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    • 专利摘要:
    polypropylene composition, article and use of low molecular weight linear isotactic polypropylene. The present invention relates to a polypropylene composition having a high melt flow rate and strength while maintaining high impact strength. The composition of the present invention is obtained by using a flowable polypropylene for a high molecular weight high melt strength and impact strength polypropylene. The inventive composition can be used for the production of different articles.
    公开号:BR112012028742B1
    申请号:R112012028742-7
    申请日:2010-11-29
    公开日:2019-09-24
    发明作者:Susana Filipe；Katja Klimke；Anh Tuan Tran；Petar Doshev；Antti Tynys；Martin Obadal；Cornelia Kock；David Friel
    申请人:Borealis Ag；
    IPC主号:
    专利说明:

    [0001] The present invention relates to a polypropylene composition having a high melt flow rate and high melt strength, while still maintaining a high impact resistance. The composition of the present invention is obtained by using a linear low molecular weight isotactic polypropylene as a fusion enhancer for a high molecular weight polypropylene. The composition of the present invention can be used for the production of different articles.
    [0002] In the field of molded articles, it is extremely important to have a material of good fluidity with good mechanical properties, that is, a high modulus of elasticity and an acceptable impact resistance. Good flow capacity is necessary to achieve good processability in various methods of article making, for example, extrusion and molding processes, thus allowing the high production speed required in this mass production market.
    [0003] It is well known that polyolefins produced by low pressure processes are generally linear materials characterized by no or very moderate melt strength and deformation hardening behavior. In order to improve its suitability in applications such as, for example, foam and fiber production, different approaches were taken to give rise to the long chain branch and, ultimately, to greater melt strengths. Long chain branching can be initiated by post reactor treatment (peroxide, irradiation). In the case of treatment in
    Petition 870190058423, of 06/24/2019, p. 7/42
    2/28 post-reactor with peroxide, an external polyfunctional component (eg 1,3-Bis (citraconimidomethyl) benzene, low molecular weight polybutadiene) should be used as a chain extender. This approach is used in the production of high-strength polypropylene from the melt (HMS-PP). In addition to the improved melt strength, the presence of long chain branches imposes very good impact resistance, which can be interesting for applications such as injection molding. However, these applications usually require higher flow rates of the composition used.
    [0004] The post reactor modification approach has inherent limitations with regard to the maximum attainable flow rate, because of the competition between chain splitting and chain development. A conventional viscorreduction is also not possible, as it will result in the splitting of the side chains and a consequent decrease in impact resistance.
    [0005] EP1382638 claims a polypropylene composition of a propylene homopolymer or random propylene copolymer with up to 50% by mass, high melt strength and a β-nucleating agent. The resulting mixture exhibits good impact balance rigidity and can be used for storage and household applications. However, the predominant β modification generates a reduction in the melting temperature and in the thermomechanical stability.
    [0006] WO2008 / 074715 A1 refers to a charged polypropylene composition consisting of 15-55% by weight of a polymeric component, 20-80% (inorganic) charge and 4-25% elastomeric polymer or composition
    Petition 870190058423, of 06/24/2019, p. 8/42
    3/28 polymeric. The load content, however, causes an increase in density and a reduction in surface quality, which is undesirable in many applications.
    [0007] Therefore, although the described compositions exhibit good processability and good mechanical properties, there is still a need for compositions with a high flow rate and, therefore, with excellent processability properties, maintaining their good mechanical properties, that is, there are a need for materials with long chain branches with high flow rate and high impact.
    [0008] Thus, the purpose of the present invention is to provide a polypropylene composition with high flow capacity, that is, good processability, which at the same time has high melt strength and good mechanical properties; in particular, the composition exhibits an improved balance of impact resistance and processability properties.
    [0009] Surprisingly, it has been found that the above purpose can be achieved if a high strength polypropylene polymer of the melt, exhibiting good deformation hardening behavior, is mixed with a low molecular weight linear isotactic polypropylene with a high flow rate. This results particularly from the mutual cocrystallization of both miscible stereoregular components.
    [0010] Thus, the present invention provides a polypropylene composition comprising (A) 70 to 95% by weight, based on the total mass of the polypropylene composition, of a component of
    Petition 870190058423, of 06/24/2019, p. 9/42
    4/28 high molecular weight polypropylene with a strain-hardening factor (SHF) in the range of 3.5 to 15 when measured at a strain rate of 3.0 s _1 and a Hencky strain of 2.5, and (B) 5 wt% to 30 wt%, based on the total mass of the polypropylene composition, of a linear low molecular weight isotactic polypropylene component with an MFR2 in the range 500 to 5000 g / 10min, measured in accordance with ISO 1133 (230 ° C, 2.16 kg load).
