to a third polymerization stage;
[0222] (E) polymerize propylene and at least one comonomer in the presence of the copolymer composition (X) in the third polymerization stage at a temperature of 65 to 90 ° C and a pressure of 10 to 100 bar by introducing streams of propylene, hydrogen and at least one comonomer, to produce the multimodal propylene copolymer (U) comprising the copolymer composition (X) and an additional component of propylene copolymer (Y), in which the propylene copolymer multimodal (U) has an MFR2 flow rate of 0.05 to 1.00 g / 10 min;
[0223] wherein the multimodal propylene copolymer (U) comprises 75 to 98% by weight, preferably 85 to 95% by weight of said copolymer composition (X) and 2 to 25% by weight, so preferably, 5 to 15% by weight of said propylene copolymer (Y); Y
[0224] wherein the comonomer content of the propylene copolymer (Y) is 9.0 to 40 mol%;
[0225] (F) continuously extracting a stream comprising the multimodal propylene copolymer (U) from the third polymerization stage and, optionally, mixing the multimodal propylene copolymer (U) with additives; Y
[0226] (G) Extrude the multimodal propylene copolymer (U) into granules.
[0227] It is more preferred that the multi-stage process, according to the present invention, comprises the following process stage preceding stage (A):
[0228] (AA) polymerize a vinyl compound of the formula (1), as defined above or later, preferably, vinylcyclohexane (VCH) in the presence of a catalyst system comprising the solid catalyst component (I) to obtain a modified catalyst system which is the reaction mixture comprising the solid catalyst component (I) and the polymer produced from the vinyl compound of formula (1), preferably, and in which, the weight ratio (g) of the polymer of the vinyl compound of the formula (1) with respect to the solid catalyst component (I) is up to 5 (5: 1), preferably, up to 3 (3: 1), most preferably, it is from 0.5 (1: 2) to 2 (2: 1), and the modified catalyst system obtained is introduced in the polymerization stage (A) of the multistage process for the production of the multimodal propylene copolymer (U) .
[0229] The multistage process of the present invention is described in greater detail below with reference to the production of the first random propylene copolymer (V) and the second preferred propylene random copolymer (W), however, without being limited thereto. Accordingly, the following description provides the general principles of the process of the present invention and can be adapted to the preparation of the optional propylene homopolymer as one of the first and second propylene polymers (V) and (W):
[0230] a) Prepolymerization stage
[0231] In a preferred embodiment, the prepolymerization step is carried out in a continuous manner as a mass suspension polymerization in liquid propylene, that is, the liquid phase mainly comprises propylene, with a smaller amount of other reagents and, optionally, inert components dissolved therein. Preferably, the prepolymerization step is carried out in a continuous stirred tank reactor or a loop reactor. The prepolymerization reaction is usually carried out at a temperature of 0 to 60 ° C, preferably 10 to 50 ° C. The pressure in the prepolymerization reactor is not critical, but must be high enough to keep the reaction mixture in liquid phase. Thus, the pressure can be from 20 to 100 bar, for example, from 30 to 70 bar. Reaction conditions are well known in the art, as described, inter alia, in GB 1580635. It is also possible to introduce comonomers in the prepolymerization stage. Some examples of suitable comonomers are ethylene or alpha-olefins having 4 to 10 carbon atoms. Especially suitable comonomers are ethylene, 1-butene, 1-hexene, 1-octene or mixtures thereof. The amount of polymer produced in the prepolymerization step does not exceed 5% by weight of the amount of the total polymer, preferably, does not exceed 3% by weight of the amount of the total polymer and, in particular, does not exceed 2 % by weight or even 1% by weight of the amount of total polymer produced in all polymerization steps.
[0232] b) First stage of polymerization
[0233] In the first polymerization stage, the first random propylene copolymer (V) is produced. This is done by introducing a polymerization catalyst, preferably, through the prepolymerization stage as described above, in the first polymerization stage together with the mixture of propylene-containing monomers and, optionally, a comonomer selected from ethylene and alpha-olefins containing 4 to 10 carbon atoms.
[0234] The content of the comonomer, if present, is controlled to obtain a desired comonomer content in the first random propylene copolymer (V). Preferably, the first random propylene copolymer (V) contains 0.1 to 6.0 mole% of units derived from the comonomer and 94 to 99.9 mole percent of propylene units.
[0235] The first random propylene copolymer (V) preferably has an MFR2 of 0.3 to 5.0 g / 10 min.
[0236] As indicated by the comonomer content, the first random propylene copolymer (V) is semi-crystalline and non-amorphous (i.e., the elastomeric phase is not present). The fraction of cold xylene soluble polymer at 25 ° C in the first random propylene copolymer (V) is 1.0 to 20.0% by weight.
[0237] The polymerization in the first polymerization stage is preferably carried out in suspension in a loop reactor. Next, the polymer particles formed in the polymerization, together with the catalyst fragmented and dispersed in the particles, are suspended in a liquid hydrocarbon. The suspension is stirred to allow the transfer of reagents from the liquid to the particles. In loop reactors, the suspension is circulated with a high speed along a closed tube by means of the use of a circulation pump. Loop reactors are well known in the art and examples are provided, for example, in US 4582816, US 3405109, US 3324093, EP 479186 and US 5391654. Suspension polymerization is preferably a polymerization referred to in mass. By "mass polymerization" is meant a process in which the polymerization is carried out in a liquid monomer essentially in the absence of an inert diluent. However, as is known to one skilled in the art, the monomers used in commercial production are never pure, but always contain aliphatic hydrocarbons as impurities. For example, the propylene monomer can contain up to 5% propane as impurity. As propylene is consumed in the reaction and is also recycled from the reaction effluent back to the polymerization, the inert components tend to accumulate and, thus, the reaction medium can comprise up to 40% by weight of others. compounds that are not monomer. It should be understood, however, that said polymerization process is still within the meaning of "mass polymerization", as defined above.
[0238] The temperature of the suspension polymerization is usually 60 to 100 ° C, preferably 60 to 75 ° C and, in particular, 65 to 72 ° C. The pressure is from 10 to 100 bar, preferably, from 25 to 80 bar and, most preferably, from 40 to 65 bar. The pressure is normally selected to be higher than the vapor pressure of the liquid reaction mixture at the selected working temperature. Hydrogen is normally introduced into the reactor to control the molecular weight, or MFR2, of the first polymer. Typically, hydrogen is introduced to maintain a constant molar ratio of hydrogen to propylene in the reactor. It has been found for certain catalysts that when the ratio of hydrogen to propylene is in the range of 0.1 to 4.0 mol / kmol (or, mol / 1000 mol), preferably 0.3 to 3.0 mol / kmol and, most preferably, from 0.4 to 2.5 mol / kmol, the MFR2 of the first polymer is within the preferred limits necessary for the present invention.
