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    • 专利摘要:
    polypropylene composition, process of producing a polypropylene composition, coated article, process for coating an article and use of a polypropylene composition polypropylene composition comprising a polypropylene base resin, the polypropylene base resin having an mfr (2 , 6 kg, 230cº iso 1133) from 8 to 24 g / 10 min and a laos-nlf factor> 2.8, where laos - nlf = where g1 first order fourier coefficient g3 second order fourier coefficient .
    公开号:BR112012028741B1
    申请号:R112012028741-9
    申请日:2011-01-21
    公开日:2020-02-18
    发明作者:Katja Klimke；Juha Yli-Peltola；Elke Pachner；Doris Machl；Hermann Braun；Susana Filipe；Anh Tuan Tran
    申请人:Borealis Ag；
    IPC主号:
    专利说明:

    POLYPROPYLENE COMPOSITION, PROCESS OF PRODUCTION OF A POLYPROPYLENE COMPOSITION, COATED ARTICLE, PROCESS TO COVER AN ARTICLE AND USE OF A POLYPROPYLENE COMPOSITION [0001] The present invention relates to a polypropylene composition suitable for extrusion coating, a process for the provision of such polypropylene compositions and articles coated by extrusion, and a process for producing them.
    [0002] In general, extrusion coating of substrates, as well as paper, cardboard, fabrics and metal sheets with a thin layer of plastic, is practiced on a large scale. The coating composition is extruded in a first step, whereby the flow of molten polymeric material passes through a flat matrix to obtain a film with a thickness of a few microns. In the second stage, that is, the coating stage, the film is placed on a support and passed over a cooling cylinder. As a result of cooling, the polymer adheres to its support.
    [0003] Low density polyethylene (LDPE) is often used in coating because of the ease of processing although LDPE's rigidity, barrier properties and temperature resistance are not satisfactory. Polypropylene is attractive due to advantages such as heat tolerance and transparency. However, polypropylene suffers from poor processability, as well as the formation of a long neck and a low maximum coating speed. The limiting processing properties of polypropylene can be partially minimized by high-strength polypropylene from the melt, being characterized by branches in the chain
    Petition 870190119240, of 11/18/2019, p. 7/59
    2/42 main of linear polymer. This can be achieved by means of post reactor treatment, by copolymerization with dienes, or by polymerization with specific catalysts.
    [0004] High speed extrusion coating requires relatively high flow rates of MFR2, 15 g / 10min or greater. Such fluidity rates can usually be obtained only by viscorreduction, that is, treatment with peroxide in the absence of dienes. However, the main reaction, that is, branching reaction, caused by treatment with peroxide leading to a higher degree of branching, unfortunately is always accompanied by beta fission as a secondary reaction, that is, significant degradation of polypropylene. Such degradation is responsible for the formation of gels, which limits the use of polypropylene compositions in high demand applications, as well as in the medical field.
    [0005] WO 2009/133016 presents two-component adhesion compositions suitable for extrusion coating, comprising a mixture of high strength polypropylene from the melt and a component selected from the group of (i) polypropylene modified with maleic anhydride (MAPP), ( ii) polypropylene wax modified with maleic anhydride, (iii) polypropylene homopolymer with high flow rate or (iv) adhesive based on hot melted ethylene-vinyl acetate.
    This composition allows extrusion coating only at limited line speeds.
    [0006] KR 681871 B1 is intended for mixtures of copolymers of polypropylene and low density polyethylene for extrusion coating. However, the characteristics of
    Petition 870190119240, of 11/18/2019, p. 8/59
    3/42 desired flow rates are achieved by adding low density polyethylene, leading to limited thermal stability. [0007] WO 2008/100720 presents a mixture of polypropylene and low density polyethylene for extrusion coating. [0008] EP 1 847 555 presents a polypropylene with low g 'branching index, showing a pronounced deformation hardening at high deformation rates, that is, the faster the material is stretched, the higher the deformation hardening index ( SHI) and, consequently, the material is more stable. The material originates from the branching of the long chains inside the reactor.
    [0009] Polypropylene with deformation-hardening behavior is, for example, described in EP 1 903 070, describing a polypropylene having a high melt strength due to a large number of side chains (branched polypropylene), also leading to relatively stiffness high. The use of a specific polypropylene is described only for the matrix referring to heterophasic polypropylenes.
    [0010] EP 1 847 555 refers to multi-branched polypropylene homo and copolymers. The material exhibits extension fluidity properties, leading to high stability in extrusion processes. The use of specific polypropylene is described only for the matrix in a heterophasic polypropylene. [0011] Polypropylenes comprising a base resin consisting of two different types of polypropylene homo or copolymers and a linear low density ethylene homo or copolymer are presented in EP 2 133 389, having good heat resistance and can be processed with flow magnified.
    Petition 870190119240, of 11/18/2019, p. 9/59
    4/42 [0012] EP 1 892 264 is directed to articles comprising a substrate that is coated by extrusion with compositions based on polypropylene, being multi-branched.
    [0013] There is still a need for alternative or improved polymeric compositions suitable for extrusion coating for a wide variety of substrates having excellent processability, low gel content, and being able to withstand high temperatures. There is a particular need for polymeric propylene compositions suitable for extrusion coating without the need for the addition of processing aids, such as LDPE or the use of heterophasic materials.
    [0014] The present invention is based on the discovery that the above objective can be achieved by a polypropylene having long chain branching of a homogeneous and high-grade nature, reflected by a high viscoelastic LAOS (LAOS - NLF) factor, defined as
    LAOS - NLF = where G'1- first order Fourier coefficient
    G'3- Third order Fourier coefficient [0015] The present polypropylene invention comprising a base resin that has an MFR provides a polypropylene base resin composition, (2.16 kg, 230 ° C, ISO 1133) of
    8.0 to 2 4 g / 10min and a LAOS - NFL> 2.8, defined as
    LAOS - NLF =
    G'i
    G 3 where G'1- first order Fourier coefficient
    G'3- third order Fourier coefficient
    Petition 870190119240, of 11/18/2019, p. 10/59
    5/42 [0016] The term “polypropylene composition” used here denotes compositions consisting of 96% by weight of polypropylene-based resin, and stabilizers in an amount of up to 4% by weight relative to the total polypropylene composition.
    [0017] The term "polypropylene based resin" as used here denotes both polypropylene homopolymers and random polypropylene copolymers. A “polypropylene-based resin” is a single-phase resin.
    [0018] A single-phase resin denotes a resin having only one Tg when subjected to DSC.
    [0019] Catalyst denotes the organometallic compound containing the reaction center of polymerization.
    [0020] Catalyst system denotes the mixture of the catalyst, the optional cocatalyst and the optional support.
    [0021] Viscorreduction denotes the subjection of a polymeric resin to treatment with peroxide in the absence of a bifunctional unsaturated molecule, as well as a diene.
    [0022] "A polypropylene derived from an asymmetric catalyst" denotes a polypropylene produced in the presence of an asymmetric catalyst.
    [0023] The polypropylene-based resin according to the present invention is either a polypropylene homopolymer or a random polypropylene copolymer.
    [0024] It is preferable that the polypropylene-based resin be a homopolymer.
    [0025] When the polypropylene based resin is a random copolymer of polypropylene, the comonomer content is preferably less than 15 mol%, more preferably less than 10 mol%, and preferably less than 4 mol%. The)
    Petition 870190119240, of 11/18/2019, p. 11/59
    6/42 comonomer (s) is / are preferably selected from the group of ethylene and alpha olefins, more preferably ethylene and alpha olefins C4 to C12, more preferably ethylene or butene.
