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    • 专利摘要:
    POLYOLEFINE COMPOSITION. The invention relates to a polyolefin composition comprising a first heterophasic propylene copolymer and a second heterophasic propylene copolymer, wherein the first heterophasic propylene copolymer comprises: from 70-90% by weight of a first polypropylene having an index of melting flow of 5585 g / 10min, measured according to ISO 1133 (2.16kg and 230 ° C), 10-30% by weight of a first ethylene- (Alpha) olefin copolymer having a melt flow index 2.5-5.0 g / 10min according to ISO 1133 (2.16kg and 230 ° C), the respective amounts of the first polypropylene and first ethylene (Alpha) -olefin copolymer being based on the weight of the first carbon copolymer heterophasic propylene, and the second heterophasic propylene copolymer comprises: 60-85% by weight of a second polypropylene having a melt flow index of 50-100g / 10min, measured according to ISO 1133 (2.16kg, 230 ° C), 15-40% by weight of a second ethylene- (Alpha) -olefin copolymer having a melt flow index of 0.050-0.30 g / 10min according to ISO 1133 (2.16kg and 230 ° C), the respective amounts of the second polypropylene and second ethylene (Alpha) -olefin copolymer being based on the weight of the second heterophasic propylene copolymer, and a weight ratio of (...).
    公开号:BR112016013611B1
    申请号:R112016013611-0
    申请日:2014-12-10
    公开日:2021-01-05
    发明作者:Peter Neuteboom；Pieter Valkier
    申请人:Saudi Basic Industries Corporation；Sabic Global Technologies B.V.；
    IPC主号:
    专利说明:

    The present invention relates to a polyolefin composition comprising a first heterophasic polypropylene copolymer and a second heterophasic polypropylene copolymer. The present invention also relates to a heterophasic propylene copolymer containing a rubber phase of relatively high viscosity. The present invention also relates to a heterophasic propylene copolymer containing a rubber phase of relatively low viscosity.
    [002] In the automotive industry, polypropylene-based materials are often used for their desirable combination of good mechanical properties and low cost. In particular, so-called impact propylene copolymers are often used in applications such as bumper fenders and instrument panels. Needs for automotive applications include low Linear Thermal Expansion Coefficient (CLTE), good impact resistance, good rigidity, scratch resistance and good optical surface properties. In order to obtain a low CLTE along with the desired mechanical properties, polypropylene based materials usually contain a certain amount of inorganic filler, such as in particular talc.
    [003] The addition of talc, however, is known to deteriorate the optical surface properties. In particular, this increases the risk for so-called "tiger stripes (TS)". Tiger stripes as used here refer to variations in color and gloss on the surface of an injection molded article, which occurs because of the unstable mold filling properties of the molten polymer as it is being injected into the mold and formed into the desired shape. . Usually these variations can be observed as alternating areas of low and high brightness and / or light or dark color, where the areas are usually substantially perpendicular to the flow direction of an injection molded article. Tiger stripes can also be referred to as tiger marks or tiger (flow) markings.
    [004] Tiger stripes typically occur in materials based on polypropylene containing polypropylene, a rubber dispersed in polypropylene and an inorganic filler, in particular talc.
    [005] Examples of such an appearance and a more scientific debate on the cause of tiger stripes can be found in the publication by Hirano et al, Journal of Applied Polymer Science, Vol. 104, 192 199 (2007). Another publication entitled "Morphological Analysis of TigerStripe and Striped Pattern Deterioration on injection Molding of Polypropylene / Rubber / Talc Blends" in the name of K. Hirano, Y. Suetsugu, S. Tamura and T. Kanai, provides further background on the matter.
    [006] Solutions for the reduction of tiger stripes have been proposed in the prior art.
    [007] WO02 / 28958, WO2004 / 087805 and WO2010 / 0108866 provide a solution that generally consists of providing a standard batch that can be diluted with additional polyolefins in order to provide a compound having the performance and mechanical properties of tiger stripe desired.