    [0011] The inventive composition is obtained by mixing the two components as described above, that is, component (A) with component (B), in which the use of linear low molecular weight isotactic polypropylene (B) as a fluidity enhancer in a specific amount it generates an increase in fluidity of at least three orders of magnitude, maintaining a high melt strength and preserving the impact resistance of the composition.
    [0012] The component of high molecular weight polypropylene (A) is a polypropylene of high fluidity due to the presence of long chain branches in the polymer.
    [0013] Polymers with long chain branches exhibit a smaller rotation radius in solution than the respective species with identical molecular mass. The theoretical branch index g ch is then ™ <* 2 > - ^ Σ: '= ιΣ = Ι V where <s 2 > is the radius of rotation resulting from the sum of the end-to-end distance of the polymer molecules. Because
    Petition 870190058423, of 06/24/2019, p. 10/42
    5/28 proportionality between the radius of rotation and the intrinsic viscosity, the branch index g'â ff can be simply calculated value for linear polymer is calculated from the measurement by SEC with a usual ratio and the branched polymer is measured directly in solution.
    [0015] The ε exponent is usually between 0.5 and 1. Just like g th , g f is always less than 1 for long-chain polymers. A lower value reflects a greater degree of branching. Details of the calculation and the relationship with the chain structure can, for example, be found in a paper by BM Zimm and WM Stockmayer (J. Chemical Physics 17 (1949) 1301-1310).
    [0016] The intrinsic viscosity required to determine the branching index g f is measured according to DIN ISO 1628/1, October 1999 (in decalin at 135 ° C).
    [0017] It is preferable that the high molecular weight component (A) used in the inventive polypropylene composition has a branching index less than 1, more preferably less than 0.9, and preferably less than 0.7. In a preferred embodiment, the high molecular weight component (A) has a branching index of 0.6 to 0.9.
    [0018] It is also preferable that the high molecular weight polypropylene component (A) has a LAOS non-linearity factor (LAOS-NLF) in a range of 4.0 to 10, preferably in a range of 4.5 to 9.
    Petition 870190058423, of 06/24/2019, p. 11/42
    6/28 [0019] The method of measurement of oscillatory shear in large amplitudes (LAOS) is a method of characterization very sensitive and at the same time very simple, being frequently used in scientific literature. 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, ...). Analysis by
    Fourier transform allows the recovery of intensities and phases. As the intensity of the higher harmonics decreases rapidly, which can lead to very low values of the 5 and higher harmonics, the reason
    LAOS - NLF = provides the most reliable characterization of the polymer structure.
    [0020] A LAOS - NLF greater than 2.5 indicates a high degree of long chain branching.
    [0021] Furthermore, the high molecular weight polypropylene component (A) and the polypropylene composition according to the present invention exhibit good deformation hardening behavior.
    [0022] The high molecular weight polypropylene component (A) has a strain-hardening factor (SHF) in the range of 3.5 to 15, preferably in the range of 4.5 to 12.5, more preferably in the range of 5.0 to 10, when measured at a strain rate of 3.0 s _1 and a Hencky strain of 2.5.
    Petition 870190058423, of 06/24/2019, p. 12/42
    7/28 [0023] In addition, the high molecular weight polypropylene component (A) preferably has a strain-hardening factor (5f7F) in the range of 2.4 to 8.0, more preferably in the range of 2.8 to 7.5, even more preferably in the range of 3.0 to 7.0, when measured at a strain rate of 1.0 s -1 and a Hencky strain of 2.0.
    [0024] The strain hardening factor is defined as ^ LVE (0 + (C where the uniaxial extensional viscosity is; and θ three times the time-dependent shear viscosity in the linear strain range).
    [0025] The determination of linear viscoelasticity in extension using IRIS Rheo Hub 2008, requires the calculation of the discrete spectrum of relaxation time from the module of
    data from storage and loss 0 given away gives linear viscoelasticityC (^) is obtained by measurements in sweep frequency. The Principles basic From 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), which is incorporated by reference.
    [0026] IRIS RheoHub 2008 expresses the relaxation time spectrum as a sum of N Maxwell forms
    Petition 870190058423, of 06/24/2019, p. 13/42
    8/28
    The tf -1 Where g t and A É are material parameters and G 0 is the modulus of
    balance .
    [0027] The choice of the maximum number of JV forms used to
    Determination of the discrete relaxation spectrum is done using the IRIS RheoHub 2008 optimum option. The balance module G g is fixed at zero. The nonlinear adjustment used to obtain it is performed on IRIS RheoHub 2008, using the Doi-Edwards model.