    [0026] The polypropylene composition according to the present invention preferably comprises the polypropylene-based resin having an MFR (2.16 kg, 230 ° C, ISO 1133) of 8.0 to
    4 g / 10min and a LAOS - NFL> 2.5, defined as
    LAOS - NLF =
    G'1
    G'3 where G - first order Fourier coefficient
    G'3- Fourier coefficient of third order in an amount of 96% by weight, more preferably 97% by weight, and preferably 98% by weight in relation to the total polypropylene composition.
    [0027] The polypropylene composition according to the present invention preferably consists of polypropylene-based resin having an MFR (2.16 kg, 230 ° C, ISO 1133) of 8.0 to
    4 g / 10min and a LAOS - NFL> 2.8, defined as
    LAOS - NLF =
    G'1
    G'3 where G 1 - first order Fourier coefficient
    G'3- Third order Fourier coefficient and modifiers and / or additives in an amount of up to 4% by weight, more preferably up to 3% by weight, and preferably up to 2% by weight in relation to the total polypropylene composition.
    [0028] Most preferably, the modifiers are selected from poly-1-butene, poly-4-methyl-1-pentene, as well as mineral fillers such as talc or calcium carbonate. Suitable additives include stabilizers, lubricants,
    Petition 870190119240, of 11/18/2019, p. 12/59
    7/42 nucleating agents, pigments and foaming agents. These modifiers and / or additives can be included during the polymerization process or after polymerization by mixing the melt. However, it is preferable that the modifiers do not decrease the melting temperature of the composition. It is particularly preferable that the polypropylene composition according to the present invention does not contain LDPE, recognizable by the absence of any melting points below 135 ° C in the DSC.
    [0029] A very sensitive and at the same time very simple characterization method often used in the scientific literature is oscillatory shear in large amplitudes (LAOS). In this method, a single excitation frequency is applied and the torque response is analyzed. The non-linear response generates higher harmonic mechanical frequencies at (3,5,7, ...). Fourier Transform analysis allows the recovery of intensities and phases. As the intensity of the higher harmonics decreases rapidly, which can lead to very low values of 5 and higher harmonic why
    LAOS - NLF =
    G'3 where G'1- first order Fourier coefficient
    G'3 - third order Fourier coefficient provides the most reliable characterization of the polymer structure.
    [0030] Another option of characterizing the structure of the polymer being primarily responsible for the benefits of the present invention, particularly the nature of long chain branching, is the strain hardening factor, being defined as
    Petition 870190119240, of 11/18/2019, p. 13/59
    8/42 SHF = 7+ (ί , έ =
    VlveC) 3η + ( Α) where rç + ( t, ε) is the uniaxial extensional viscosity; and
    PLVE ( t) is three times the time-dependent shear viscosity tf + (t) in the linear strain range. The determination of linear viscoelasticity in extension is based on IRIS
    Rheo Hub 2008, requiring the calculation of the discrete relaxation time spectrum from the storage and loss data module (G ', G (m))). Details on the method can be found in the experimental section. The strain hardening factor mainly reflects the degree of dispersion (heterogeneity) of the branches in relation to the main polymer chain. Secondly, the strain-hardening factor also provides information on the degree of branching.
    [0031] Another method of characterizing the structure of branched polypropylene is Rheotens measurement. Branched polypropylene shows greater melt strength with increased shear applied to the polymer, as well as during melt extrusion. This property is well known as deformation hardening. In the Rheotens test, the polymer deformation hardening behavior is analyzed by the Rheotens equipment (product of Gottfert, Siemensstr.2, 74711 Buchen, Germany) in which a molten filament is elongated, stretching it to a defined acceleration. The force F dependent on the drawing speed v is recorded. The test procedure is carried out at a temperature of 23 ° C. Further, details are given in the experimental part.
    Petition 870190119240, of 11/18/2019, p. 14/59
    9/42 [0032] The polypropylene composition according to the present invention preferably includes a polypropylene based resin having a LAOS - NFL defined as
    LAOS - NLF =
    G'3 where G'1- first order Fourier coefficient
    G'3- Third order Fourier coefficient greater than 2.8, more preferably greater than 3.0, and preferably greater than 3.5.
    [0033] LAOS - NFL greater than 2.8 indicates a high degree of long chain branching.
    [0034] The polypropylene composition according to the present invention preferably includes a polypropylene-based resin having a strain-hardening factor (SHF) of 2.3 to 7.0, preferably 2.5 to 6.5, more preferably 2.8 to 6.5, and preferably 3.3 to 5.0, when measured at a strain rate of 3.0 s-1 and a Hencky strain of 2.5.
    [0035] Furthermore, the polypropylene composition according to the present invention preferably includes a polypropylene-based resin having a strain-hardening factor (SHF) of 1.7 to 6.0, more preferably 1.75 to 5, 5, and preferably 1.8 to 5.0, when measured at a strain rate of 1.0 s -1 and a Hencky strain of 2.0.
    [0036] It should be understood that the preferred strain-hardening factors, as mentioned above, may be present individually, but may also be present in combination.
    Petition 870190119240, of 11/18/2019, p. 15/59
    The polypropylene composition according to the present invention further preferably includes a polypropylene-based resin having a melt strength of F30 of 4.6 cN or more, more preferably 6.0 cN or more, and of preferably 9.0 cN or more, at 200 ° C, when subjected to melt strength tests in Rheotens, as described in the experimental part. Generally, the resistance of the F30 cast does not reach greater than 20 cN.
    [0038] The polypropylene composition according to the present invention preferably has a melting temperature Tm in the range 135 to 165 ° C, more preferably 140 to 162 ° C, and preferably 150 to 161 ° C. High melting temperatures allow the provision of materials capable of withstanding steam sterilization. Higher melting temperatures can be achieved with polypropylene homopolymers and higher crystallinity.
    [0039] The polypropylene composition according to the present invention preferably includes a polypropylene based resin having a 2-1 regioinversion above 0.1 mol% when measured by means of 13 C-NMR, according to the methodology described by JC Randall in “Polymer sequence determination 13 C NMR method”, Academic Press 1977. The content of regioinversions is calculated based on the relative concentrations of methylene S (alpha, beta) + S (beta, beta) sequences. Further, details are given in the experimental part. Regioinversion can be mainly influenced by modification of the catalyst.
    [0040] The polypropylene composition according to the present invention preferably includes a resin based on
    Petition 870190119240, of 11/18/2019, p. 16/59
    11/42 polypropylene, being characterized by a high resistance of the F30 melt in the Rheotens test, as described above, and at the same time a high flow rate MFR2. The polypropylene-based resin is preferably characterized by a melt strength product F30 x MFR2 (2.16 kg, 230 ° C, ISO 1133) of 130 cNg / 10min or greater, more preferably 140 cNg / 10min or greater, and preferably 145 cNg / 10min or greater. For practical reasons, the melt strength product of F30 x MFR2 will normally be limited to about 200 cNg / 10min.
    [0041] The present invention relates to a process for the production of a polypropylene composition according to the present invention.
    [0042] The process according to the present invention involves the production of an intermediate polypropylene based resin, having an MFR (2.16 kg, 230 ° C) of 1.0 to 6.0 g / 10min, determined according to with ISO 1133, in the presence of an asymmetric catalyst. The intermediate polypropylene base resin is then mixed with peroxide and a diene, at a temperature of 20 to 90 ° C, for at least 2 minutes, to form a premixed material. The pre-mixed material is then subjected to a mixture of the molten material in a melt mixing equipment, at a cylinder temperature in the range of 180 to 300 ° C.
    [0043] It is essential that the whole process does not involve viscoreduction, that is, subject any intermediate product to treatment with peroxide in the absence of a diene, such as butadiene.
    [0044] Suitable dienes are conjugated or unconjugated dienes, linear or branched dienes, containing 4 to 20
    Petition 870190119240, of 11/18/2019, p. 17/59
    12/42 carbon atoms. Preferred dienes include isoprene, 2,3-dimethylbutadiene, 1,3-pentadiene, 1,3-hexadiene, 1,4-octadiene and butadiene. The most preferable diene is butadiene.