    [008] WO2013 / 079539 discloses a polyolefin composition comprising a. 35 to 90% by weight, based on the weight of the polyolefin composition, of a heterophasic polypropylene composition comprising i. 10 to 50% by weight, based on the weight of the heterophasic polypropylene composition, of a first polypropylene (PP1) having an MFR2 measured according to ISO 1133 from 30 to 80 g / 10 min (230 ° C, 2.16 kg ), ii. 20 to 65% by weight, based on the weight of the heterophasic polypropylene composition, of a second polypropylene (PP2) having an MFR2 measured according to ISO 1133 from 100 to 250 g / 10 min (230 ° C, 2.16 kg ), iii. 5 to 30% by weight, based on the weight of the heterophasic polypropylene composition of a first cold soluble xylene fraction (XS1) having an intrinsic IVXS1 viscosity of 2.0 to 3.0 dl / g, iv. 5 to 25% by weight, based on the weight of the heterophasic polypropylene composition of a second cold soluble fraction of xylene (XS2) having an intrinsic viscosity IVxs2 of 1.5 to 2.8 d / g, with the proviso that IVxsi # IVXS2, b. 5 to 40% by weight, based on the weight of the polyolefin composition, of an inorganic filler, and c. 5 to 25% by weight, based on the weight of the polyolefin composition, of an ethylene / propylene elastomer.
    [009] US 2002/0035209 discloses a polypropylene resin composition containing two types of specific propylene-ethylene block copolymers having mutually different structures. More particularly, this reference discloses a polypropylene resin composition providing a molded article excellent in appearance when formed into a molded article because flow marks hardly generate, in other words, a mold swelling is high and few fish eyes do. More particularly this reference discloses a polypropylene resin composition comprising:
    [0010] 95 to 80% by weight of a polypropylene resin (A) selected from the group consisting of a propylene-ethylene block copolymer (i) having a propylene homopolymer portion
    [0011] and propylene-ethylene random copolymer portion, and a mixture (ii) of the propylene-ethylene block copolymer (i) and a propylene homopolymer, wherein an intrinsic viscosity [n] AEP of the homopolymer portion of propylene when resin (A) is copolymer (i), or the total portion of propylene homopolymer and propylene homopolymer when resin (A) is mixture (ii) is not more than 1.3 dl / g, and an intrinsic viscosity [n] AEP of the random propylene-ethylene copolymer portion is no more than 3.0 dl / g; and
    [0012] 5 to 20% by weight of a propylene-ethylene block copolymer (B) composed of a portion of propylene homopolymer and portion of random propylene-ethylene copolymer in which an intrinsic viscosity [n] BEP of the random copolymer propylene-ethylene is 8.0 to 15 dl / g, and where the polypropylene resin composition has a melt flow rate (MFR) of 5.0 to 150 g / 10 min., and the sum of ( A) and (B) is 100% by weight.
    [0013] EP 2495280 discloses a polyolefin composition comprising a. 35 to 90% by weight, based on the weight of the polyolefin composition, of a heterophasic polypropylene composition comprising i. 10 to 50% by weight, based on the weight of the heterophasic polypropylene composition, of a first propylene homopolymer (PPH1) having an MFR2 measured according to ISO 1133 from 30 to 80 g / 10 min (230 ° C, 2, 16 kg), ii. 20 to 65% by weight, based on the weight of the heterophasic polypropylene composition, of a second propylene homopolymer (PPH2) having an MFR2 measured according to ISO 1133 from 100 to 250 g / 10 min (230 ° C, 2, 16 kg), iii. 5 to 30% by weight, based on the weight of the heterophasic polypropylene composition of a first cold soluble xylene fraction (XS1) having an intrinsic IVXS1 viscosity of 2.0 to 3.0 dl / g, iv. 5 to 25% by weight, based on the weight of the heterophasic polypropylene composition of a second cold soluble xylene fraction (XS2) having an intrinsic IVXS2 viscosity of 1.5 to 2.8 dl / g, with the proviso that IVxsi # IVXS2 b. 5 40% by weight, based on the weight of the polyolefin composition, of an inorganic filler, and c. 5 to 25% by weight, based on the weight of the polyolefin composition, of an ethylene / 1-butene elastomer.
    [0014] Tiger stripes are undesirable in automotive applications, particularly in the case where the material based on polypropylene is not provided with an additional layer such as paint or a lamination layer.
    [0015] At the same time automotive applications differ in terms of mechanical requirements and melt flow rate, such that there is a need for material suppliers to have the opportunity to satisfy the combination of good tiger stripe performance, satisfy properties of flow rate and mechanics, in particular rigidity and impact properties, while at the same time maintaining a reasonable cost level.