    [0028] It is still preferable that the high molecular weight polypropylene component (A) has a melt strength
    F30 num 6.0 to 30 cN, preferably in a range interval 8.0 to 29.5 cN at 200 ° C, determined in the test in Rheotens, as described in the experimental part. [0029] The inventive composition comprises the component of
    high molecular weight polypropylene (A) in an amount of
    70 to 95% in bulk, preferably in an amount of 73 to
    92% by mass, and preferably in an amount of 80 to 90% by mass, based on the total amount of the composition.
    [0030] In addition, it is preferable that the
    high molecular weight polypropylene (A) has an MFR2 of 0.5 to 5.0 g / 10 min, more preferable from 1.0 to 4.5 g / 10 min, and preferably 1.5 to 4.0 g / 10min, measured in accordance with ISO 1133 (230 ° C, 2.16 kg load).
    [0031] 0 high molecular weight polypropylene component (A) can be a homo or copolymer component. In case the
    Petition 870190058423, of 06/24/2019, p. 14/42
    9/28 component of high molecular weight polypropylene (A) is a copolymer, it will typically contain ethylene and / or alpha-olefin (s) C4-C12 in an amount of 0.5 to 10% by weight.
    [0032] However, it is preferable that component (A) is a homopolymer component of polypropylene.
    [0033] According to the present invention, the linear low molecular weight isotactic polypropylene component (B) is preferably used in the composition in an amount of 8 to 27% by weight, more preferably in an amount of 10 to 20% by weight, based on the total mass of the polypropylene composition.
    [0034] In addition, the linear low molecular weight isotactic polypropylene component (B) has an MFR2 of 500 g / 10min to 5000 g / 10min, preferably 600 to 3000 g / 10min, more preferably 700 to 2500 g / 10min, measured according to ISO 1133 (230 ° C, 2.16 kg load).
    [0035] As explained above, the use of the linear low molecular weight isotactic polypropylene component (B) as a fluidity enhancer in the inventive composition generates a fluidity increase of at least three orders of magnitude, maintaining a high melt strength and conserving resistance to the impact of the composition.
    0036] Thus, the polypropylene composition according to the present invention preferably has an MFR2 of 5.0 to 30 g / 10min, more preferably of 5.5 to 25 g / 10min, and preferably 6.0 to 20 g / 10min, measured according to ISO
    1133 (230 ° C, 2.16 kg load).
    Petition 870190058423, of 06/24/2019, p. 15/42
    10/28 [0037] In addition, the linear low molecular weight isotactic polypropylene (B) component preferably has a soluble xylene content (XSC), measured as described in the experimental part, from 0.1 to 15% by mass, more preferably from 0.5 to 10% by weight, and preferably between 0.8 and 8.0%, based on the total amount of component (B).
    [0038] The polypropylene composition according to the present invention comprises the high molecular weight component (A) and the low molecular weight component (B). The terms high and low do not define absolute values, but denote the relationship between the two components with respect to their molecular masses. Each of the two components has its own molecular mass distribution.
    [0039] The molecular weight distribution MWD is defined as the ratio between the average weight molecular weight Mw and the average numerical molecular weight Μη. MWD is measured by GPC.
    [0040] The strain-hardening factor (S // F) of the inventive composition is preferably in the range of 2.0 to 9.0, more preferably of 2.3 to 8.0, measured at a strain rate 3.0 s _1 and a Hencky strain of 2.5, and preferably in a range of 1.3 to 5.0, more preferably 1.5 to 4.5, measured at a strain rate of 1.0 s _1 and Hencky deformation of 2.0.
    [0041] It is also preferable that the inventive composition has a LAOS non-linearity factor (LAOS — NLF) in a range of
    2.5 to 8.0, more preferably 3.0 to 7.0, measured according to the LAOS method, as described in the experimental part.
    Petition 870190058423, of 06/24/2019, p. 16/42
    11/28 [0042] Furthermore, it is preferable that the inventive composition has a melt strength F30 in the range of 4.0 to 30 cN, more preferable in the range of 5.0 to 25 cN at 200 ° C, determined in the test in Rheotens, as described in the experimental part.
    [0043] Furthermore, the inventive composition preferably has an impact resistance in the Charpy test with a notch of 3.5 to 10 kJ / m 2 , more preferably 3.8 to 8.5 kJ / m 2 , and preferably 4 , 0 to 7.5 kJ / m 2 at 23 ° C, measured according to ISO 179: 2000 1 eA.
    [0044] In addition, the polypropylene composition of the present invention preferably has an elastic modulus in the range of 1600 to 4000 MPa, more preferably in the range of 1700 to 3500 MPa, and preferably in the range of 1800 to 2000 MPa, measured according to with ISO 572-2.