[0239] The comonomer is introduced to achieve the desired content of comonomer units in the polymer. The actual amount of the comonomer is, preferably, within the range of 1.0 to 30.0 mol / kmol, preferably, 3.0 to 10.0 mol / kmol and, most preferably, from 5.0 to 8.5 mol / kmol. The suspension is It can be continuously or intermittently removed from the reactor. A preferred way of intermittent extraction is the use of settling legs, in which the increase of the solids concentration of the suspension is allowed before the extraction of a batch of the concentrated suspension from the reactor. The use of settling legs is disclosed, among others, in documents US 3374211, US 3242150 and EP 1310295. Continuous extraction is disclosed, among others, in documents EP 891990, EP 1415999, EP 1591460 and EP 1860125. Continuous extraction can be combined with a suitable concentration procedure, as disclosed in EP 1860125 and EP 1591460.
[0240] Other components are introduced in the first polymerization stage as is known in the art. Process additives, such as an antistatic agent, can be introduced into the reactor to facilitate stable operation of the process.
[0241] According to a preferred embodiment of the present invention, the suspension is carried out directly in a second subsequent polymerization stage. By "directly" is meant that the suspension is introduced from the first to the second stage of polymerization without a rapid stage ("flash") between both stages of polymerization for the extraction, at least, of a part of the reaction mixture of the polymer. This type of direct feed is disclosed in EP 887379, EP 887380, EP 887381 and EP 991684. Thus, there is no separation stage between the stages. However, it is within the scope of the present invention to take small samples or sample streams of the polymer or liquid phase or both for the analysis of the polymer and / or the composition of the reaction mixture.
[0242] Second stage of polymerization
[0243] In the second polymerization stage, the propylene copolymer composition (X) comprising the first random propylene copolymer (V) and the second random propylene copolymer (W) is formed. This is done by introducing the particles of the first random propylene copolymer (V), which contains the active catalyst dispersed therein, together with additional propylene and, optionally, comonomer, in the second polymerization stage. Hydrogen is introduced to control molecular weight. This causes the second random propylene copolymer (W) to be formed on the particles containing the first random propylene copolymer (V).
[0244] The MFR2 of the propylene copolymer composition (X) is 0.05 to 1.0 g / 10 min. In addition, the MFR2 of the propylene copolymer composition (X) is lower than the MFR2 of the first random propylene copolymer (V). Preferably, the ratio of the MFR2 of the propylene copolymer composition (X) with respect to the MFR2 of the first random propylene copolymer (V), MFR2, x / MFR2, v has a value of 0.20 to 0.80 . As is well known in the art, the MFR2 of the second random propylene copolymer (W) produced in the second polymerization stage cannot be measured directly because the second random propylene copolymer (W) cannot be isolated from the composition of propylene copolymer (X). However, knowing the weight fractions of the polymer and the flow rates of the first random propylene copolymer (V) and the propylene copolymer composition (X), it is possible to calculate the MFR2 of the second random propylene copolymer (W). This will be done by using equation 2:
[0245] Míb = (w * • M / r00965 W2 • M / 2- ° 0965) “Sshi (2)
[0246] Where w is the weight fraction of the component in the mixture, MI is the MFR2 and the subscripts b, 1 and 2 refer to the mixture, component 1 and component 2, respectively. When calculating the MFR2 of the second random propylene copolymer (W), it can be found that it is within the range of 0.04 to 0.60 g / 10 min.
[0247] The comonomer is selected from ethylene and alpha-olefins containing from 4 to 8 carbon atoms. The comonomer used in the second polymerization stage may be the same or different from the comonomer used in the first polymerization stage. Preferably, the same comonomer is used in the first and second polymerization stages. The content of the comonomer in the second polymerization stage is controlled to obtain the desired comonomer content of the propylene copolymer composition (X). Usually, the propylene copolymer composition (X) contains from 2.0 to 12.0 mole% of units derived from the comonomer and from 88.0 to 98.0 mole percent of propylene units. In addition, the comonomer content of the propylene copolymer composition (X) is greater than the comonomer content of the first random propylene copolymer (V). Preferably, the proportion of the comonomer content of the first random propylene copolymer (V) with respect to the comonomer content of the propylene copolymer composition (X) (both expressed in mole%), Cv / Cx, is 0 , 50 to 0.98.
[0248] The comonomer content of the second random propylene copolymer (W) cannot be measured directly. However, by using the standard mixing rule, it can be calculated from the comonomer content of the propylene copolymer composition (X) and the first random propylene copolymer (V).
[0249] where C is the comonomer content in% by weight, w is the weight fraction of the component in the mixture and the subscripts b, 1 and 2 refer to the overall mixture, component 1 and component 2, respectively.
[0250]
[0251] Therefore, it can be seen that the second random propylene copolymer (W) contains 3.0 to 12.0 mole% of units derived from the comonomer and 88.0 to 97.0 mole percent of propylene units. As is well known by the person skilled in the art, the comonomer content on a weight basis in a binary copolymer can be converted into the comonomer content on a molar base by using the following equation 4:
[0252]
[0253]
[0254]
[0255]
[0256] where cm is the molar fraction of comonomer units in the copolymer, Cw is the weight fraction of comonomer units in the copolymer, MWc is the molecular weight of the comonomer (such as ethylene) and MWm is the molecular weight of the monomer main (i.e. propylene). As indicated by the comonomer content, the second random propylene copolymer (W) is semi-crystalline and non-amorphous (i.e., the elastomeric phase is not present).
[0257]
[0258] The fraction of xylene-soluble polymer at 25 ° C in the propylene copolymer composition (X) is 3.0 to 20.0% by weight.
[0259]
[0260] The content of the xylene soluble polymer in the second random propylene copolymer (W) cannot be measured directly. However, the quantity can be estimated by using the standard mixing rule:
[0261]
[0262]
[0263]
[0264]
[0265] where XS is the content of polymer soluble in xylene in% by weight, w is the fraction by weight of the component in the mixture and the subscripts b, 1 and 2 refer to the overall mixture, component 1 and component 2 respectively. It can be seen that the second random propylene copolymer (W) usually has a xylene soluble polymer content not exceeding 20% by weight, preferably not exceeding 15% by weight. Usually, the fraction of xylene soluble polymer in the second random propylene copolymer (W) is at least 1% by weight, preferably at least 5% by weight. The propylene copolymer composition (X) comprises 30 to 60% by weight of the first random propylene copolymer (V) and 40 to 70% by weight of the second random propylene copolymer (W). The propylene copolymer composition (X) is semi-crystalline and non-amorphous (that is, the elastomeric phase is not present).
[0266]
[0267] The second polymerization stage is preferably carried out in a fluidized bed gas phase reactor. It is often necessary to introduce additional hydrogen into the second polymerization stage to control the MFR of the propylene copolymer composition. Suitably, the hydrogen feed is controlled to maintain a constant ratio of hydrogen to propylene in the fluidization gas. The actual ratio depends on the catalyst. Good results have been obtained by maintaining the ratio within the range of 0.1 to 4 mol / kmol. Although the actual ratio of comonomer to monomer depends on the type of comonomer and the type of catalyst used in the process, the feed of the monomer composition and the comonomer is properly adjusted so that the fluidizing gas preferably, it has a proportion of comonomer with respect to propylene of approximately 10 to 100 mol / kmol (or, mol / 1000 mol), preferably, 15 to 70 mol / kmol and, most preferably, from 25 to 40 mol / kmol. It has been observed that such proportions provide good results for some catalysts.