    [0016] Therefore, it is an objective of the present invention to provide a polyolefin composition that allows the manufacture of automotive parts having good tiger stripe performance while being able to satisfy a variety of mechanical and melt flow properties.
    [0017] It is in particular an object of the present invention to provide a polyolefin composition including both an ethylene-propylene elastomer and an inorganic filler which, when molded into a final piece for automotive application, exhibits good tiger stripe performance.
    [0018] It is another objective to supply a heterophasic propylene copolymer with a reduced tiger streak problem, which is suitable for impact resistant applications, such as automotive parts such as bumper fenders.
    [0019] Yet another objective of the present invention is to provide a polyolefin composition that exhibits good tiger stripe performance as well as good scratch resistance.
    To that extent, the present invention provides a polyolefin composition comprising a first heterophasic propylene copolymer and a second heterophasic propylene copolymer,
    [0021] wherein the first heterophasic propylene copolymer comprises: from 70 to 90% by weight of a first polypropylene having a melt flow index of 55 to 85 g / 10 min as measured according to ISO 1133 (2 , 16 kg and 230 ° C), from 10 to 30% by weight of a first ethylene-α-olefin copolymer having a melt flow index of 2.5 to 5.0 g / 10 min according to ISO 1133 (2.16 kg and 230 ° C),
    [0022] the respective amounts of first polypropylene and first ethylene-α-olefin polymer being based on the weight of the first heterophasic propylene polymer,
    [0023] and wherein the second heterophasic propylene copolymer comprises: from 60 to 85% by weight of a second polypropylene having a melt flow index of 50 to 100 g / 10 min as measured according to ISO 1133 ( 2.16 kg, 230 ° C), from 15 to 40% by weight of a second ethylene-α-olefin copolymer having a melt flow index of 0.050 to 0.30 g / 10 min according to ISO 1133 (2.16 kg and 230 ° C),
    [0024] the respective amounts of second polypropylene and second ethylene-α-olefin copolymer being based on the weight of the second heterophasic propylene copolymer,
    [0025] wherein preferably a weight ratio of said first and second heterophasic propylene copolymer is from 1 to 10.
    [0026] In a preferred embodiment the present invention provides a polyolefin composition comprising a first heterophasic propylene copolymer and a second heterophasic propylene copolymer,
    [0027] wherein the first heterophasic propylene copolymer comprises: from 70 to 90% by weight of a first polypropylene having a melt flow index of 55 to 85 g / 10 min as measured according to ISO 1133 (2 , 16 kg and 230 ° C), from 10 to 30% by weight of a first ethylene-α-olefin copolymer having a melt flow index of 2.5 to 4.0 g / 10 min according to ISO 1133 (2.16 kg and 230 ° C),
    [0028] the respective amounts of the first polypropylene and first ethylene-α-olefin polymer being based on the weight of the first heterophasic propylene polymer,
    [0029] and wherein the second heterophasic propylene copolymer comprises: from 60 to 85% by weight of a second polypropylene having a melt flow index of 50 to 80 g / 10 min as measured according to ISO 1133 ( 2.16 kg, 230 ° C), from 15 to 40% by weight of a second ethylene-α-olefin copolymer having a melt flow index of 0.050 to 0.30 g / 10 min according to ISO 1133 (2.16 kg and 230 ° C),
    [0030] the respective amounts of the second polypropylene and second ethylene-α-olefin copolymer being based on the weight of the second heterophasic propylene copolymer,
    [0031] wherein preferably a weight ratio of said first and second heterophasic propylene copolymer is from 1 to 10.
    [0032] The present inventors have found that the application of two categories of heterophasic propylene composition all having distinct and different characteristics allows the melting flow and mechanical properties to be adjusted to a desired level while at the same time maintaining good tiger stripe performance .
    [0033] Therefore, by application of the present inventors at least part of the previously mentioned objectives is satisfied.
    [0034] The term heterophasic propylene copolymer is known in the art. A heterophasic propylene copolymer basically has at least a two-phase structure, consisting of a propylene-based matrix (semicrystalline) and a dispersed rubber phase, typically an ethylene-α-olefin rubber, such as an ethylene- propylene (EPR). These heterophasic polypropylenes are generally prepared in a series of reactors, by polymerization of propylene in the presence of a catalyst system, and subsequent polymerization of a propylene-α-olefin mixture. However, they can also be manufactured by combining different (co) polymers. The advantage of heterophasic polypropylene is improved impact resistance, especially at lower temperatures.