    [0045] The polypropylene intermediate resin base is pre-mixed with diene and peroxide in a powder mixing equipment, such as a horizontal mixer with paddle stirrer. The premix is preferably carried out at a temperature of the powdered polymer of 25 to 80 ° C, preferably in a range of 30 to 75 ° C. The residence time of the polymer in the premix stage is preferably 5 to 30 minutes, preferably 8 to 20 minutes.
    [0046] The pre-mixed material is then mixed in the molten state at a cylinder temperature of 180 to 300 ° C, preferably in a molten state mixing equipment, such as a mono-screw extruder, a co-rotating twin screw extruder or a co-kneader.
    [0047] The temperature of the cylinder is preferably between 200 and 280 ° C. More preferably, a specific temperature profile is maintained along the thread of the melt mixing equipment, having an initial temperature T1 in the feed zone, a maximum temperature T2 in the compression zone and a final temperature T3 in the termination zone, all temperatures being defined as cylinder temperatures and fulfilling the following relationship: T1 <T3 <T2. The temperature of cylinder T1 is preferably between 180 and 210 ° C. The temperature of cylinder T2 (in the compression zone) is preferably between 280 and 300 ° C. The temperature of cylinder T3 (in the termination zone) is preferably between 260 and 290 ° C.
    Petition 870190119240, of 11/18/2019, p. 18/59
    13/42 [0048] The thread speed of the melt mixing equipment is preferably adjusted to a range of 150 to 800 revolutions per minute (rpm).
    [0049] Following the melt mixing step, the resulting molten polymer is pelletized either in an underwater pelletizer or, after the solidification of one or more filaments in an immersion tank, in a filament pelletizer.
    [0050] The present invention also relates to a polypropylene composition comprising a polypropylene based resin, with an MFR (2.16 kg, 230 ° C) of 8.0 to 24 g / 10min, obtained by:
    - production of an intermediate polypropylene based resin, with an MFR (2.16 kg, 230 ° C) of 1.0 to 6.0 g / 10min, determined according to ISO 1133 in the presence of an asymmetric catalyst;
    - mixing the intermediate polypropylene base resin with peroxide and a diene, at a temperature of 20 to 90 ° C for at least 2 minutes, to form a pre-mixed material;
    - mixing of the melted premixed material in a melt mixing equipment, at a cylinder temperature in the range of 180 to 300 ° C.
    [0051] The molten material mixing equipment preferably includes a feed zone, a compression zone and a termination zone, with a temperature of the initial cylinder T1 being maintained in the feeding zone, a temperature of the cylinder T2 being maintained at compression zone, and a cylinder temperature of the T3 matrix is maintained in the termination zone. Preferably, cylinder temperatures T1, T2 and T3 satisfy the following relationship: T1 <T3 <T2.
    [0052] Suitable dienes are conjugated or unconjugated dienes, linear or branched dienes, containing 4 to 20
    Petition 870190119240, of 11/18/2019, p. 19/59
    14/42 carbon atoms. Preferred dienes include isoprene, 2,3-dimethylbutadiene, 1,3-pentadiene, 1,3-hexadiene, 1,4-octadiene and butadiene. The most preferable diene is butadiene.
    [0053] The polypropylene composition according to the present invention is obtained preferably by pre-mixing in the presence of 0.3 to 1.0% by weight of peroxide, more preferably in the presence of 0.4 to 0.7% in peroxide mass. Even more preferably, the polypropylene composition according to the present invention is obtained by premixing in the presence of 0.3 to 1.0 mass%, more preferably 0.4 to 0.7 mass% of tert-butylperoxy isopropyl carbonate (CAS No. 2372-21-6), commercially available as Trigonox® BPIC-C75 (Akzo Nobel, NL) - 75% turpentine solution.
    [0054] Even more preferably, the polypropylene composition is obtained by pre-mixing in the presence of a diene in a concentration of 0.3 to 2.0% by mass, and preferably the polypropylene composition is obtained by pre-mixing in the presence of butadiene in a concentration of 0.3 to 2.0% by mass.
    [0055] It should be understood that the addition of diene and peroxide can be performed at once in the pre-mixing stage or can be divided into two additions, a first addition in the pre-mixing stage and a second addition in the pre-mixing stage mixing of the molten material. Complete addition of diene and peroxide in the premix stage is preferable.
    [0056] The intermediate base resin preferably has a 2-1 regioinversion above 0.1 mol%, more preferably above 0.2 mol%, and preferably above 0.3 mol%, when measured by means of 13 C -NMR, according to the methodology described by JC Randall in “Polymer sequence determination 13 C NMR
    Petition 870190119240, of 11/18/2019, p. 20/59
    15/42 method ”, Academic Press 1977. The content of regioinversions is calculated based on the relative concentrations of methylene sequences S (alpha, beta) + S (beta, beta). Further, details are given in the experimental part. Regioinversion can be mainly influenced by modification of the catalyst.
    [0057] The intermediate polypropylene base resin having an MFR (2.16 kg, 230 ° C) of 1.0 to 6.0 g / 10min, determined in accordance with ISO 1133, is preferably obtained by a catalyst system comprising an asymmetric metallocene catalyst. According to a specific embodiment, the catalyst system has a porosity of less than 1.40 ml / g, more preferably less than 1.30 ml / g, and preferably less than 1.00 ml / g. Porosity was measured according to DIN 66135 (N2). In another preferred embodiment, the porosity is below the detection limit when determined with the method applied in accordance with DIN 66135.
    [0058] The catalyst system may further comprise an activator such as a cocatalyst, as described in WO 03/051934, which is included here for reference.
    [0059] An asymmetric metallocene catalyst according to this invention is a catalyst comprising at least two organic binders, which differ in their chemical structure.
    [0060] Furthermore, it is preferable that the catalyst system has a surface area of less than 25 m 2 / g, more preferably less than 20 m 2 / g, even more preferable less than 15 m 2 / g, more preferable even less than 10 m 2 / g, and preferably less than 5 m 2 / g. The surface area according to this invention is measured according to ISO 9277 (N2).
    Petition 870190119240, of 11/18/2019, p. 21/59
    It is particularly preferred that the catalyst system according to this invention comprises an asymmetric catalyst, i.e., a catalyst as defined above. In a specific modality, the porosity of the catalyst system is not detectable when applying the method according to DIN 66135 (N2) and has a surface area measured according to ISO 9277 (N2) less than 5 m 2 / g.
    [0062] Preferably, the asymmetric catalyst employed comprises an organometallic compound of a transition metal
    from groups 3 to 10 or from the periodic table (IUPAC) , or a
    actinide or lanthanide.
    [0063] The asymmetric catalyst of a compound of metal
    transition of formula (I) is more preferable:
    (L) m R n MX q (I) where
    M is a transition metal from group 3 to 10 or from the periodic table (IUPAC), or from an actinide or lanthanide, each X is independently a monovalent anionic ligand, such as σ-ligand,
    each L is independently an organic binder, what is
    coordinated to M,
    R is a bonding group joining two ligands L, m is 2 or 3, n is 0 or 1, q is 1, 2 or 3, m + q is equal to the valence of the metal, and with the condition of at least two ligands L are of different chemical structures.
    Petition 870190119240, of 11/18/2019, p. 22/59
    17/42 [0064] Said asymmetric catalyst is preferably a single site catalyst (SSC).