    0045] It is also preferable that the inventive composition has a crystallization temperature in the range of 120 to 145 ° C, more preferable in the range of 125 to 140 ° C, determined in accordance with ISO 11357-1, -2 and -3.
    0046] In addition, the polypropylene composition preferably has a melting temperature in the range 150 to 175 ° C, more preferably in the range 158 to 170 ° C, determined in accordance with ISO 11357-1, -2 and -3 .
    The polypropylene composition according to the present invention can comprise additional polyolefinic components and can also contain non-polymeric additives.
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    12/28 [0048]
    The polymeric part of the polypropylene composition is denoted as a base resin.
    [0049] Preferably, the base resin consists of components (A) and (B) as described above.
    [0050] It is also preferable that both component (A) and component (B) are stabilized by suitable additives, which are preferably used in an amount of 0.05 to 2.0% by weight, more preferably in an amount of 0 , 1 to 1.0% by weight, based on the amount of each component.
    [0051] Due to the great difference in molecular mass of components (A) and (B), the base resin of the polypropylene composition has a multimodal molecular weight distribution, preferably bimodal.
    [0052] The multimodal expression used here refers to the polymer modality, that is, the shape of its molecular mass distribution curve, which is the graph of the molecular mass component as a function of its molecular mass. As will be explained below, the base resin of the present invention can be produced in a sequential step process, using reactors in series and operating under different reaction conditions. As a consequence, each component prepared in a specific reactor will have its own
    distribution in pasta molecular . When the curves in distribution in pasta molecular of these components are overlapping for get the curve mass distribution
    molecular weight of the final polymer, this curve can show one or more maximums or at least be distinctly extended when compared to the curves of the individual components. a
    Petition 870190058423, of 06/24/2019, p. 18/42
    13/28 polymer, produced in two or more steps in series, is called bimodal or multimodal, depending on the number of steps.
    [0053] The base resin of the composition in polypropylene wake up with the present invention can to be a composition multimodal preferably bimodal . [0054] The two components (A) and (B) and optionally
    Additional components can be produced in separate steps and mixed after composition polymerization.
    [0055] Alternatively and preferably, the two components (A) and (B) and optionally additional components are produced in different reactors each, reactors which are connected in series, and each component is produced in the presence of the product of the reactor (s) preceding (s), except for the first component.
    [0056] The preferred multistage process described is a “gas-loop-phase” process, as developed by Borealis A / S, Denmark (known for BORSTAR® technology) described, for example, in the patent literature, as in EP 0 887 379 or WO 92/12182. Optionally, the process may also comprise a prepolymerization step in a manner known in the art and which may precede the first polymerization step (a).
    [0057] It is preferable that the polymerization catalyst is a Ziegler-Natta catalyst, as described, for example, in WO 92/19653, or a single site catalyst, as described, for example, in EP 09013647 or EP 1741725 A1 .
    0058] As already indicated above, the polypropylene composition can comprise conventional adjuvants, as well as
    Petition 870190058423, of 06/24/2019, p. 19/42
    14/28 additional additives, fillers and reinforcing agents or impact modifiers.
    [0059] These modifiers and / or additives can be included during the polymerization process or after the polymerization by mixing the molten material. Suitable modifiers include other thermoplastics such as polyethylene homo or copolymers, poly-1-butene, poly-4-methylpentene-1 and / or thermoplastic elastomers such as ethylene-propylene rubber or styrene elastomers, as well as mineral fillers such as talc or carbonate calcium. Suitable additives include stabilizers, lubricants, nucleating agents, pigments and foaming agents. Such additives will normally be present in the final composition in an amount of 0.05 to 2.0% by weight, preferably 0.1 to 10% by weight, based on the total amount of the composition.
    [0060] The compositions of the present invention are preferably used for the production of molded articles, preferably injection molded articles.
    Experimental Part
    Measurement Methods
    a) Flow Rate [0061] The flow rate is measured as the MFR2, according to ISO 1133 (230 ° C, 2.16 kg load) for polypropylene, and 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.
    Petition 870190058423, of 06/24/2019, p. 20/42
    15/28
    b) Comonomer Content [0062] 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.
    [0063] The calibration procedure, based on results obtained from 13 C-NMR spectroscopy, was performed in the conventional manner well documented in the literature.