    [0035] Higher amounts of dispersed phase generally result in improved impact properties. However, at the same time tiger stripe stiffness and performance can deteriorate. Consequently, the matrix and phase ratio dispersed in a heterophasic polypropylene can be used as a tool to tune the balance between stiffness and impact resistance. First heterophasic propylene copolymer.
    [0036] The first heterophasic propylene copolymer comprises a first polypropylene having a melt flow index of 55 to 85 g / 10 min as measured according to ISO 1133 (2.16 kg; 230 ° C). In addition it comprises a first ethylene-αolefin copolymer having a relatively high melt flow index of 2.5 to 5.0 g / 10 min, preferably 2.5 to 4.0 g / 10 min, preferably 3 , 0 to 4.0 g / 10 min, according to ISO 1133 (2.16 kg; 230 ° C). As a consequence of its composition, the first heterophasic propylene copolymer allows a combination of good impact properties as well as a relatively high melt flow index.
    [0037] The melt flow index of the ethylene-αolefin copolymer is said to be "in accordance with ISO1133" for the reason that this melt flow index was calculated rather than actually measured. The calculation was performed as follows:
    [0038] Log (MFIcopol) = Xmatrix * Log (MFImatrix) + Xdispersed * Log (MFIdispersed)
    [0039] Where:
    [0040] MFIcopol = Melt flow index of heterophasic propylene copolymer
    [0041] MFImatrix = Melt flow index of the matrix phase, ie the first polypropylene
    [0042] MFIdispersed = Melt flow index of the dispersed to be calculated
    [0043] Xmatriz and Xdisperso represent the fractions by weight of the matrix and dispersed phase respectively.
    [0044] The amount of the first polypropylene is preferably 75 to 85% by weight.
    [0045] The amount of the first ethylene-α-olefin copolymer is preferably 15 to 25% by weight.
    [0046] The first polypropylene is a propylene homopolymer or a propylene-α-olefin copolymer having a propylene content of at least 97% by weight, based on the weight of the first polypropylene.
    [0047] The first ethylene-α-olefin copolymer is preferably an ethylene-propylene copolymer having an ethylene content of 40 to 65% by weight, preferably 40 to 60% by weight, more preferably 50 to 58% by weight , based on the weight of the ethylenepropylene copolymer.
    [0048] The first heterophasic propylene copolymer is preferably a reactor grade copolymer.
    [0049] The first heterophasic propylene copolymer is preferably an unsubstituted or non-visceduced copolymer. The term non-viscorreduced is known in the art, yet to avoid doubts this means that the materials have not been treated such as to modify the molecular weight and / or the molecular weight distribution of the polymer directly after polymerization. In other words, non-viscored polymers are not treated with peroxides, radiation, or any other initiating source for chain break reactions to occur. An advantage of non-viscored polypropylenes over viscored polypropylenes is that the former generally suffer less from the release of low molecular weight materials, such materials being inherently produced during viscoreduction. For the avoidance of doubt, the term reactor grade involves that the copolymer is non-viscored (or not replaced).
    [0050] For the purpose of the present invention the combined amount of first polypropylene and first ethylene-αolefin copolymer in the first heterophasic propylene copolymer is substantially 100% by weight based on the weight of the first heterophasic propylene copolymer. In addition to the first polypropylene and first ethylene-α-olefin copolymer, no other material is comprised in the first heterophasic propylene copolymer except for a small optional amount of stabilizers and / or additives common in the art.
    [0051] The previously mentioned preferred features can be combined in any way and any combination is considered to be disclosed here.
    [0052] While it is preferred that the first heterophasic propylene copolymer is comprised of a single material, that is, a single grade, a combination of more than a first heterophasic propylene copolymer can also be considered and should be considered to fall in scope of the present invention. Second heterophasic propylene copolymer.
    [0053] The second heterophasic propylene copolymer comprises a second polypropylene having a melt flow index of 50 to 100 g / 10 min as measured according to ISO 1133 (2.16 kg; 230 ° C). In addition, it contains a second ethylene-αolefin copolymer having a relatively low melt flow index of 0.05 to 0.30 g / 10 min according to ISO 1133 (2.16 kg; 230 ° C). As a consequence of its composition, the second heterophasic propylene, when used in combination with the first heterophasic propylene copolymer, allows impact properties to be tuned to the desired level.