    [0065] In a more preferable definition, each L is independently:
    (a) a substituted or unsubstituted cycloalkyl diene, that is, a cyclopentadiene, or a mono, bi, or multifused derivative of a cycloalkyl diene, that is, a cyclopentadiene, which optionally supports additional substituents and / or one or more atoms of a hetero ring from Group 13 to 16 of the Periodic Table (IUPAC); or (b) a η 1 to η 4 or n 6- acyclic linker composed of atoms from Groups 13 to 16 of the Periodic Table, and in which the open chain linker can be fused with one or two, preferably two, aromatic rings or non-aromatic and / or support additional substituents; or (c) a σ-, η 1 - to η 4 - or n 6 -cyclic, mono, bi or multidentate linker, composed of unsubstituted or substituted, mono, bi or multicyclic ring systems, selected from aromatic or non-aromatic or partially saturated rings, and containing carbon atoms in the ring and optionally one or more hetero atoms selected from Groups 15 and 16 of the Periodic Table.
    [0066] The term σ-ligand is understood throughout the description in a known way, that is, a group attached to the metal in one or more places via a sigma bond. A preferable monovalent anionic binder is halogen, in particular chlorine (Cl).
    [0067] In a preferred embodiment, the asymmetric catalyst is preferably of a transition metal compound of formula (I):
    Petition 870190119240, of 11/18/2019, p. 23/59
    18/42 (L) m R n MX q (I) where
    M is a transition metal from group 3 to 10 or from the periodic table (IUPAC), or from an actinide or lanthanide,
    each X is independently one binder monovalent anionic, like this how σ-ligand, each L is independently one binder organic, the which is coordinated to M, where the ligand organic it's a binder cyclic
    unsaturated organic substance, more preferably a substituted or unsubstituted cycloakylthiene, that is, a cycloalkylthiene, or a mono, bi or multifused cycloalkylthiene derivative, that is, a cyclopentadiene, which optionally supports additional substituents and / or one or more atoms a hetero ring from a Group 13 to 16 of the Periodic Table (IUPAC),
    R is a linking group joining two L linkers,
    m is 2 or 3, n is 0 or 1, q is 1, 2 or 3,
    m + q is equal to the valence of the metal, and with the proviso that at least two L ligands are of different chemical structures.
    [0068] According to a preferable embodiment, said asymmetric catalyst compound (I) is a group of compounds known as metallocenes. The aforementioned metallocenes support at least one organic binder, generally 1, 2 or 3, for example 1 or 2, which is η-bonded to the metal, for example, a η 2-6 linker, as well as a n- 5- linker. Preferably, a metallocene is a transition metal from Group 4 to 6, more preferably zirconium, which contains at least one n 5 -linker.
    Petition 870190119240, of 11/18/2019, p. 24/59
    19/42 [0069] Preferably, the asymmetric catalyst compound has a formula (II):
    (Cp) m R n MX q (II) where
    M is Zr, Hf or Ti, preferably Zr, each X is independently a monovalent anionic ligand, as σ-ligand, each Cp is independently an unsaturated organic cyclic ligand, which is coordinated to M,
    R is a bonding group joining two ligands L, m is 2, n is 0 or 1, more preferably 1, q is 1, 2 or 3, more preferably 2, m + q is equal to the valence of the metal, and at least a Cp-ligand, preferably the two Cp-ligands, is / are selected from the group consisting of unsubstituted cyclopentadienyl, unsubstituted indenyl, unsubstituted tetrahydroindenyl, unsubstituted fluorenyl, substituted cyclopentadienyl, substituted indenyl, substituted tetrahydroindenyl, substituted and substituted fluorenyl, with the proviso that, in case the two Cp-ligands are selected from the group established above, the two Cpligants must differ chemically from each other.
    [0070] Preferably, the asymmetric catalyst is of formula (II) indicated above, where
    M is Zr, each X is Cl,
    Petition 870190119240, of 11/18/2019, p. 25/59
    20/42 n is 1, q is 2.
    [0071] Preferably, the two Cp-ligands have different residues to obtain an asymmetric structure.
    [0072] Preferably, the two Cp-ligands are selected from the group consisting of substituted cyclopentadienyl ring, substituted indenyl ring, substituted tetrahydroindenyl ring, and substituted fluorenyl ring, where the Cp-ligands differ from the substituents attached to the rings.
    [0073] The one or more optional substituent (s) attached to cyclopentadienyl, indenyl, tetrahydroindenyl, or fluorenyl, can be independently selected from a group including halogen, hydrocarbyl (for example C1-C20alkyl, C2-C20-alkenyl, C2-C20-alkynyl, Ca-C12-cycloalkyl, C6C20-aryl or C7-C20-arylalkyl), C3-C12-cycloalkyl containing 1,
    2, 3 or 4 heteroatom (s) in the ring portion, C6-C20-heteroaryl,
    C1-C2o-haloalkyl, -SiRa, -OSiRa, -SR, -PR2 and -NR2, in which each R is independently a hydrogen or hydrocarbil, for example C1-C20-alkyl, C2-C20-alkenyl, C2-C20- alkynyl, C3-C12cycloalkyl or C6-C20-aryl.
    [0074] More preferably, the two Cp-linkers are indenyl moieties, so that each indenyl moiety supports one or more substituents, as defined above. More preferably, each Cp-linker is an indenyl moiety bearing two substituents, as defined above, with the proviso that the substituents are chosen in such a way that the two Cpligants are of different chemical structures, that is, both Cp-ligands differ in at least one substituent attached to the
    Petition 870190119240, of 11/18/2019, p. 26/59
    21/42 indenyl, differing in particular in the substituent attached to the five membered ring of the indenyl portion.
    [0075] Even more preferably, both Cp are indenyl moieties which comprise in the five-membered ring of the indenyl moiety, more preferably in position 2, at least one substituent selected from the group consisting of alkyl, as well as C1-C6 alkyl, for example methyl, ethyl, isopropyl, and trialkyloxysiloxy, in which each alkyl is independently selected from C1-C6 alkyl, such as methyl or ethyl, with the proviso that the indenyl portions of both Cp must differ chemically from each other, i.e. that is, the indenyl moieties of both Cp comprise different substituents.
    [0076] Even more preferably, both Cp are indenyl moieties which comprise in the six-membered ring of the indenyl moiety, more preferably in position 4, at least one substituent selected from the group consisting of a C6-C20 aromatic moiety ring, as well as phenyl or naphthyl, preferably phenyl, which is optionally substituted with one or more substituents, such as C1-C6 alkyl, and a heteroaromatic ring moiety, with the proviso that the indenyl moieties of both Cp comprise different substituents.
    [0077] More preferably, both Cp are indenyl moieties which comprise in the five-membered ring of the indenyl moiety, more preferably in position 2, a substituent, and in the six-membered ring of the indenyl moiety, more preferably in position 4, one additional substituent, where the five-membered ring substituent is selected from the group consisting of alkyl, as well as C1-C6 alkyl, eg methyl, ethyl, isopropyl, and trialkyloxysiloxy, in which each
    Petition 870190119240, of 11/18/2019, p. 27/59
    22/42 alkyl is independently selected from C1-C6 alkyl, such as methyl or ethyl, and the additional six-membered ring substituent is selected from the group consisting of a C6-C20 aromatic ring portion, as well as phenyl or naphthyl, preferably phenyl, which is optionally substituted by one or more substituents, such as C1-C6 alkyl, and a heteroaromatic ring portion, with the proviso that the indenyl portions of both Cp comprise different substituents. In particular, it is preferable that both Cp are indenyl rings comprising two substituents each and differ in the substituents attached to the five member ring of the indenyl rings.
    [0078] Regarding the R portion, it is preferable that R has the formula (III):
    Where
    Y is C, Si or Ge, and
    R 'is C1 to C20 alkyl, C6-C12 aryl, or C7-C12 arylalkyl.