    [0064] The amount of the comonomer (JV) was determined as a percentage by mass (% by mass) by:
    í -) + ^ 2 VR / where A is the maximum defined absorbance of the comonomer range, fi is the maximum absorbance defined as the reference peak height and with the linear constants q and 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.
    c) Xylene Soluble Fraction [0065] The xylene soluble fraction (XCS), as defined and described in the present invention, is determined as follows: 2.0 g of polymer were dissolved in 250 ml of 135 ° p-xylene C under agitation. After 30 minutes, the solution was cooled for 15 minutes at room temperature and then left to stand for 30 minutes at 25 ± 0.5 ° C with stirring. The solution
    Petition 870190058423, of 06/24/2019, p. 21/42
    16/28 was filtered with filter paper in two 100 ml flasks. The solution of the first 100 ml container was evaporated by nitrogen injection and the residue was vacuum dried at 90 ° C until constant mass was reached. The fraction soluble in xylene (percent) can be determined as follows:
    100 X m. | X v n
    XCS ----------- rrijj X where designates the amount of initial polymer (grams), mL defines the residue mass (grams), defines the initial volume (milliliters) and defines the volume of the sample analyzed ( milliliters). The fraction insoluble in p-xylene at 25 ° C (XCU) is then equal to 100% - XCS%.
    d) branching index [0066] The branching index indicates the number of long chain branches per 1000 carbon atoms. Both parameters can be determined from a combination of size exclusion chromatography (SEC) at high temperature with viscosimetry. Basic SEC investigations are carried out at 135 ° C on 1,2,4-trichlorobenzene with solutions of 0.25 g / dl concentration. Molecular weight distributions are calculated from the results of a refractometric detector using the universal calibration method adjusted for polypropylene. Parallel to this, the intrinsic viscosity of the complete polymer is determined at 135 ° C in 1,2,4-trichlorobenzene with solutions of 0.05 g / dl concentration.
    e) Strain Hardening Factor (5HF)
    Petition 870190058423, of 06/24/2019, p. 22/42
    17/28 [0067] The strain hardening factor is defined as =
    VlVe (. ^ Where ^ (ί, έ) is the uniaxial extensional viscosity; and it is three times the time-dependent shear viscosity 77 + (t) in the linear strain range.
    [0068] The determination of linear viscoelasticity in VlveCQ extension / using IRIS Rheo Hub 2008, requires the calculation of the discrete relaxation time spectrum from the storage and loss data module (G f , G ff (a>)). The linear viscoelasticity data (G f , G ff (üj)) is obtained by frequency scanning measurements carried out at 180 ° C, in 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), which is fully incorporated as a reference.
    [0069] IRIS RheoHub 2008 expresses the relaxation time spectrum as a sum of N forms of Maxwell o N _L
    G (t) = G e . £ g, .e * · where βι and 4 É are material parameters and G g is the equilibrium module.
    Petition 870190058423, of 06/24/2019, p. 23/42
    18/28 [0070] 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 g is fixed at zero.
    [0071] The non-linear adjustment used to obtain θ performed on IRIS RheoHub 2008, using the Doi-Edwards model.
    [0072] The uniaxial extensional viscosity is obtained from uniaxial extensional flow measurements, conducted on an Anton Paar MCR 501 coupled with Sentmanat extensional fixation (SER-1). The temperature for the uniaxial extensional flow measurements was fixed at 180 ° C, ds applying extension rates (deformation) - in a range of 0.3 s _1 to 10 s _1 and covering a deformation range of
    Hencky with the original fixing length of the sample being the actual fixing length, from 0.3 to 3.0. 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.
    f) LAOS non-linear viscoelastic ratio
    Petition 870190058423, of 06/24/2019, p. 24/42
    19/28 [0073] The investigation of nonlinear viscoelastic behavior under shear flow was performed using the Large Amplitude Oscillatory Shear. The method requires the application of a sinusoidal strain amplitude, y a , imposed at a given angular frequency, ω, for a given time, t. As long as the applied sinusoidal strain is high enough, 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 [1-4] can be expressed by a Fourier series, which includes the greatest harmonic contributions:
    σ (£,
    ηωή + G. cos (ntwt)] with, a - voltage response t - time ω - frequency
    Xo - strain range n - harmonic number
    G - elastic Fourier coefficient of order n
    G ff n - viscous Fourier coefficient of order n [0074] The non-linear viscoelastic response was analyzed by applying Large Amplitude Oscillatory Shear (LAOS).
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    20/28
    Time scan measurements were performed on an Alpha Tecnologies RPA 2000 rheometer coupled with 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. The Large Amplitude Oscillatory Shear Factor (LAOS-NFL) is defined as:
    LAOS-NLF = where first order Fourier coefficient £ j f a - third order Fourier coefficient
    1. J. M. Dealy, K. F. Wissbrun, Melt Rheology and Its Role in Process Plastics: Theory and Applicatons; 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, Procedures of the Annual European Rheology Conference, 135 (2010)
    g) Rheotens test
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    21/28 [0075] The test described here follows ISO 16790: 2005.