    [0054] The melt flow index of the ethylene-αolefin copolymer is said to be "in accordance with ISO1133" for the reason that this melt flow index was calculated rather than actually measured. The calculation was performed as follows:
    [0055] Log (MFIcopol) = Xmatrix * Log (MFImatrix) + Xdispersed * Log (MFIdispersed)
    [0056] Where:
    [0057] MFIcopol = melt flow index of heterophasic propylene copolymer
    [0058] MFImatrix = Melt flow index of the matrix phase, ie the second polypropylene
    [0059] MFIdispersed = Melt flow index of the dispersed to be calculated
    [0060] Xmatriz and Xdisperso represent the weight fractions of the matrix and dispersed phase respectively.
    [0061] The amount of the second polypropylene is preferably 65 to 80% by weight.
    [0062] The amount of the second ethylene-α-olefin copolymer is preferably from 20 to 35% by weight, more preferably 25 to 35% by weight, more preferably from 30 to 35% by weight.
    [0063] The second polypropylene is a propylene homopolymer or a propylene-α-olefin copolymer having a propylene content of at least 97% by weight, based on the weight of the first polypropylene.
    [0064] The second ethylene-α-olefin copolymer is preferably an ethylene-propylene copolymer having an ethylene content of 30 to 65% by weight, preferably from 30 to 50% by weight, more preferably from 35 to 40% by weight. weight, based on the weight of the ethylene-propylene copolymer. The present inventors have found that a lower ethylene content, i.e. a higher propylene content, allows the rubber particles to be more finely dispersed in the second polypropylene forming the matrix. This has the effect that impact properties are maintained at an appropriate level while increased rigidity is achieved. In other words, the present inventors have found that such a lower ethylene content (or higher propylene content) provides a heterophasic propylene copolymer having an improved balance of impact and stiffness.
    [0065] The second heterophasic propylene copolymer is preferably a reactor grade copolymer.
    [0066] The second heterophasic propylene copolymer is preferably an unsubstituted or non-visceduced copolymer.
    [0067] For the purpose of the present invention the combined amount of second polypropylene and second ethylene-αolefin copolymer in the second heterophasic propylene copolymer is substantially 100% by weight based on the weight of the second heterophasic propylene copolymer. In addition to the second polypropylene and second ethylene-α-olefin copolymer, no other material is comprised in the second heterophasic propylene copolymer except for an optional small amount of stabilizers and / or additives common in the art.
    [0068] According to the present invention the melt flow index of the first polypropylene and the second polypropylene can be the same or different.
    [0069] Any or all of the aforementioned preferred features can be combined in any way and any combination is considered to be disclosed here.
    [0070] While it is preferred that the second heterophasic propylene copolymer is comprised of a single material, i.e. a single grade, a combination of more than a second heterophasic propylene copolymer can also be considered and should be considered to fall in scope of the present invention.
    [0071] The first and second heterophasic copolymers can be manufactured by methods known in the art. Such methods generally involve the use of two or more polymerization reactors placed in series, in which in a first reactor the matrix phase comprised of the first polypropylene or the second polypropylene (as the case may be) is produced. Once polymerization in the first reactor is completed the resulting polymeric powder is transferred to a second reactor in which the first ethylene-α-olefin copolymer or the second ethylene-α-olefin copolymer (as the case may be) is produced. It is preferred that the polymerization is carried out using a Ziegler Natta type catalyst. Ziegler Natta catalyst systems are known in the art and comprise a catalyst component, a cocatalyst component and an external donor. The catalyst component of the capitalist system mainly contains magnesium, titanium, halogen and an internal donor. Electron donors control stereo-specific properties and / or improve the activity of the catalyst system. Various electron donors including ethers, esters, polysilanes, polysiloxanes, and alkoxysilanes are known in the art. In a preferred embodiment, heterophasic propylene compositions are manufactured using a double stage polymerization catalyzed by the SHAC 320 catalyst, as available from Grace company. Polyolefin composition and compound
    [0072] The polyolefin composition according to the present invention is a heterophasic polyolefin composition, comprising a continuous phase and a discontinuous phase. For the avoidance of doubt, it is observed that the first polypropylene of the first heterophasic propylene copolymer and the second polypropylene of the second heterophasic propylene copolymer, although miscible, are different. That is, the first polypropylene and the second polypropylene together can form the continuous phase.