[0268]
[0269] In a fluidized bed gas phase reactor, the olefins are polymerized in the presence of a polymerization catalyst in a gas stream that moves upwards. The reactor usually contains a fluidized bed comprising the growing polymer particles containing the active catalyst, said fluidized bed having its base above a fluidization grid and at a higher level in the gas phase reactor. The polymer bed is fluidized with the aid of the fluidization gas comprising the olefin monomer, possible comonomer or final comonomers, possible chain growth controllers or chain transfer agents, such as hydrogen, and possible inert gas. The fluidization gas is introduced into an inlet chamber at the bottom of the reactor. To ensure that the gas flow is distributed evenly across the cross-sectional surface area of the inlet chamber, the inlet tube may be equipped with a flow dividing element as is known in the art, for example, in the US 4933149 and EP 684871. Usually, one or more of the components mentioned above are added continuously in the fluidization gas to compensate for losses caused, among other reasons, by reaction or product extraction.
[0270]
[0271] From the inlet chamber, the flow of gas in upward motion is passed through a fluidization grid to the fluidized bed. The purpose of the fluidization grid is to divide the gas flow evenly across the cross-sectional area of the bed. Sometimes, the fluidization grid may be arranged to establish a stream of gas that drags along the reactor walls, as disclosed in WO 2005/087361. Other types of fluidization networks are described, among others, in US 4578879, EP 600414 and EP 721798. In Geldart and Bayens: The Design of Distributors for Gas-fluidized Beds ("The design of fluidized gas bed distributors" ), Powder Technology, volume 42, 1985, an overview is provided. The fluidization gas passes through the fluidized bed. The surface velocity of the fluidization gas must be greater than the minimum fluidization rate of the particles contained in the fluidized bed, since otherwise fluidization would not occur. On the other hand, the gas velocity must be lower than the transport velocity, since otherwise the entire bed would be carried along with the fluidization gas. The porosity of the bed is usually less than 0.8, preferably, less than 0.75 and, more preferably, less than 0.7. In general, the porosity of the bed is at least 0.6. In Geldart: Gas Fluidization Technology, J. Wiley & Sons, 1986, in chapters 2.4 and 2.5 (pages 17-18), as well as in chapters 7.3 to 7.5 (pages 169-186 , especially in Figure 7.21 on page 183), among others, an overview is provided. When the fluidizing gas comes into contact with the bed containing the active catalyst, the reactive components of the gas, such as monomers and chain transfer agents, react in the presence of the catalyst to produce the polymer product. At the same time, the gas is heated by the heat of reaction. The unreacted fluidization gas is extracted from the top of the reactor and cooled in a heat exchanger to remove the heat of reaction. The gas is cooled to a temperature that is lower than that of the bed to avoid heating the bed due to the reaction. It is possible to cool the gas to a temperature at which a part of it condenses. When the liquid droplets enter the reaction zone they evaporate. Therefore, the heat of vaporization contributes to the elimination of the heat of reaction. This type of operation is called condensed mode and variations thereof are disclosed, among others, in WO 2007/025640, US 4543399, EP 699213 and WO 94/25495. It is also possible to add condensing agents into the recycle gas stream, as disclosed in EP 696293. The condensing agents are non-polymerizable components, such as n-pentane, isopentane, n-butane or isobutane, which are at least partially condensed in the refrigerant. Next, the gas is compressed and recycled into the reactor inlet chamber. Prior to entering the reactor, freshly prepared reagents are introduced into the fluidization gas stream to compensate for the losses caused by the reaction and product extraction. In general, it is known to analyze the composition of the fluidization gas and introduce the gas components to keep the composition constant. The actual composition is determined by the desired properties of the product and the catalyst used in the polymerization.
[0272]
[0273] The polymer product can be extracted from the gas phase reactor continuously or intermittently. You can also use combinations of these procedures. Continuous extraction is disclosed, among others, in WO 00/29452. Intermittent extraction is disclosed, among others, in US 4621952, EP 188125, EP 250169 and EP 579426. The upper part of the gas phase reactor may include a zone called separation. In said zone, the diameter of the reactor is increased to reduce the speed of the gas and allow the particles that are transported from the bed with the fluidization gas to be deposited again in the bed. The level of the bed, that is, the upper level, can be observed by different techniques known in the sector. For example, the pressure difference between the bottom of the reactor and a specific bed height can be recorded over the entire length of the reactor and the bed level can be calculated based on the pressure difference values. This calculation produces a level averaged over time. It is also possible to use ultrasonic sensors or radioactive sensors. With these procedures, instantaneous levels can be obtained, which, of course, can then be averaged over time to obtain a bed level averaged over time.
[0274]
[0275] If necessary, an antistatic agent or agents can also be introduced into the gas phase reactor. Suitable antistatic agents and procedures for their use are disclosed, among others, in US 5026795, US 4803251, Us 4532311, US 4855370 and EP 560035. Usually, they are polar compounds and include, among others, water, ketones, aldehydes and alcohols. The reactor may also include a mechanical stirrer to further facilitate mixing in the fluidized bed. An example of a suitable agitator design is disclosed in EP 707513.
[0276]
[0277] The fluidized bed polymerization reactor operates at a temperature in the range of 60 to 100 ° C, preferably 65 to 90 ° C, and most preferably 75 to 85 ° C. The pressure is suitably from 10 to 100 bar, preferably from 15 to 30 bar and, most preferably, from 19 to 25 bar.
[0278]
[0279] c) Third stage of polymerization
[0280]
[0281] In the third polymerization stage, the multimodal propylene copolymer (U) comprising the propylene copolymer composition (X) and a propylene copolymer (Y) is formed. This is done through the introduction of the particles of the propylene copolymer composition (X), which contains the active catalyst dispersed therein, together with additional propylene and a comonomer, in the third stage of polymerization. Hydrogen can be introduced to control molecular weight. This causes the propylene copolymer (Y) to be formed on the particles containing the propylene copolymer composition (X).
[0282] The MFR2 of the multimodal propylene copolymer (U) is from 0.05 to 1.00 g / 10 min. The MFR of the multimodal propylene copolymer (U) is lower than the MFR of the propylene copolymer composition (X). Preferably, the ratio of the MFR2 of the multimodal propylene copolymer (U) with respect to the MFR2 of the propylene copolymer composition (X) is at most 0.95. Usually, the proportion is not less than 0.4.
[0283] As explained above for the propylene copolymer composition (X), the MFR2 of the propylene copolymer (Y) cannot be measured because the propylene copolymer (Y) cannot be isolated from the multimodal propylene copolymer (U) . However, the MFR2 of the propylene copolymer (Y) can be calculated using equation 2 above. In this case, component 1 is the propylene copolymer composition (X), component 2 is the propylene copolymer (Y) and the final mixture is the multimodal propylene copolymer (U). Therefore, it can be seen that the MFR2 of the propylene copolymer (Y) is 0.0001 to 0.1 g / 10 min. Accordingly, the comonomer content of the propylene copolymer (Y) can be calculated using equation 3.