    [0076] The deformation hardening behavior is determined by a method such as that 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 a 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.
    [0077] The experiment at Rheotens simulates industrial spinning (spinning) and extrusion processes. At first, a melt is pressed and extruded through a round die and the resulting filament 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 laboratory extruder HAAKE Polylab 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 line of spin (spine) 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 slowly increasing the adhesion speed of the Rheotens' wheels until the polymeric filament ruptured. The acceleration
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    22/28 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 as values for melt strength and drag speed.
    h) Melting temperature, crystallization temperature [0078] 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 / cooling / 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.
    i) Charpy notch impact resistance [0079] Charpy impact resistance was determined according to ISO 179-1eA: 2000 in samples with 80x10x4 mm 3 V notches at 23 ° C (Charpy NIS + 23 ° C) and a standard impact speed of 2.9 m / s. The test samples were prepared by injection molding in accordance with ISO 1872-2, using a melting temperature of 200 ° C and a mold temperature of 40 ° C.
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    23/28
    j) Tensile test, tensile strength and elastic modulus [0080] The tensile strength at break is measured according to ISO 572-2 (cross-slit speed of 50 mm / min at 23 ° C). The modulus of elasticity is measured according to ISO 572-2 (cross slot speed of 1 mm / min at 23 ° C) using injection molded samples as described in EN ISO 1872-2 (dog bone shape, 4 mm thick).
    k) Density [0081] The density of the polymer was measured according to ISO 1183 / D.
    Examples [0082] The polypropylene compositions according to the present invention were produced by mixing both fused polypropylene components (A) and (B).
    [0083] The low molecular mass component (B) was produced using a single site catalyst (SSC) or a Ziegler-Natta catalyst (ZNC) as a polymerization catalyst, whereas for the high molecular mass component (A) , a Daploy WB135HMS category of high strength polypropylene of the cast was used.
    a) Component (A) [0084] Daploy WB135HMS is a high strength polypropylene homopolymer of the melt provided by Borealis Polyolefine GmbH (Austria), having an MFR (230 ° C / 2.16 kg) of 2.4 g / lOmin and a density of 905 kg / m 3 . It has a long chain branch structure with a g f value of 0.8, a
    Petition 870190058423, of 06/24/2019, p. 29/42
    24/28 resistance of the F30 melt of 28.6 cN as determined in the Rheotens test at 200 ° C, a SHF of 6.5 when measured at a strain rate of 3.0 s _1 and a Hencky strain of 2.5 , a SHF of 3.6 when measured at a strain rate of 1.0 s _1 and a Hencky strain of 2.0, and a LAOS - NFL of
    4.93.
    b) Component (B)
    VPPP ssc [0085] The experimental polypropylene homopolymer VPPP SSC was produced in a Borstar PP pilot plant as follows:
    [0086] The catalyst, as described in example 1 of EP 1741725 Al, was fed together with triethyl aluminum as a cocatalyst, in a ratio and Al / Zr [mol / mol] of 910, in a tank prepolymerization reactor stirred with propylene and hydrogen at a rate of 0.2 mol / kmol of propylene, the reactor being operated at 35 ° C with an average residence time of 0.4 hours.
    [0087] The main stage of polymerization was carried out in a loop reactor at a temperature of 70 ° C and a pressure of 6000 kPa, feeding additional propylene at 150 kg / h with hydrogen in a ratio of 0.70 mol / kmol of propylene, maintaining an average residence time of 0.65 hours, reaching a catalyst productivity of 17.5 kg / g.
    [0088] After deactivating the catalyst with steam and drying the resulting powdered polymer with heated nitrogen, the resulting polypropylene homopolymer was combined together with 0.07% by weight of calcium stearate and 0.60%
    Petition 870190058423, of 06/24/2019, p. 30/42
    25/28 of Irganox B225 (antioxidant combination provided by Ciba Specialty Chemicals) in a twin screw extruder at 230 to 250 ° C.
    [0089] The resulting propylene homopolymer has an MFR (230 ° C / 2.16 kg) of 710 g / 10min, a density of 902 kg / m 3 , a melting point of 152 ° C and an XS content of 1.0% by mass.
    VPPP ZNC [0090] The experimental propylene homopolymer VPPP ZNC was produced in a Borstar PP pilot plant as follows:
    [0091] The catalyst used in the polymerization was prepared according to WO 92/19653 with dioctyl phthalate as dialkyl phthalate of the formula (III) and ethanol as alcohol, the cocatalyst was triethyl aluminum and, as an external donor (ED), diethylaminotriethoxysilane was used.