    [0073] The discontinuous phase (or dispersed phase) of the polyolefin composition of the present invention comprises the first ethylene-α-olefin copolymer and the second α-olefin copolymer. Although said copolymers may be miscible to some extent (low) they will be present as separately dispersed phases in the final product made from the polyolefin composition.
    [0074] In a preferred embodiment of the polyolefin composition the first heterophasic propylene copolymer as well as the second heterophasic propylene copolymer are reactor grade copolymers.
    [0075] In a preferred embodiment the first and second ethylene-α-olefin copolymers are ethylene-propylene copolymers. In such a preferred embodiment it is still preferred that: the first ethylene-propylene copolymer has an ethylene content of 40 to 65% by weight, more preferably 40 to 60% by weight, even more preferably 50 to 58% by weight based by weight of the first ethylene-propylene copolymer, and / or the second ethylene-propylene copolymer has an ethylene content of 30 to 65% by weight, preferably 30 to 50% by weight, more preferably 35 to 40% by weight weight based on the weight of the second ethylene-propylene copolymer.
    [0076] The present inventors have found that the ethylene content of the second ethylene-α-olefin copolymer is of importance for good mechanical properties. In particular, they found that an ethylene-propylene copolymer having a relatively low ethylene content (or high propylene content) results in significantly improved mechanical properties, such as impact resistance and stiffness, while at the same time having no adverse effect of tiger stripe performance. In addition to these reduction properties, in particular the CLTE (Linear Thermal Expansion Coefficient) has been found to improve during the highest propylene content.
    [0077] The present invention also relates to a compound comprising the polyolefin composition as defined herein.
    The compound according to the present invention preferably contains from 1 to 30, preferably from 1 to 25% by weight, more preferably from 5 to 20% by weight, even more preferably from 5 to 15% by weight of such an inorganic filler. as talc, based on the weight of the compound.
    [0079] The compound according to the present invention may further comprise from 1 to 25% by weight, based on the weight of the compound, of an ethylene-α-olefin copolymer elastomer. Such an ethylene-α-olefin copolymer elastomer is preferably selected from one or more ethylene-butene copolymer elastomer, ethylene-hexene copolymer elastomer and ethylene-octene copolymer elastomer. Even more preferably, the ethylene-α-olefin copolymer elastomer is selected from one or more of a metallocene-ethylene-octene copolymer elastomer and a metallocene-ethylene-butene copolymer elastomer. Typically, these elastomers are added to further improve impact resistance. The density of such elastomers can be from 860 to 885 kg / m3. The melt flow index for the elastomer can be from 0.10 to 10 g / 10 min (ISO1133, 2.16 kg, 230 ° C).
    [0080] Preferably the compound according to the present invention comprises from 5 to 20% by weight, or 7 to 18% by weight, or 10 to 15% by weight of elastomer.
    [0081] The compound of the present invention preferably has a medium tiger stripe rating, as defined herein below at least 6.0, preferably at least 6.5.
    [0082] The compound according to the present invention has a melt flow index of 1 to 50 g / 10 min, preferably 2 to 35 g / 10 min, more preferably 5 to 20 g / 10 min (ISO 1133 , 2.16 kg, 230 ° C).
    [0083] The compound according to the present invention can be used for the manufacture of automotive parts, in particular exterior automotive parts.
    [0084] The compound according to the present invention can be manufactured by melting the individual components according to any conventional procedure known in the art. Melting mixing devices suitable for this process are batch and continuous mixers, double screw extruders and single screw extruders with mixing sections and special mixers. Other aspects of the invention
    [0085] In another aspect the invention relates to the use of the compound as defined herein in an injection molding process to reduce tiger streaks.