    [0079] In the case of the two Cp-ligands of the asymmetric catalyst as defined above, in the particular case of two indenyl moieties, they are joined with a bonding member R, the bonding member R being typically located in position 1. The bonding member R may contain one or more linker atoms selected from, for example, C, Si and / or Ge, preferably from C and / or Si. A preferable R linker is —Si (R ') 2 -, where R ! is independently selected from one or more, for example, C1-C10 alkyl, C1-C20 alkyl, as well as C6-C12 aryl, or C7-C40, as well as C7-C12 arylalkyl, where alkyl as such or as part of arylalkyl is preferably C1-C6 alkyl, as well as ethyl or methyl, preferably methyl, and aryl
    Petition 870190119240, of 11/18/2019, p. 28/59
    23/42
    it is preferably phenyl. The ligand —Si ( R '^ 2 - is
    preferably, for example, —Si (C1 - C 6 alkyl) 2 -, —Si (/ eniZ) 2 - or —Si (C1 - C 6 alkyl) (phenyl) -, as well as —Si (Me) 2 -.
    [0080] In a preferred embodiment, the asymmetric catalyst is defined by formula (IV):
    (Cp) 2 ^ iZr% 2 (IV) where each X is independently a monovalent anionic ligand, such as σ-ligand, in particular halogen the two Cp are coordinated to M and selected from the group consisting of unsubstituted cyclopentadienyl, non-indenyl
    substituted, unsubstituted tetrahydroindenyl, fluorenil not
    substituted, substituted cyclopentadienyl, substituted indenyl, substituted tetrahydroindenyl, and substituted fluorenyl, with the proviso that both Cp-ligands must differ chemically from each other, and
    R is a linking group joining two L linkers, where R is defined by formula (III):
    —Y (R ') 2 - (III) where
    Y is C, Si or Ge, and
    R 'is C1 to C20 alkyl, C6-C12 aryl, or C7-C12 arylalkyl.
    [0081] More preferably, the catalyst asymmetric is
    defined by formula (IV), in which the two Cp are selected from a group consisting of substituted cyclopentadienyl, substituted indenyl, substituted tetrahydroindenyl, and substituted fluorenyl.
    [0082] Most preferably, the asymmetric catalyst is defined by formula (IV), in which the two Cp are
    Petition 870190119240, of 11/18/2019, p. 29/59
    24/42 selected from a group consisting of substituted cyclopentadienyl, substituted indenyl, substituted tetrahydroindenyl, and substituted fluorenyl, with the proviso that both Cp-ligands differ in the substituents, that is, the substituents, as defined above, linked to the cyclopentadienyl , indenyl, tetrahydroindenyl, or fluorenyl.
    [0083] Even more preferably, the asymmetric catalyst is defined by formula (IV), in which the two Cp are indenyl and both indenyl differ in a substituent, that is, in a substituent, as defined above, attached to the five-membered ring of indenil.
    [0084] It is particularly preferable that the asymmetric catalyst is a non-silica supported catalyst, as defined above, in particular a metallocene catalyst, as defined above.
    [0085] In a preferred embodiment, the asymmetric catalyst is dimethylsilyl [(2-methyl- (4'-tertbutyl) -4-phenylindenyl) (2-isopropryl- (4'-tertbutyl) -4-phenyl-indenyl)] dichloride of zirconium. More preferably, the support of said asymmetric catalyst is not silica.
    [0086] The components of the asymmetric catalyst described above are prepared according to the methods described in WO 01/48034.
    [0087] In a preferred embodiment, the asymmetric catalyst system is obtained by emulsion solidification technology, as described in WO 03/051934. This document is included here in its entirety as a reference. Thus, in this specific modality, the asymmetric catalyst is
    Petition 870190119240, of 11/18/2019, p. 30/59
    25/42 preferably in the form of solid catalyst particles, obtained by a process comprising the steps of:
    The) prepare a solution in one or more components of asymmetric catalyst; B) disperse the mentioned solution in an immiscible solvent, forming a emulsion in what one or more components of
    mentioned catalyst are present in the droplets of the dispersed phase;
    c) solidifying said dispersed phase in order to convert said droplets into solid particles and, optionally, recovering said particles to obtain said catalyst.
    [0088] Preferably a solvent, more preferably an organic solvent, is used to form said solution. Even more preferably, the organic solvent is selected from the group consisting of a linear alkane, cyclic alkane, linear alkene, cyclic alkane, aromatic hydrocarbon and halogen-containing hydrocarbon.
    [0089] In addition, the immiscible solvent forming the continuous phase is an inert solvent. More preferably, the immiscible solvent comprises a fluorinated organic solvent and / or a functionalized derivative thereof. Even more preferably, the immiscible solvent comprises a semi, highly or perfluorinated hydrocarbon and / or a functionalized derivative thereof. In particular, it is preferable that said immiscible solvent comprises a perfluorhydrocarbon or a functionalized derivative thereof, preferably perfluoralkanes, -alkenes or -cycloalkenes, C3-C30, more preferably perfluoralkanes, -alkenes or
    Petition 870190119240, of 11/18/2019, p. 31/59
    C4-C10 cycloalkenes, particularly preferably perfluorhexane, perfluorheptane, perfluoroctane or perfluor (methylcyclohexane), or a mixture thereof.
    [0090] Furthermore, it is preferred that the emulsion comprising said continuous phase and said dispersed phase is a bi or multiphase system, as known in the art. An emulsifier can be used to form the emulsion. After the formation of the emulsion system, said catalyst is formed in situ from the catalyst components in said solution.
    [0091] In principle, the emulsifying agent can be any suitable agent that contributes to the formation and / or stabilization of the emulsion and that has no adverse effect on the catalytic activity of the catalyst. The emulsifying agent can, for example, be a surfactant based on hydrocarbons optionally interrupted by (a) heteroatom (s), preferably halogenated hydrocarbons, optionally having a functional group, preferably semi, highly or perfluorinated hydrocarbons, as known in the art. Alternatively, the emulsifying agent can be prepared during the preparation of the emulsion, for example, by reacting a surfactant precursor with a compound of the catalyst solution. Said surfactant precursor can be a halogenated hydrocarbon with at least one functional group, for example a highly fluorinated C1 to C30 alcohol, which reacts for example with a cocatalyst component, as well as an aluminoxane.
    [0092] In principle, any solidification method can be used to form solid particles from dispersed droplets. According to a preferable modality, the
    Petition 870190119240, of 11/18/2019, p. 32/59
    27/42 solidification is effected by a temperature change treatment. In this way, the emulsion is subject to a gradual change in temperature up to 10 ° C / min, preferably 0.5 to 6 ° C / min and more preferably 1 to 5 ° C / min. Even more preferably, the emulsion is subjected to a temperature change of more than 40 ° C, preferably more than 50 ° C, in less than 10 seconds, preferably less than 6 seconds.
    [0093] The recovered particles preferably have an average size in a range of 5 to 200 μη, more preferably 10 to 100 μη.
    [0094] Furthermore, the shape of the solidified particles preferably has a spherical shape, a predetermined particle size distribution and a surface area mentioned above preferably less than 25 m 2 / g, more preferably less than 20 m 2 / g , even more preferably less than 15 m 2 / g, more preferably still less than 10 m 2 / g, and preferably less than 5 m 2 / g, so that the mentioned particles are obtained by the process as described above.
    [0095] For further details, modalities and examples of the continuous and dispersed phase system, emulsion formation method, emulsifying agent and solidification methods, reference is made, for example, to the application of the international patent WO 03/051934 mentioned above.
    Preferred as cocatalysts for metallocenes and non-metallocenes, if desired, are aluminoxanes, in particular C1-C10-alkylaluminoxanes, more particularly methylaluminoxane (MAO). Such aluminoxanes can be used as a single cocatalyst or in conjunction with other cocatalyst (s). So, in addition to aluminoxanes, or in addition to them, another complex
    Petition 870190119240, of 11/18/2019, p. 33/59
    28/42 cationic forming catalyst activators can be used. The mentioned activators are commercially available or can be prepared according to the prior art in the literature.