    [0092] The combination of catalysts, having an Al / Ti ratio of 45 mol / mol and an Al / ED ratio of 30 mol / mol, was fed at a rate of 8.3 g / h in a tank prepolymerization reactor stirred together with propylene and hydrogen at a rate of 0.4 mol / kmol of propylene, the reactor being operated at 30 ° C with an average residence time of 0.37 hours.
    [0093] The first part of the main polymerization step was carried out in a loop reactor at a temperature of 75 ° C and a pressure of 5600 kPa, feeding additional propylene at 150 kg / h with hydrogen in a ratio of 30 mol / kmol of propylene , and maintaining an average residence time of 0.33 hours.
    Petition 870190058423, of 06/24/2019, p. 31/42
    26/28 [0094] This was followed by the second part of the main polymerization step in a gas phase reactor at a temperature of 90 ° C and a pressure of 1900 kPa, feeding additional propylene at 30 kg / h with hydrogen at a ratio of 160 mol / kmol of propylene, and maintaining an average residence time of 0.7 hours. Total catalyst productivity of 4.0 kg / g has been achieved.
    [0095] After deactivating the catalyst with steam and drying the resulting powdered polymer with heated nitrogen, the resulting polypropylene homopolymer was combined together with 0.07% by weight of calcium stearate and 0.60% of Irganox B225 ( antioxidant combination provided by Ciba Specialty Chemicals) in a twin screw extruder at 230 to 250 ° C.
    [0096] The resulting propylene homopolymer has an MFR (230 ° C / 2.16 kg) of 2300 g / 10min, a density of 904 kg / m 3 , a melting point of 158 ° C and an XS content of 7.2% by mass.
    c) Composition [0097] The inventive compositions are produced by mixing the melted material WB135HMS as component (A) with VPPP SSC or VPPP ZNC as component (B). The comparative example CE1 is related to a composition including only component (A).
    [0098] Table 1 lists the compositions of the examples and their respective MFR values (230 ° C / 2.16 kg).
    Petition 870190058423, of 06/24/2019, p. 32/42
    27/28
    Table 1: Composition and values of the MFR of the comparative example
    CE1 and inventive examples IE1 to IE6.
    Component CE1 IE1 IE2 IE3 IE4 IE5 IE6 WB135HMS[% in large scale] 100 90 85 80 90 85 80 VPPP SSC[% in large scale] 0 10 15 20 0 0 0 VPPP ZNC[% in large scale] 0 0 0 0 10 15 20 MFR[g / 10min] 2.4 8.0 8.7 12.5 7.4 10.6 11.3
    [0099] As can be seen from Table 1, the flow rate of the high molecular weight polypropylene component increases when the component is mixed with a linear low molecular weight isotactic polypropylene component, having a high flow rate.
    [0100] Furthermore, it can be demonstrated that the addition of low molecular weight material (component (B)) led to an increase of 5 orders of magnitude of the MFR, maintaining a high melt strength and the same degree of impact resistance (cf. Table 2). The effect is more or less independent of the type of resin-LMW (ie based on catalyst-SS or catalyst-ZN).
    Petition 870190058423, of 06/24/2019, p. 33/42
    28/28
    Table 2: Thermal, mechanical and rheological characterization of the examples.
    Component CE1 IE1 IE2 IE3 IE4 IE5 IE6 MFR[g / 10min] 2.4 8.0 8.7 12.5 7.4 10.6 11.3 Tm (DSC)[° C] 162 162 161 161 162 163 163 TC (DSC)[° C] 127 127 128 127 128 128 128 Mod. elasticity[MPa] 2166 1876 1881 1873 1915 1923 1963 Breaking stress[MPa] 43.3 39.8 39.8 39.6 40.5 40.5 41.1 Charpy NIS + 23 ° C [kJ / m 2 ] 4.5 4.8 4.7 4.4 4.9 4.6 4.0 SHF (3 / 2.5)[-] 6.5 n.d. 2.6 n.d. n.d. 2.8 n.d. SHF (1/2)[-] 3.6 n.d. 1.8 n.d. n.d. 2.4 n.d. LAOS NLF[-] 4.93 n.d. 4.06 n.d. n.d. 3.96 n.d. F30[cN] 28.6 n.d. 15.2 n.d. n.d. 13.2 n.d.
    Petition 870190058423, of 06/24/2019, p. 34/42
    权利要求:
    Claims (15)
    [1]
    1. Polypropylene composition characterized by comprising (a) 70 to 95% by weight, based on the total mass of the polypropylene composition, of a high molecular weight polypropylene component with a stress hardening factor in a range of 3, 5 to 15, when measured at a stress rate of 3.0 s -1 and a Hencky stress of 2.5, and
    b) 5% by weight to 30% by weight, based on the total mass of the polypropylene composition, of a linear low molecular weight isotactic polypropylene component with MFR2 in a range of 500 to 5000 g / 10 min, measured according to with ISO 1133 (230 ° C, 2.16kg load).