[0284] The hydrogen feed is adjusted to achieve a desired flow rate (or molecular weight) of the polymer. Suitably, the hydrogen feed is controlled to keep the ratio of hydrogen to propylene constant in the reaction mixture. The actual ratio depends on the catalyst, as well as the type of polymerization. Good results have been obtained in the gas phase polymerization by maintaining the proportion within the range of 0.1 to 3.0 mol / kmol, preferably 0.2 to 2.0 mol / kmol and, of most preferably, from 0.3 to 1.5 mol / kmol.
[0285] The comonomer is selected from ethylene and alpha-olefins containing from 4 to 8 carbon atoms. The comonomer used in the third polymerization stage may be the same or different from the comonomer used in the preceding polymerization steps. Preferably, the same comonomer is used in all polymerization steps. Very suitably, ethylene is used as a comonomer. The content of the comonomer in the third polymerization stage is controlled to obtain the desired comonomer content of the multimodal propylene copolymer (U). Usually, the multimodal propylene copolymer (U) contains from 3.5 to 12.0 mol% of units derived from the comonomer and from 88.0 to 96.5 mol% of propylene units. The content of comonomer units in the multimodal propylene copolymer (U) is greater than the content of comonomer units in the propylene copolymer composition (X). Preferably, the proportion of the content of comonomer units in the propylene copolymer composition (X) with respect to the content of comonomer units in the multimodal propylene copolymer (U), C ^x / C ^u , in which both C ^x as C ^u expressed in% molar, is 0.50 to 0.96.
[0286] As described above for the propylene copolymer composition (X), the comonomer content of the propylene copolymer (Y) cannot be measured directly. Instead, it can be calculated using equation 3 above. In this case, component 1 is the propylene copolymer composition (X), component 2 is propylene polymer (Y) and the final mixture is the multimodal propylene copolymer (U). The content of the comonomer units in the propylene copolymer (Y) is from 9 to 40.0 mol% and a content of propylene units from 60.0 to 91.0 mol%. The molar ratio of comonomer to propylene is preferably 50 to 500 mol / kmol, preferably 100 to 350 mol / kmol and, most preferably 150 to 300 mol / kmol. The multimodal propylene copolymer (U) comprises 75 to 98% by weight of the propylene copolymer composition (X), and 2 to 25% by weight of the propylene copolymer (Y). The third stage of polymerization is preferably carried out in a fluidized bed gas phase reactor, as described above.
[0287] The third stage is carried out at a temperature in the range of 60 to 100 ° C, preferably 65 to 90 ° C and, most preferably, 75 to 85 ° C. The pressure is suitably from 10 to 100 bar, preferably from 15 to 30 bar and, most preferably, from 19 to 25 bar.
[0288] Extrusion:
[0289] When the polymer has been removed from the last stage of polymerization, it is preferably subjected to process steps to remove residual hydrocarbons from the polymer. Such procedures are well known in the art and may include pressure reduction stages, purge stages, drag extraction stages, extraction stages, and so on. Combinations of different stages are also possible. After removal of the residual hydrocarbons, the second propylene copolymer composition is preferably mixed with additives, as is well known in the art. Such additives include antioxidants, process stabilizers, neutralizers, lubricating agents, nucleating agents, pigments, and so on. The polymer particles are then extruded into granules, as is known in the art. Preferably, a twin-screw extruder is used for the stage of extrusion. Such extruders are manufactured, for example, by Coperion (Werner & Pfleiderer) and Japan Steel Works. Article of the invention:
[0290] In addition, the present invention relates to an article comprising the multimodal polypropylene composition according to the present invention.
[0291] In a preferred embodiment, the article is selected from an extruded article, preferably, a pipe application, or an application of molded article, preferably, an injection molded or blow molded article, more preferably, a accessory for pipe applications, comprising the multimodal polypropylene composition of the present invention. The pipe and the fitting produced from the polypropylene composition, according to the present invention, preferably have good mechanical properties, as described above and shown below in the experimental part. Thus, the pipe, according to the present invention, is preferably described as a pressure pipe.
[0292] The pipe of the present invention can be
[0293] a monolayer pipe, in which the pipe layer preferably comprises the multimodal polypropylene composition of the present invention, or
[0294] - a multi-layer pipe, in which at least one layer preferably comprises the multimodal polypropylene composition of the present invention.
[0295] The preferred pipe of the present invention has, at a minimum, a layer comprising, preferably, consisting of the multimodal polypropylene composition of the present invention. The preferred pipe is a pressure pipe, more preferably, a pressure pipe for hot and cold water applications. The accessory of the present invention preferably consists of the multimodal polypropylene composition of the present invention.
[0296] Manufacture of the pipe of the invention:
[0297] The pipes can be manufactured from the multimodal polypropylene composition, according to the present invention, according to the procedures known in the art. Thus, according to a preferred method, the multimodal polypropylene composition is extruded through an annular nozzle to a desired internal diameter, after which the multimodal polypropylene composition is cooled.
[0298] The pipe extruder operates, preferably, at a relatively low temperature and, therefore, excessive heat accumulation should be avoided. Extruders having a high proportion of length with respect to diameter L / D of more than 15 are preferred, preferably at least 20 and in particular at least 25. Modern extruders usually have an L / D ratio from about 30 to 35.
[0299] The polymer melt is extruded through an annular nozzle, which can be arranged in a feed configuration by the end or side. Side feed nozzles are often mounted with their axes parallel to that of the extruder, which requires a right angle turn in the connection to the extruder. The advantage of the lateral feed nozzles is that the mandrel can be extended through the nozzle and this allows, for example, easy access for the water cooling pipes to the mandrel.
[0300] After the plastic melt leaves the nozzle, it is calibrated to the correct diameter. In one procedure, the extruded material is directed to a metal tube (calibration sleeve). The interior of the extruded material is pressurized so that the plastic is pressed against the tube wall.
[0301] According to another procedure, the extruded material exiting the nozzle is directed to a tube that has a perforated section in the center. A slight vacuum is drawn through the perforation to keep the pipe against the walls of the sizing chamber.
[0302] After sizing, the pipe is cooled, usually in a water bath that is approximately 5 meters or more in length.
[0303] Manufacture of accessories of the invention:
[0304] The accessories of the present invention can be manufactured from the multimodal polypropylene composition, according to the present invention, using the methods and equipment known in the art. Thus, according to a preferred method, the multimodal polypropylene composition is molded, preferably, injection molded or blow molded, more preferably, injection molded, in a conventional manner using conventional molding equipment, in the form of an accessory for a pipe.
[0305] Determination Procedures
[0306] a) Fluency index
[0307] The flow rate (MFR) is determined according to ISO 1133 and is indicated in g / 10 min. The MFR is an indication of the fluidity and, therefore, of the processing capacity of the polymer. The higher the flow rate, the lower the viscosity of the polymer. The MFR2 of polypropylene is at a temperature of 230 ° C and a load of 2.16 kg.
[0308] In this document, it is assumed that the flow rate MFR2 follows the following mixing rule (equation 1):
[0309]
[0310]
[0311]
[0312]
[0313] Where w is the weight fraction of the component in the mixture, MI is the melt index MFR2 and the subscripts b, 1 and 2 refer to the mixture, component 1 and component 2, respectively.