    [0097] Additional aluminoxane cocatalysts are described, among others, in WO 94/28034, which is incorporated herein by reference. These are linear or cyclic oligomers having up to 40, preferably 3 to 20, repeat units - (Al (R ') O) - (where R' is hydrogen, C1-C10-alkyl (preferably methyl) or C6-C18-aryl or mixtures thereof).
    [0098] The use and quantities of such activators are within the skills of a specialist in the field. As an example, with a boron activator, a 5: 1 to 1: 5 ratio, preferably 2: 1 to 1: 2, as well as 1: 1, of the transition metal of the boron activator can be used. In the case of preferable aluminoxanes, such as methylaluminoxane (MAO), the amount of Al, provided by the aluminoxane, can be chosen to provide a molar ratio of Al: transition metal eg in a range of 1 to 10,000, suitably 5 to 8000, preferably 10 to 7000, for example, 100 to 4000, as well as 1000 to 3000. Typically in the case of a solid (heterogeneous) catalyst, the ratio is preferably below 500.
    [0099] The amount of cocatalyst to be used in the catalyst of the invention is, therefore, variable, and depends on the conditions and the particular transition metal compound chosen in a manner well known to a person skilled in the art.
    [0100] Any additional components to be contained in the solution comprising the organotransition compound can be
    Petition 870190119240, of 11/18/2019, p. 34/59
    29/42 added to the mentioned solution before or alternatively after the dispersion step.
    [0101] The present invention further relates to a coated article including the polypropylene composition, as described herein, as a layer. The layer can be placed on a cellulosic-based sheet, for example, paper, cardboard, cardboard and the like. The layer can also be placed on metal sheets, for example, tinplate, aluminum film and the like. The term "placed on" means that the layer formed by the polypropylene composition according to the present invention is in direct contact with the substrate, without any intermediate layer. The main end use for such extruded coated articles is in packaging applications, such as liquid packaging for milk, juice, wine or other liquids, flexible packaging for meat, cheese and medical products, rigid packaging such as detergent packaging, glasses, plates and trays for use in the oven or microwave, or sterilizable food packaging, as well as on photographic paper or industrial applications, such as paper spools and reams packages.
    [0102] The process of coating a coated article according to the present invention, applying the polypropylene composition as described above, is characterized by drawing speeds of 300 m / min, more preferably 400 m / min and preferably 500 m / min, in relation to the stretching of 10 g of coating layer per square meter of substrate.
    [0103] More preferably, the process of coating an article coated according to the present invention, applying
    Petition 870190119240, of 11/18/2019, p. 35/59
    30/42 the polypropylene composition as described above, is characterized by very little neck formation. This very little neck formation is, moreover, surprisingly independent of the stretching speed. When the stretching lag is 20 g / m 2 of coating, the neck formation is preferably less than 120 mm, more preferably less than 110 mm, at a stretch of 100 m / min. The neck formation is preferably less than 110 mm and more preferably less than 100 mm in a 200 m / min stretch. In a 300 m / min stretch, the neck formation is preferably less than 110 mm and more preferably less than 105 mm, whereas, in a 400 m / min stretch, the neck formation is preferably less than 115 mm and more preferably less than 110 mm.
    [0104] The present invention is also related to the use of the polypropylene-based resin according to the present invention for extrusion coating.
    Examples
    l.Methods
    a) Flow Rate [0105] The flow rate (MFR) according to ISO 1133 is indicated in g / 10min. The MFR is an indication of the flow capacity and, therefore, the processability of the polymer. The higher the flow rate, the lower the viscosity of the polymer. The polypropylene MFR2 is determined at a temperature of 230 ° C and a load of 2.16 kg.
    b) Melting and crystallization temperature
    Petition 870190119240, of 11/18/2019, p. 36/59
    31/42 [0106] The melting and crystallization temperatures Tm and Tc are determined according to ISO 11357-3 with a TA-lnstruments 2920 Dual-Cell with RSC cooling device and station data. A heating and cooling rate of 10 ° C / min is applied in a heat / cold / heat cycle between +23 and + 210 ° C, the crystallization temperature Tc being determined in the cooling step and the melting temperature Tm being determined in the second heating step.
    c) Comonomer Content [0107] Quantitative Fourier Transform Infrared Spectroscopy (FTIR) was used to quantify the amount of comonomer. Calibration was performed by correlation with comonomer levels determined by quantitative nuclear magnetic resonance (NMR) spectroscopy.
    [0108] The calibration procedure, based on results obtained from 13 C-NMR spectroscopy, was carried out in the conventional manner well documented in the literature.
    [0109] The amount of the comonomer (N) was determined as a percentage by mass (% by mass) via:
    N = + k 2 where A is the maximum absorbance defined for the comonomer range, R is the maximum absorbance defined for the reference peak height and with the linear constants k1 and k 2 obtained by calibration. The range used to quantify the ethylene content is selected depending on whether the ethylene content is random (730 cm -1 ) or block (720 cm -1 ). The absorbance at 4324 cm -1 was used as a reference range.
    d) Strain Hardening Factor (SHF)
    Petition 870190119240, of 11/18/2019, p. 37/59
    32/42 [0110] The strain hardening factor is defined as ^ + (ί, έ) _ η + ί, έ) ^ lveO 3η + ( ΐ ') where
    VeCA) is the uniaxial extensional viscosity; and g + vE (t) is three times the time-dependent shear viscosity ^ + (t) in the linear strain range.
    [0111] The determination of linear viscoelasticity in extension 7zVE (t) , using IRIS Rheo Hub 2008, requires the calculation of the discrete spectrum of relaxation time from the storage and loss data module (G ', 6 ”(ω) ). The linear viscoelasticity data (G ', G (m)) is obtained by scanning frequency measurements performed at 180 ° C, on an Anton Paar MCR 300 coupled with 25 mm parallel plates. The basic principles of the calculations used to determine the discrete relaxation spectrum are described in Baumgãrtel M, Winter HH, “Determination of the discrete relaxation and retardation time spectra from dynamic mechanical data”, Rheol Acta 28:51 1519 (1989), the which is incorporated as a reference.
    0112] IRIS RheoHub 2008 expresses the relaxation time spectrum as a sum of N Maxwell forms W _L ° G ( t ) = G e . ^ Gi- eÁí where gt e are material parameters and G e is the equilibrium module.
    [0113] The choice of the maximum number of N shapes, used to determine the discrete relaxation spectrum, is made using the “optimum” option of the IRIS RheoHub 2008. The balance module G e is fixed at zero.
    Petition 870190119240, of 11/18/2019, p. 38/59
    33/42 [0114] The non-linear adjustment used to obtain ^ LVE (t) is performed in IRIS RheoHub 2008, using the Doi-Edwards model.
    [0115] The uniaxial extensional viscosity ^ + (t, ã) is obtained from uniaxial extensional flow measurements, conducted on an Anton Paar MCR 501 coupled with Sentmanat extensional fixation (SER-1). The temperature for uniaxial extensional flow measurements was fixed at 180 ° C, applying extension rates (deformation) - in a range of 0.3 s -1 dt to 10 s -1 and covering a range of Hencky deformation £ _ ( l ~ lp) * 0 with l 0 with the original fixation length of the sample being the current link, from 0.3 to 3.0.
    [0116] Special care was taken in preparing the samples for extensional flow. The samples were prepared by means of compression modeling at 230 ° C, followed by slow cooling to room temperature (no water or forced ventilation was used). This procedure allowed obtaining well-formed samples free of residual stresses.