    [2]
    2. Polypropylene composition according to claim 1, characterized by having an MFR2 of 5.0 to
    30 g / 10 min, measured according to ISO 1133 (230 ° C,
    2.16kg of load).
    [3]
    Polypropylene composition according to claim 1 or 2, characterized in that the high molecular weight polypropylene component (A) has an MFR2 of 0.5 to
    5.0 g / 10 min, measured according to ISO 1133 (230 ° C,
    2.16kg of load).
    [4]
    Polypropylene composition according to any one of claims 1 to 3, characterized in that the high molecular weight component (A) has a non-linearity factor LAOS (LAOS-NLF) in a range of 4.0 to 10.
    Petition 870190058423, of 06/24/2019, p. 35/42
    2/3
    [5]
    Polypropylene composition according to any one of claims 1 to 4, characterized in that the high molecular weight component (A) has a melt resistance F30, as determined in the Rheotens test at 200 ° C, in a range of 6 , 0 to 30 cN.
    [6]
    Polypropylene composition according to any one of claims 1 to 5, characterized in that the high molecular weight polypropylene component is a homopolymer component.
    [7]
    7. Polypropylene composition according to any one of claims 1 to 6, characterized in that the polypropylene composition has a Charpy impact resistance with a notch of 3.5 to 10kJ / m 2 at 23 ° C, measured in a body of injected proof, according to ISO 179: 2000 1eA.
    [8]
    8. Polypropylene composition according to any one of claims 1 to 7, characterized in that the polypropylene composition has an elasticity modulus in the range of 1600 to 4000 MPa, measured in an injected specimen, according to ISO 572-2.
    [9]
    Polypropylene composition according to any one of claims 1 to 8, characterized in that the polypropylene composition has a crystallization temperature in the range of 120 to 145 ° C.
    [10]
    10. Polypropylene composition according to any one of claims 1 to 9, characterized in that the polypropylene composition has a strain-hardening factor (SHF) in the range of 2.0 to
    Petition 870190058423, of 06/24/2019, p. 36/42
    3/3
    9.0, when measured at a stress rate of 3.0 s 1 and a Hencky stress of 2.5.
    [11]
    11. Polypropylene composition according to any one of claims 1 to 10, characterized in that the polypropylene composition has a LAOS non-linearity factor (LAOS-NLF) in a range of 2.5 to 8.0.
    [12]
    Polypropylene composition according to any one of claims 1 to 11, characterized in that the polypropylene composition has a melt strength F30, as determined in the Rheotens test at 200 ° C, in a range of 4.0 to 30 cN .
    [13]
    13. Article characterized by being made from the polypropylene composition as defined in claims 1 to 12.
    [14]
    14. Use of low molecular weight linear isotactic polypropylene characterized by the low molecular weight linear isotactic polypropylene having an MFR2 in a range of 500 to 5000 g / 10 min, measured according to ISO
    1133 (230 ° C, 2.16 kg load), and because the high molecular weight polypropylene has a stress-hardening factor in the range of 3.5 to 15, when measured at a stress rate of 3.0 s -1 and a Hencky tension of 2.5.
    [15]
    15. Use of low molecular weight linear isotactic polypropylene according to claim 14, characterized in that low molecular weight linear isotactic polypropylene is used in an amount of 5 to 30% by weight, based on the total mass of linear isotactic polypropylene low molecular weight and high molecular weight polypropylene.
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    同族专利:
    公开号 | 公开日
    EP2386601B1|2012-07-04|
    EP2386601A1|2011-11-16|
    CN102971372A|2013-03-13|
    EA022013B1|2015-10-30|
    US20130123431A1|2013-05-16|
    WO2011141044A1|2011-11-17|
    CN102971372B|2015-01-07|
    BR112012028742A2|2017-10-24|
    US8722805B2|2014-05-13|
    KR101460873B1|2014-11-11|
    KR20130019436A|2013-02-26|
    EA201291029A1|2013-05-30|
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    法律状态:
    2019-04-24| B06T| Formal requirements before examination [chapter 6.20 patent gazette]|
    2019-07-30| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|
    优先权:
    申请号 | 申请日 | 专利标题
    EP10004991A|EP2386601B1|2010-05-11|2010-05-11|High flowability long chain branched polypropylene|
    EP10004991.5|2010-05-11|
    PCT/EP2010/007227|WO2011141044A1|2010-05-11|2010-11-29|High flowability long chain branched polypropylene|
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