[0314] b) Density
[0315] The density of the polymer was measured according to ISO 1183-1: 2004, Procedure A, in compression molded samples prepared according to EN ISO 1872-2 (February 2007) and indicated in kg / m3.
[0316] c) Content of comonomer
[0317] The comonomer content was determined by infrared spectroscopy with quantitative Fourier transform (FTIR) after the basic allocation calibrated through quantitative nuclear magnetic resonance (Rm N) spectroscopy of 13C in a manner well known in the art. Thin films are pressed to a thickness of between 100 and 500 micrometers and the spectra are recorded in transmission mode. Specifically, the ethylene content of a polypropylene-co-ethylene copolymer is determined using the area of the corrected peak at the baseline of the quantitative bands found at 720-722 and 730-733 cm -1. Specifically, the butene or hexene content of a polypropylene copolymer is determined using the area of the corrected peak at the baseline of the quantitative bands found at 1377-1379 cm -1. Quantitative results are obtained based on the reference to the thickness of the film.
[0318] In this document, it is assumed that the comonomer content follows the mixing rule (equation 2):
[0319]
[0320]
[0321]
[0322] Where C is the comonomer content in% by weight, w is the weight fraction of the component in the mixture and the subscripts b, 1 and 2 refer to the overall mixture, component 1 and component 2, respectively.
[0323] As is well known to the person skilled in the art, the comonomer content on a weight basis in a binary copolymer can be converted into the comonomer content on a molar base by using the following equation
[0324]
[0325]
[0326]
[0327]
[0328] where cm is the molar fraction of comonomer units in the copolymer, cw is the weight fraction of comonomer units in the copolymer, MWc is the molecular weight of the comonomer (such as ethylene) and MWm is the molecular weight of the monomer main (i.e. propylene).
[0329] d) Cold xylene soluble fraction
[0330] The content of the cold xylene soluble fraction (XCS,% by weight) was determined at 25 ° C according to ISO 16152; first edition; July 1, 2005.
[0331] Here, it is assumed that the content of xylene soluble polymer follows the mixing rule (equation 4):
[0332]
[0333]
[0334]
[0335]
[0336] Where XS is the content of polymer soluble in xylene in% by weight, w is the fraction by weight of the component in the mixture and subscripts b, 1 and 2 refer to the overall mixture, component 1 and component 2 respectively.
[0337] e) Flexural modulus
[0338] The flexural modulus was determined according to ISO 178. Test samples were prepared having a dimension of 80 x 10 x 4.0 mm3 (length x width x thickness) by injection molding according to EN ISO 1873-2. The length of the section between the supports was 64 mm, the test speed was 2 mm / min and the force was 100 N.
[0339] f) Tensile stress at the creep point, deformation at the creep point
[0340] The tensile stress at the creep point and the strain at the creep point were determined according to ISO 527-1: 1996 and ISO 527-2: 1996 on a test sample of a molded sample of type 1A according to the standard ISO 527-2: 1996, performing injection molding according to ISO 1873-2: 2007.
[0341] g) Charpy type impact resistance with notch
[0342] The impact resistance of Charpy type with notch (Charpy NIS) was determined according to ISO 179-1: 2000 on samples with notches of 80 x 10 x 4 mm, cut from test samples according to ISO 527-2 : 1996 Type 1A. Samples with notches were used for impact according to ISO 179-1 / 1eA: 2000. The test temperature is 23 ± 2 ° C for Charpy NIS at 23 ° C and 0 ± 2 ° C for Charpy NIS at 0 ° C. Injection molding was carried out according to ISO 1873-2: 2007.
[0343] h) Crystallization temperature, melting temperature
[0344] The crystallization temperature Tc and the melting temperature Tm were measured with a differential scanning calorimetry device (DSC) Mettler TA820 on samples of 3 ± 0.5 mg according to ISO 11357-3: 1999. A crystallization temperature was obtained during cooling and heating sweeps of 10 ° C / min between 30 ° C and 225 ° C.
[0345] Crystallization temperatures were taken as the peaks of the exotherms of said peaks.
[0346] Melting temperatures were taken as the peaks of the endotherms.
[0347] i) Distribution of molecular weights MWD, Mw, Mn and Mz
[0348] The average molecular weight in weight Mw and the molecular weight distribution (MWD = Mw / Mn, in which Mn is the average molecular weight in number and Mw is the average molecular weight in weight) are measured by a standards-based procedure ISO 16014-1: 2003 and ISO 16014-4: 2003. A Waters Alliance GPCV 2000 instrument was used, equipped with a refractive index detector and an in-line viscometer, with 3 columns of TSK-gel (GMHXL-hT) from TosoHaas and 1,2,4-trichlorobenzene (TCB, stabilized with 2,6-di-tert-butyl-4-methylphenol 200 mg / ml) as a solvent at 145 ° C and with a constant flow rate of 1 ml / min. 216.5 p.l of sample solution was injected by analysis. The column set was calibrated using a relative calibration with 19 narrow MWD polystyrene (PS) standards in the range of 0.5 kg / mol to 11,500 kg / mol and a set of well-characterized wide polypropylene patterns. All samples were prepared by dissolving 5 to 10 mg of polymer in 10 ml (at 160 ° C) of stabilized TCB (same as the mobile phase) and maintaining continuous stirring for 3 hours before sampling in the CPG instrument .
[0349] In the case of PP the constants are: K: 19 x 10-3 ml / g and a: 0.725 for PP.
[0350] j) Rheological parameters, polydispersity index
[0351] Polymer melt characterization by dynamic shear measurements complies with ISO 6721-1 and 6721-10 standards. The measurements were made on a rotational rheometer controlled by the Anton Paar MCR501 tension, equipped with a 25 mm parallel plate geometry. The measurements were carried out on compression molded plates, using a nitrogen atmosphere and establishing a tension in the linear viscoelastic regime. The oscillatory shear tests were performed at 190 ° C applying a range of frequencies between 0.01 and 600 rad / s and establishing a space of 1.3 mm.
[0352]
[0353] In a dynamic shear experiment, the probe is subjected to a homogeneous deformation to a shear deformation or shear stress that varies sinusoidally (mode controlled by deformation and tension, respectively). In a controlled strain experiment, the probe undergoes a sinusoidal strain that can be expressed by
[0354]
[0355] y (t) = Vo sin (o) t) (6)
[0356] If the applied strain is within the linear viscoelastic regime, the response of the resulting sinusoidal stress can be indicated by
[0357]
[0358] cr (t) = (Jq sen (<Dt 5) (7)
[0359] in which 00 and 70 are the amplitudes of tension and deformation, respectively; m is the angular frequency; 8 is the phase change (lost angle between the applied strain and the stress response); t is the time.