    The sample was left for five minutes at the test temperature to ensure thermal stability (temperature setting ± 0.1 ° C), before performing uniaxial extensional flow measurements.
    e) Non-linear viscoelastic ratio LAOS [0117] The investigation of non-linear viscoelastic behavior under shear flow was performed using the Large Amplitude Oscillatory Shear. The method requires the application of a sinusoidal strain amplitude, y 0 , imposed at a given angular frequency, ω, for a given time, t. As long as the applied sinusoidal strain is high enough,
    Petition 870190119240, of 11/18/2019, p. 39/59
    34/42 a non-linear response will be provided. The stress σ is, in this case, a function of the applied strain amplitude, time and angular frequency. Under these conditions, the response to non-linear stress is still a periodic function; however, it can no longer be expressed by a single harmonic sinusoid. The stress resulting from a non-linear viscoelastic response [1-3] can be expressed by a Fourier series, which includes the greatest harmonic contributions:
    σ (ί, ω, γ 0 ) = γ 0 . Σ (G η (ω, γ 0 ). Sen (ncüt) + G n (co, y 0 ). Cos (nwt)] with, σ - stress response t - time ω - frequency γ 0 - strain range η - harmonic number
    G ' n - Fourier elastic coefficient of order n G n - Viscous Fourier coefficient of order n [0118] The non-linear viscoelastic response was analyzed by applying Large Amplitude Oscillatory Shear (LAOS). Time scan measurements were performed on an Alpha Tecnologies RPA 2000 rheometer coupled to a standard biconic matrix. During the course of the measurement, the test chamber is sealed and a pressure of about 6 MPa is applied. The LAOS test is performed by applying a temperature of 190 ° C, an angular frequency of 0.628 rad / s and a strain range of 10. In order to ensure that steady-state conditions are achieved, the non-linear response is determined only after completing at least 20 cycles per measurement.
    Petition 870190119240, of 11/18/2019, p. 40/59
    35/42 [0119] The Nonlinear Oscillatory Shear Factor of
    Large Amplitude (LAOS-NFL) is defined as:
    LAOS - NLF =
    G'i
    G ' 3 where G' 1 - first order Fourier coefficient
    G'3- third order Fourier coefficient
    0120] More details regarding the measurement are found in
    1. J. M. Dealy, K. F. Wissbrun, Melt Rheology and Its Role in Plastics Processing: Theory and Applications; edited by Van Nostrand Reinhold, New York (1990)
    2. S. Filipe, Non-Linear Rheology of Polymer Melts, AIP
    Conference Proceedings 1152, pp. 168-174 (2009)
    3. M. Wilhelm, Macromol. Mat. Eng. 287, 83-105 (2002)
    4. S. Filipe, K. Hofstadler, K. Klimke, A. T. Tran, NonLinear Rheological Parameters for Characterization of Molecular
    Structural Properties in Polyolefins, Annual Procedures
    European Rheology Conference, 135 (2010) documents (1) to (4) being incorporated here as a reference.
    f) Rheotens test [0121] The test described here follows ISO 16790: 2005.
    [0122] The deformation hardening behavior is determined by the method as described in the article “RheotensMastercurves and Drawability of Polymer Melts”, MH Wagner, Polymer Engineering and Sience, Vol. 36, pages 925 to 935. The content of the document is included as reference. The polymer deformation hardening behavior is analyzed by the Rheotens equipment (product of Gottfert, Siemensstr.2, 74711 Buchen, Germany), in which a molten filament is elongated, stretching it to a defined acceleration.
    Petition 870190119240, of 11/18/2019, p. 41/59
    36/42 [0123] The experiment at Rheotens simulates industrial spinning and extrusion processes. At first, a melt is pressed and extruded through a round die and the resulting wire is dragged. The stress in the extrudate is recorded as a function of melting properties and measurement parameters (especially the ratio between the exit and drag speeds, practically a measure of the extension rate). For the results presented below, the materials were extruded with a HAAKE Polylab laboratory extruder and a gear pump with cylindrical matrix (L / D = 6.0 / 2.0 mm). The gear pump was preset at a filament extrusion rate of 5 mm / s, and the melting temperature was set at 200 ° C. The length of the spinline between the matrix and the wheels of the Rheotens was 80 mm. At the beginning of the experiment, the adhesion speed of the Rheotens' wheels was adjusted to the speed of the extruded polymer filament (zero traction force). Then the experiment was started by the slow increase in the adhesion speed of the Rheotens' wheels until the polymeric filament broke.
    The acceleration of the wheels was small enough that the tractive force was measured under quasi-stationary conditions. The drag acceleration of the molten filament is 120 mm / s 2 . The Rheotens was operated in combination with the EXTENS computer program. This is a real-time data acquisition program, which shows and stores the measured data of the pulling force and the drag speed. The end points of the Rheotens curve (force versus rotational speed of the pulley) are considered to be values of melt and drag resistance.
    g) Regioinversion
    Petition 870190119240, of 11/18/2019, p. 42/59
    37/42 [0124] The 13 C-NMR spectra were acquired on a DPX-400 spectrometer operating at 100.61 MHz in Fourier transform mode at 120 ° C. The samples were dissolved in 1,1,2,2 tetrachloroethane-d2 at 120 ° C with a concentration of 8% mass / volume. Each spectrum was acquired with a 90 ° pulse, 15 second interval between pulses and CPD (waltzl [omicron]) to remove the 1 H- 13 C coupling. About 3000 transients were stored at 32K of data points using a 6000 Hz spectral window.
    2.Compositions [0125] The intermediate product EI1 was produced in a Borstar PP pilot plant in a two-stage polymerization process, starting in a bulk phase loop reactor, followed by polymerization in a gas phase reactor , varying the molecular mass by appropriate hydrogen feed. The catalyst used in the polymerization process was a metallocene catalyst, as described in example 1 of EP 1741725 A1. The reaction conditions are listed in table 1.
    Petition 870190119240, of 11/18/2019, p. 43/59
    38/42
    Table 1 - Reaction conditions in polymerization
    Resin HEY Pre-polymerization Residence time [h] 0.32 Temperature [° C] 30 Type reactorloop Temperature [° C] 75 Residence time [h] 0.4 MFR2 [g / 10min] 0.8 Gas phase reactor Temperature [° C] 85 Residence time [h] 0.6 MFR2 [g / 10min] 2.9 Final MFR2 [g / 10min] 2.9 2.1 molar% regiodefects 0.8
    [0126] The intermediate product EI1 was subjected to reactive extrusion in the presence of butadiene and peroxide, as described below. Both butadiene and peroxide were pre-mixed with the polymer powder before the mixing step of the molten material in a horizontal mixer with paddle stirrer, at a temperature of 65 ° C, maintaining an average residence time of 15 minutes. The premix was transferred in an inert atmosphere to a co-rotating twin screw extruder of the type Theyson TSK60, having a cylinder diameter of 60 mm and an L / D ratio of 48, equipped with a high intensity mixing screw, having three compression zones and a two-stage degassing installation. A melting temperature profile with initial temperature T1 = 220 ° C was selected in the feed zone, maximum temperature T2 = 240 ° C in the last compression zone, and a final temperature T3 = 230 ° C in the termination zone, all temperatures being
    Petition 870190119240, of 11/18/2019, p. 44/59
    39/42 defined as the cylinder. The thread speed was adjusted to 350 rpm. After the melt mixing step, the resulting polymer was pelleted in an underwater pelletizer, or, after the solidification of one or more filaments in an immersion tank, in a filament pelletizer with water at a temperature of 40 ° C. Reaction conditions and rheological parameters are summarized in table 2.
    [0127] The reactive extrusion was repeated modifying the conditions.
    Petition 870190119240, of 11/18/2019, p. 45/59
    40/42
    Table 2 - Parameters for modifying the reaction and rheological characterization of the examples.
    EI2 EI3 EI4 EI5 Reagents andconditions Peroxide [% inpasta] 0.475 0.6 0.6 0.6 Butadiene [% inpasta] 1.20 1.36 1.20 0.96 Intervaltemperature [° C] 200 -240 200 -240 200 -240 200 -240 Speedthread [rpm] 350 350 350 350 Flow rate [kg / h] 190 190 190 190 Product EI2 EI3 EI4 EI5 Final properties MFR2 [g / 10min] 9.6 10 14.3 20 LAOS-NFL [-] 4.21 4.24 4.98 4.31 SHF (3 / 2.5) [-] * 3.36 4.48 4.43 3.36 SHF (1 / 2.0) [-] ** *** 2.33 2.07 1.98 1.88 Resistance ofcast F30 [cN] 11.0 13.5 9.5 6.0
    * strain-hardening factor (SHF) measured at a strain rate of 3.0 s -1 and a Hencky strain of 2.5.
    ** strain-hardening factor (SHF) measured at a strain rate of 1.0 s -1 and a Hencky strain of 2.0.
    *** Terc-butylperoxy isopropyl carbonate (CAS No. 2372-21-6) Trigonox® BPIC-C75 (Akzo Nobel, NL) - 75% solution in turpentine; the amount given in Table 2 refers to the total amount of the solution (including turpentine).
    Petition 870190119240, of 11/18/2019, p. 46/59
    41/42 [0128] The following table shows the evaluation of the stretch in the extrusion coating versus comparative high strength melt materials. The commercial homopolymer HMS-PP (WF420HMS), available from Borealis Polyolefine GmbH and produced from a homopolymer ZN-PP, was used as a comparative example. This polymer has an MFR2 of 22 g / 10min, a LAOSNFL of 2.63, an SHF of 2.03 measured at a deformation rate of
    3.0 s -1 and a Hencky strain of 2.0, and a resistance of the F30 melt of 4.0 cN determined in a test on Rheotens at
    200 ° C.
    [0129] Extrusion coating tests were carried out on a Beloit coextrusion coating line. The line had two identical extruders 1 & 2 with a cylinder diameter of 4.5 ”and an L / D ratio of 24, at a flow rate of 450 kg / h; and an extruder 3 with a cylinder diameter of 2.5 ”and an L / D ratio of 30, the flow rate is 170 kg / h. The line also has Peter Cloeren's matrix equipment with internal and external deckling and a five-layer power block. The line length was
    600 - 800 mm and the maximum line speed was 1000 m / min (design value). In the coating line, a UG kraft paper having a weight of 70 g / m 2 was coated with 20 g / m 2 of the inventive or comparative compositions. A second series of tests with a coating mass of 10g / m2 was also carried out. The temperature of the molten polymer was set at 290 ° C and the temperature profile of the extruder was 200-240-290-290 ° C. The cooling cylinder was frosted and its surface temperature was 15 ° C. The die orifice used was 0.65 mm and the distance between the cylinders (nip) was 160 mm. The molten film touched the substrate for the first time + 10 mm from the nip until
    Petition 870190119240, of 11/18/2019, p. 47/59
    42/42 the side of the substrate. The pressure of the compression roller was 3.0 kp / cm 2 . The line speed varied between 100 and 500 m / min; the maximum stretching speed reached for both masses and the neck for a coating mass of 20g / m 2 and various speeds are listed in table 3.
    Table 3 - Results of extrusion coating tests
    CategoryMFR [g /10min] Stretch speed [m / min] Neck at 20 g / m2[mm] 100 m / mi n 200 m / mi n 300 m / mi n 400 m / mi n 20 g / m 2 10g / m2 WF420HMS CE1 22 > 500 300 179 162 162 164 LCB-SSC-PP E2 10 500 300 109 102 106 111 E3 10 500 290 93 88 92 96 E4 14 > 600 400 107 99 104 105 E5 20 > 600 > 500 117 105 107 110
    Petition 870190119240, of 11/18/2019, p. 48/59
    权利要求:
    Claims (13)
    [1]
    1. Polypropylene composition characterized by comprising a polypropylene-based resin, the polypropylene-based resin having an MFR (2.16 kg, 230 ° C, ISO 1133) of 8 to 24 g / 10 min and a LAOS- factor NLF> 2.8 and
    LAOS - NLF = where 6} - First order Fourier coefficient
    G'3 - Third order Fourier coefficient
    [2]
    2. Polypropylene composition according to claim 1, characterized in that the polypropylene-based resin has a strain-hardening factor (SHF) of 2.3 to 7.0, when measured at a strain rate of 3.0 s -1 and a Hencky strain of 2.5.
    [3]
    3. Polypropylene composition according to the claim
    1, characterized in that the polypropylene-based resin has a strain hardening factor of 1.7 to 6.0, when measured at a strain rate of 1.0 s -1 and a Hencky stress of 2.0.
    [4]
    Polypropylene composition according to any one of claims 1 to 3, characterized in that the polypropylene-based resin has a melt strength of F30 of 4.6 cN or greater at 200 ° C.
    [5]
    Polypropylene composition according to any one of claims 1 to 4, characterized in that the polypropylene-based resin is a polypropylene homopolymer.
    Petition 870190119240, of 11/18/2019, p. 50/59
    2/3
    [6]
    Polypropylene composition according to any one of claims 1 to 5, characterized in that the polypropylene-based resin has a region-inversion above 0.1 mol-%.
    [7]
    7. Polypropylene composition according to any one of claims 1 to 6, characterized in that the polypropylene-based resin has a product of [melt strength F30 x MFR2 (2.16 kg, 230 ° C, ISO 1133)] 130 cNg / 10 min or greater.
    [8]
    Polypropylene composition according to any one of claims 1 to 7, characterized in that it has a melting temperature Tm in the range of 135 to 165 ° C.
    [9]
    Process for the production of a polypropylene composition as defined in any one of claims 1 to 8 characterized by an intermediate polypropylene based resin derived from an asymmetric catalyst, with an MFR (2.16 kg, 230 ° C, ISO 1133) from 1.0 to 6.0 g / 10 min be mixed with peroxide and a diene at a temperature of 20 to 90 ° C for at least 2 minutes to form a pre-mixed material; and the premixed material is mixed with melt in a melt mixing device at a cylinder temperature in the range of 180 to 300 ° C.
    [10]
    10. Coated article characterized by including the composition of
    polypropylene as defined in Any of them of claims of 1 to 8 as a layer of coating. 11. Process for coat a article featured per
    comprising fixing a layer consisting of a polypropylene composition as defined in any one of claims 1 to 8.
    Petition 870190119240, of 18 /
    [11]
    11/2019, p. 51/59
    3/3
    [12]
    Process according to claim 11, characterized in that the speed of establishment is above 300 m / min, for a coating mass of 10 g per square meter of substrate.
    [13]
    13. Use of a polypropylene composition as defined in any one of claims 1 to 8, characterized in that it is for extrusion coating.
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    BR112012028741A2|2017-12-19|
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    法律状态:
    2019-08-20| B06U| Preliminary requirement: requests with searches performed by other patent offices: procedure suspended [chapter 6.21 patent gazette]|
    2019-12-17| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|
    2020-02-18| B16A| Patent or certificate of addition of invention granted|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 21/01/2011, OBSERVADAS AS CONDICOES LEGAIS. |
    优先权:
    申请号 | 申请日 | 专利标题
    EP10004990.7|2010-05-11|
    EP10004990A|EP2386584A1|2010-05-11|2010-05-11|Polypropylene composition suitable for extrusion coating|
    PCT/EP2011/000255|WO2011141070A1|2010-05-11|2011-01-21|Polypropylene composition suitable for extrusion coating|
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