[0360]
[0361] The results of dynamic tests are usually expressed by various different rheological functions, in particular, the shear storage module G ', the shear loss module, G ", the complex shear module, G *, the complex shear viscosity, n *, dynamic shear viscosity, n ', the out-of-phase component of complex shear viscosity n "and the tangent of losses, so n, which can be expressed as follows :
[0362]
[0363] G = - I sew [Pa] ( 8 )
[0364]
[0365]
[0366]
[0367] G * = G 'iG " [Pa] ( 10 )
[0368]
[0369] n * = n - ín "[Pa.s] (11)
[0370]
[0371]
[0372]
[0373] n = i [Pa.s] (13)
[0374] The values of the storage module (G '), loss module (G "), complex module (G *) and complex viscosity (n *) were obtained as a function of frequency (m). Thus, for example, n * 300 rad / s (eta * 300 rad / s) is used as an abbreviation for complex viscosity at the frequency of 300 rad / syn * 0.05 rad / s (eta * 0.05 rad / s) is used as abbreviation for complex viscosity at the frequency of 0.05 rad / s.
[0375]
[0376] The tangent of losses tan (delta) is defined as the ratio between the loss module (G ") and the storage module (G ') at a given frequency. Thus, for example, tanü ^ is used as an abbreviation for the ratio between the loss module (G ") and the storage module (G ') at 0.05 rad / s and tan300 is used as an abbreviation for the ratio between the loss module (G") and the storage module ( G ') at 300 rad / s.
[0377]
[0378] The equilibrium of elasticity tan0.05 / tan300 is defined as the ratio between the tangent of losses tanQ ^ and the loss tangent tan300.
[0379] The polydispersity index, PI, is defined by equation 14.
[0380]
[0381] PI = c 'ico rí'"cop" upa ra (G ' = G ") (14)
[0382] where ®oop is the angular crossover frequency, determined as the angular frequency for which the storage module, G ’, is equal to the loss module, G".
[0383] The values are determined by a single point interpolation procedure, as defined by the Rheoplus software. In situations where a given G * value is not reached experimentally, the value is determined by extrapolation using the same procedure as before. In both cases (interpolation or extrapolation), the options for Rheoplus Interpólate y-values to xvalues from parameter ’and the“ logarithmic interpolation type ’’ were applied.
[0384] References:
[0385] [1] "Rheological characterization of polyethylene fractions", Heino, E.L., Lehtinen, A., Tanner J., Seppala, J., Neste Oy, Porvoo, Finland, Theor. Appl. Rheol., Proc. Int. Congr. Rheol, 11a (1992), 1, 360-362
[0386] [2] “The influence of molecular structure on some rheological properties of polyethylene”, Heino, EL, Borealis Polymers Oy, Porvoo, Finland, Annual Transactions of the Nordic Rheology Society, 1995.).
[0387] [3] Definition of terms relating to the non-ultimate mechanical properties of polymers (Pure & Appl. Chem., Volume 70, No. 3, p.
[0388] 701-754, 1998.
[0389] k) Pipeline pressure test
[0390] The pressure test performance was measured according to ISO 1167. In this test, a sample is exposed to a constant circumferential tension (ring) of 16 MPa at an elevated temperature of 20 ° C in water-in-water or 4 , 9 MPa at a temperature of 95 ° C in water-in-water. The time in hours until the break is recorded. The tests were carried out on pipes manufactured in conventional pipe extrusion equipment, the pipes having a diameter of 32 mm and a wall thickness of 3 mm.
[0391] l) Impact test for weight loss at 0 °
[0392] The measurement was made according to EN744-1995, in which a drop height, a temperature, a type of striking element and specific weights were used.
[0393] Conditioning temperature: 0 ° C; conditioning period: 60 min; conditioning: in the air; hitting element: d25; weight: 0.25 kg; drop height: 100 cm.
[0394] The type of break was recorded.
[0395] m) Measurement of the Oharpy type impact at 0 ° O of samples prepared from test pipes according to ISO9854-1 and 2: 1994 standards
[0396] The test sample is prepared from the pipe. The dimensions of the test sample are 120 x 15 mm. The criterion in the application standard is of a breaking rate of less than 10% according to ISO15874-2.
[0397] Examples
[0398] a) Catalyst preparation
[0399] First, 0.1 mol of MgCl2 x 3 EtOH was suspended under inert conditions in 250 ml of decane in an atmospheric pressure reactor. The solution was cooled to a temperature of -15 ° C and 300 ml of cold TiCU was added, while maintaining the temperature at that level. Then, the temperature of the suspension was slowly increased to 20 ° C. At this temperature, 0.02 mol of diethylhexylphthalate (DOP) was added to the suspension. After the addition of the phthalate, the temperature was increased to 135 ° C for 90 minutes and the suspension was allowed to stand for 60 minutes. Then, another 300 ml of TiCl4 was added and the temperature was maintained at 135 ° C for 120 minutes. After this, the catalyst of the liquid was filtered and washed six times with 300 ml of heptane at 802C. Then, the solid catalyst component was filtered and dried. The concept of the catalyst and its preparation are disclosed, for example, in general, in patent publications EP 491566, EP 591224 and EP 586390.
[0400] For the preparation of the examples of the invention IE1 to IE6, as well as the comparative example CE1, triethyl aluminum (TEAL), dicyclopentyldimethoxysilane (DCPDMS) were added as a donor (Do), catalyst, as produced above, and vinylcyclohexane ( VCH), in oil, such as mineral oil, for example, Technol 68 (kinematic viscosity at 40 ° C of 62-74 cSt), in amounts such that the Al / Ti ratio was 3-4 mol / mol, Al / C was also 3-4 mol / mol and the weight ratio of VCH / solid catalyst was 1: 1. The mixture was heated to 60-65 ° C and allowed to react until the content of the unreacted vinylcyclohexane in the reaction mixture was less than 1,000 ppm. The catalyst concentration in the final oil and catalyst suspension was 10 to 20% by weight.
[0401] b) Polymerization of the examples of the invention IE1-6 and comparative example CE1
[0402] For the polymerization of the examples of the invention IE1-6 and the comparative example CE1, the catalyst, which included polymerized VCH, was introduced together with propylene into a prepolymerization reactor. Triethyl aluminum was used as cocatalyst and dicyclopentyldimethoxysilane as a donor. The polymerization and feed conditions are indicated in table 1.
[0403] The suspension of the prepolymerization stage was introduced directly into a loop reactor. Propylene, hydrogen and ethylene were additionally added to the loop reactor. The polymerization and feed conditions are indicated in table 1.
[0404] The loop reactor suspension was introduced into a gas phase reactor through a direct feed line, that is, without instantaneous vaporization of monomers between the reactors.
[0405] Propylene, ethylene and hydrogen were introduced into the first gas phase reactor and subsequently transferred to a second gas phase reactor.
[0406] The polymerization and feed conditions are indicated in table 1.
[0407] The final content of poly-VCH in the final polymers obtained from the examples of the invention IE1-6 and the comparative example CE1 was 200 ppm or less.
[0408] The preparation of comparative example CE1 was carried out, however, in the same manner, but without the third stage of polymerization and the procedure was performed as shown in Table 1.
[0409] a) Final combination
[0410] The polypropylene resins of the examples of the invention IE1-IE6 and the reference example CE1 emerging from the gas phase reactor (identified as reactor powder in Table 1) were combined together with conventional antioxidants and Ca stearate (used the same amounts for the examples of the invention and the reference example) and were granulated in a W&P ZSK 70 double screw extruder (Coperion) at a melting temperature of 240 ° C and an extrusion yield of 200 kg / h.
[0411] The polymer granules of the examples of the invention and the comparative example were prepared to test the samples for mechanical and thermal tests, as indicated below, or extruded into pipes for the purpose of testing the processability of the compositions.
[0412] Table 1: Polymerization conditions of Examples CE1-2 and IE1-6
[0413]
[0414] ^¡¡
[0415] ^;
[0416]
[0417]
[0418]
[0419] * The values are calculated
[0420] ** measured from the final composition (U) (= final multimodal polypropylene composition) after the combination step (a), as described above
[0421] b) Pipe tests:
[0422] Preparation of the pipes for the tests: The polymers of the examples of the invention were extruded into pipes by using a Reifenhauser 381-1-70-30 pipe extruder. The extruder outlet material was 46 to 48 kg / h, the melting pressure was 180 to 220 barg and the melting temperature was 180 to 230 ° C. Test pipes with varying dimensions were used in the following A-C pipe tests. The dimensions of the pipes are indicated below under each test A to C.
[0423] The contraction of the manufactured test pipes was clearly less than 5%.
[0424] A. Pressure test:
[0425] Test pipes with a diameter of 32 mm and a wall thickness of 3 mm were prepared for the polymers of the examples of the present invention IE1, IE2 and IE5.
[0426] The pressure test performance was measured according to ISO 1167. In this test, a sample is exposed to a constant circumferential tension (ring) of 16 MPa at an elevated temperature of 20 ° C in water-in-water or 4 , 9 MPa at a temperature of 95 ° C in water-in-water. The time in hours until the break is recorded. The tests were carried out on pipes manufactured in conventional pipe extrusion equipment, the pipes having a diameter of 32 mm and a wall thickness of 3 mm. Results are shown in table 2.
[0427] Table 2:
[0428] Example IE1 IE2 IE5
[0429] Pressure resistance at 20 ° C and 16 MPa [h] 20 7 9
[0430] B. Impact test for weight loss at 0 ° C
[0431] Test pipes with a diameter of 25 mm and a wall thickness of 4.2 mm were prepared for the example of the invention IE6. The number of IE6 pipe samples was 10 (for the repetition of the test). The measurement was performed according to EN744-1995, as previously indicated in the section on Determination procedures. Conditioning temperature: 0 ° C; conditioning period: 60 min; conditioning: in the air; hitting element: d25; weight: 0.25 kg; drop height: 100 cm.
[0432] The type of break was recorded. The result for IE6: no breakage.
[0433] C. Impact measurement of Charpy type at 02C of samples prepared from test pipes according to ISO9854-1 and 2: 1994 standards
[0434] Test pipes with a diameter of 32 mm and a wall thickness of 4.4 mm were prepared for the polymers of the examples of the invention IE1, IE2, IE5 and IE6.
[0435] The test pieces were prepared from the pipe. The dimensions of the test piece were 120 x 15 mm. The criterion in the application standard is of a breaking rate of less than 10% according to ISO15874-2. The results are indicated in the following table 3:
[0436] Table 3: Charpy type impact at 0 ° C, without notch, 70 mm space between supports, 15 joule hammer
[0437]
[0438]

权利要求:
Claims (16)
[1]
1. Composition of multimodal polypropylene suitable for pipe applications, comprising
a multimodal propylene copolymer (U), at least, with a comonomer selected from alpha-olefins with 2 or 4 to 8 carbon atoms in a total amount of 4.0 to 10.0 mol%,
in which the multimodal polypropylene composition has a flow rate of MFR2 (2.16 kg, 230 ° C) of 0.05 to 1.00 g / 10 min, determined according to ISO 1133,
a fraction content of cold soluble in xylene (XCS) from 4.0 to 17.0% by weight, determined at 25 ° C according to ISO 16152, and
a polydispersity index PI from 2.5 to 4.0 Pa-1, determined by rheological measurements according to ISO 6721-1 and ISO 6721-10.
[2]
2. Multimodal polypropylene composition according to claim 1, wherein the multimodal propylene copolymer (U) comprises
(A) 75 to 98% by weight of a random propylene copolymer composition (X), wherein the propylene comonomer is selected, at a minimum, from one of the group consisting of ethylene and C4-C8 alpha-olefins , Y
whereby, the propylene random copolymer composition (X) has an MFR2 flow rate of 0.05 to 1.0 g / 10 min, or a comonomer unit content of 2.0 to 12.0 mol% , or both; Y
(B) 2 to 25% by weight of a propylene copolymer (Y), in which the comonomer is selected, at least, from one of the group consisting of ethylene and C4-C8 alpha-olefins and,
whereby, the propylene copolymer (Y) has an MFR2 flow rate of 0.0001 to 0.1 g / 10 min, or a comonomer unit content of 9.0 to 40.0 mol%, or both .
[3]
3. Multimodal polymer composition according to claim 1 or 2, wherein the propylene random copolymer composition (X) comprises
30 to 60% by weight of a first propylene (V) random homopolymer or copolymer having an MFR2 of 0.3 to 5.0 g / 10 min; Y
40 to 70% by weight of a second homopolymer or random copolymer of propylene (W), having an MFR2 of 0.04 to 0.60 g / 10 min;
provided that at least one of said first propylene (V) random homopolymer or copolymer and said second propylene (W) random homopolymer or copolymer is a random propylene copolymer, preferably at least said second homopolymer or copolymer Random propylene (W) is a random copolymer of propylene.
[4]
4. Multimodal polymer composition according to any one of the preceding claims, wherein the propylene random copolymer composition (X) comprises
30 to 60% by weight of the first random propylene copolymer (V) having an MFR2 of 0.3 to 5.0 g / 10 min, or a comonomer unit content of 1.0 to 6.0 molar% , or both; Y
40 to 70% by weight of the second random propylene copolymer (W), which has an MFR2 of 0.04 to 0.60 g / 10 min, or a comonomer unit content of 3.0 to 12.0% molar, or both.
[5]
5. Multimodal polypropylene composition according to any one of the preceding claims 3 or 4, wherein the MFR2 of the first random homopolymer or copolymer of propylene (V) is greater than the MFR2 of the second homopolymer or random copolymer of propylene (W) and the MFR2 of the second propylene random homopolymer or copolymer (W) is greater than the MFR2 of the propylene copolymer (Y); optionally, and preferably, the comonomer content of the first random propylene copolymer (V) is less than the comonomer content of the second random propylene copolymer (W) and the comonomer content of the second random propylene copolymer (W) is lower than the comonomer content of the propylene copolymer (Y).
[6]
6. Multimodal polypropylene composition according to any one of the preceding claims, comprising from 0.1 to 10,000 ppm by weight of a nucleating agent (Z).
[7]
7. A multimodal propylene copolymer composition according to any one of the preceding claims, wherein the nucleating agent (Z) is a polymeric nucleating agent, preferably, at least one polymer of a vinyl compound, according to the following formula
CH2 = CH-CH1R2 (1)
wherein R1 and R2 together form a saturated, unsaturated or aromatic, 5 or 6-membered ring, or independently represent an alkyl group comprising 1 to 4 carbon atoms, preferably, together form a ring saturated, unsaturated or aromatic, 5 or 6 members, which optionally contains substituents, or are selected, independently, from C1 to C4 alkyl groups, whereby, in case R1 and R2 form an aromatic ring, the atom of hydrogen of the group -CHR1R2 is not present, and in which the amount of the nucleating agent (Z) is from 0.1 to 500 ppm based on the total weight of the multimodal polypropylene composition (100% by weight), preferably, based on the combined weight of the multimodal propylene copolymer (U) and the nucleating agent (Z).
[8]
8. A multimodal polypropylene composition according to claim 7, wherein the vinyl compound of formula (1) is selected from the group of vinylcyclohexane and / or 3-methyl-1 -butene, preferably, the vinyl compound is vinylcyclohexane and the nucleating agent is a vinylcyclohexane polymer ( ^v C ^h ).
[9]
9. The multimodal polypropylene composition according to any of the preceding claims, wherein the ratio: crystallization temperature Tc x comonomer content of the multimodal propylene copolymer (U) [° C% molar] is at least 400 ° C% molar.
[10]
10. Multimodal polypropylene composition according to any of the preceding claims, which has an impact resistance of the Charpy type with a notch at 0 ° C of at least 4.0 kJ / m2, preferably at least 5 , 0 kJ / m2, more preferably, at least, 6.0 kJ / m2, even more preferably, 7.0 kJ / m2 and, most preferably, 8.0 to 40 kJ / m2, determined according to ISO 179 / 1eA: 2000 using injection molded samples.
[11]
11. Multimodal polypropylene composition according to any of the preceding claims, which has a flexural modulus of at least 700 MPa, preferably at least 750 MPa, preferably at least 800 MPa, more preferably, at least 830 MPa, determined according to ISO 178 at a test speed of 2 mm / min and a force of 100 N in test samples having a dimension of 80 x 10 x 4.0 mm3 (length x width x thickness) prepared by injection molding according to EN ISO 1873-2.
[12]
12. Multimodal polypropylene composition according to any one of the preceding claims, wherein the multimodal propylene copolymer (U) is a multimodal propylene copolymer with ethylene comonomer.
[13]
13. Process for producing a multimodal polypropylene composition according to any one of the preceding claims 1 to 12, wherein propylene and at least one comonomer selected from alpha-olefins with 2 or 4 to 8 carbon atoms are present in the presence from
(I) a solid catalyst component comprising a magnesium halide, a titanium halide and an internal electron donor; Y
(II) a cocatalyst comprising an aluminum alkyl and, optionally, an external electron donor; and (III) an optional nucleating agent (Z), preferably, in the presence of a nucleating agent (Z) as defined in any of claims 7 or 8;
the multistage process comprising the stages of
(A) continuously polymerize propylene, optionally, a comonomer selected from the ethylene group and, at least, a C4-C8 alpha-olefin, in a first polymerization stage by introducing streams of propylene, hydrogen and, optionally, said comonomer, in the first polymerization stage at a temperature of 60 to 100 ° C and a pressure of 40 to 65 bar to produce a first propylene polymer (V), in which the first propylene polymer (V) has a MFR2 flow rate (2.16 kg, 230 ° C; ISO 1133) from 0.3 to 5.0 g / 10 min;
(B) extracting from the first stage of polymerization a stream comprising the first propylene polymer (V) and transferring said stream to a second stage of polymerization;
(C) polymerize propylene in the presence of said first propylene polymer (V) in the second polymerization stage at a temperature of 65 to 90 ° C and a pressure of 19 to 25 bar by introducing streams of propylene, hydrogen and, optionally, at least one comonomer, to produce a copolymer composition (X) of said first propylene polymer (V) and a second propylene polymer (W); provided that at least one of said first and second polymers (V) and (W) is a random copolymer of propylene, preferably, at least, the second polymer (W) is a random copolymer of propylene, more preferably, both the first and the second propylene polymer (V) and (W) are random copolymers of propylene;
said copolymer composition (X) comprising
from 30 to 60% by weight of said first propylene polymer (V) and from 40 to 70% by weight of said second propylene polymer (W) with respect to the copolymer composition (X),
wherein the copolymer composition (X) has an MFR2 flow rate of 0.05 to 1.0 g / 10 min which is lower than the MFR2 of said first polymer (V);
(D) extracting a stream comprising the copolymer composition (X) of the second polymerization stage and transferring said stream to a third polymerization stage;
(E) polymerize propylene and at least one comonomer in the presence of the copolymer composition (X) in the third polymerization stage at a temperature of 65 to 90 ° C and a pressure of 10 to 100 bar by introducing streams of propylene, hydrogen and at least one comonomer, to produce the multimodal propylene copolymer (U) comprising the copolymer composition (X) and a component additional propylene copolymer (Y), wherein the multimodal propylene copolymer (U) has a flow rate of MFR2 of 0.05 to 1.00 g / 10 min;
wherein the multimodal propylene copolymer (U) comprises 75 to 98% by weight, preferably 85 to 95% by weight of said copolymer composition (X) and 2 to 25% by weight, so preferably, 5 to 15% by weight of said propylene copolymer (Y); Y
wherein the comonomer content of the propylene copolymer (Y) is 9.0 to 40 mol%;
(F) continuously extracting a stream comprising the multimodal propylene copolymer (U) from the third polymerization stage and, optionally, mixing the multimodal propylene copolymer (U) with additives; Y
(G) Extrude the multimodal propylene copolymer (U) into granules.
[14]
14. Multi-stage method according to claim 13, wherein the multi-stage method comprises an additional stage (AA) that precedes stage (A), wherein
(AA) polymerizing a vinyl compound of the formula (1), as defined in claims 7 or 8, preferably, vinylcyclohexane (VCH), in the presence of a catalyst system comprising the solid catalyst component ( I) to obtain a modified catalyst system which is the reaction mixture comprising the solid catalyst component (I) and the polymer produced from the vinyl compound of formula (1), preferably, and in which, the proportion in Weight (g) of the polymer of the vinyl compound of the formula (1) with respect to the solid catalyst component (I) is up to 5 (5: 1), preferably up to 3 (3: 1), of most preferably, it is from 0.5 (1: 2) to 2 (2: 1), and the modified catalyst system obtained is introduced in the polymerization stage (A) of the multistage process for the production of the copolymer of multimodal propylene (U).
[15]
15. Multimodal polypropylene composition according to any one of claims 1 to 12, obtainable by the multistage process, according to preceding claims 13 or 14.
[16]
16. Item, preferably, a pipe, preferably, a pressure pipe, more preferably, a pressure pipe for hot and cold water, or an accessory for a pipe, comprising the polypropylene composition, according to any of claims 1 to 12 or 15.

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法律状态:

优先权:

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申请号 | 申请日 | 专利标题

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EP13002102.5A|EP2796501B9|2013-04-22|2013-04-22|Multimodal polypropylene composition for pipe applications|

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