    [0086] In another aspect, the invention relates to heterophasic propylene copolymer comprising: from 70 to 90% by weight of a first polypropylene having a melt flow index of 55 to 85 g / 10 min as measured by according to ISO 1133 (2.16 kg and 230 ° C), where the first polypropylene is a propylene homopolymer or a propylene-α-olefin copolymer containing at least 97% by weight of propylene, based on the weight of the first second polypropylene from 10 to 30% by weight of a first ethylene-α-olefin copolymer having a melt flow index of 2.5 to 5.0 g / 10 min according to ISO 1133 (2.16 kg and 230 ° C), wherein the first ethylene-α-olefin copolymer is an ethylene-propylene copolymer having an ethylene content of 40 to 60% by weight, preferably 50 to 58% by weight, based on weight of the ethylenepropylene copolymer.
    [0087] the respective amounts of the first polypropylene and first ethylene-α-olefin copolymer being based on the weight of the first heterophasic propylene copolymer, and
    [0088] wherein the heterophasic propylene copolymer is preferably a propylene reactor grade copolymer.
    [0089] Preferred embodiments of this heterophasic propylene copolymer apply as defined herein for the first heterophasic propylene copolymer of the polyolefin composition according to the invention.
    [0090] In another aspect the invention relates to the heterophasic propylene copolymer comprising: from 70 to 90% by weight of a first polypropylene having a melt flow index of 55 to 85 g / 10 min as measured according to with ISO 1133 (2.16 kg and 230 ° C), where the first polypropylene is a propylene homopolymer or a propylene-α-olefin copolymer containing at least 97% by weight of propylene, based on the weight of the first second polypropylene from 10 to 30% by weight of a first ethylene-α-olefin copolymer having a melt flow index of 2.5 to 4.0 g / 10 min according to ISO 1133 (2.16 kg and 230 ° C), wherein the first ethylene-α-olefin copolymer is an ethylene-propylene copolymer having an ethylene content of 40 to 60% by weight, preferably 50 to 58% by weight, based on the weight of the ethylenepropylene copolymer.
    [0091] the respective amounts of the first polypropylene and first ethylene-α-olefin polymer being based on the weight of the first heterophasic propylene polymer, and
    [0092] wherein the heterophasic propylene copolymer is preferably a propylene reactor grade copolymer.
    [0093] Preferred embodiments of this heterophasic propylene copolymer apply as defined herein for the second heterophasic propylene copolymer of the polyolefin composition according to the invention.
    [0094] In yet another aspect, the invention relates to a heterophasic propylene copolymer comprising: from 60 to 85% by weight of a second polypropylene having a melt flow index of 50 to 100 g / 10 min as measured according to ISO 1133 (2.16 kg and 230 ° C), where the second polypropylene is a propylene homopolymer or a propylene-α-olefin copolymer containing at least 97% by weight of propylene, based on weight of the second polypropylene from 15 to 40% by weight of a second ethylene-α-olefin copolymer having a melt flow index of 0.050 to 0.30 g / 10 min according to ISO 1133 (2.16 kg and 230 ° C), wherein the second ethylene-α-olefin copolymer is an ethylenepropylene copolymer having an ethylene content of 30 to 65% by weight, preferably 30 to 50% by weight, more preferably 35 to 40% by weight based on the weight of the ethylene-propylene copolymer,
    [0095] the respective amounts of the first polypropylene and first ethylene-α-olefin polymer being based on the weight of the first heterophasic propylene polymer, and
    [0096] wherein the heterophasic propylene copolymer is preferably a propylene reactor grade copolymer.
    [0097] Preferred embodiments of this heterophasic propylene copolymer apply as defined herein for the second heterophasic propylene copolymer of the polyolefin composition according to the invention.
    [0098] In yet another aspect, the invention relates to a heterophasic propylene copolymer comprising: from 60 to 85% by weight of a second polypropylene having a melt flow index of 50 to 80 g / 10 min as measured according to ISO 1133 (2.16 kg and 230 ° C), where the second polypropylene is a propylene homopolymer or a propylene-α-olefin copolymer containing at least 97% by weight of propylene, based on weight of the second polypropylene from 15 to 40% by weight of a second ethylene-α-olefin copolymer having a melt flow index of 0.050 to 0.30 g / 10 min according to ISO 1133 (2.16 kg and 230 ° C), wherein the second ethylene-α-olefin copolymer is an ethylenepropylene copolymer having an ethylene content of 30 to 65% by weight, preferably 30 to 50% by weight, more preferably 35 to 40% by weight based on the weight of the ethylene-propylene copolymer,
    [0099] the respective amounts of the first polypropylene and first ethylene-α-olefin polymer being based on the weight of the first heterophasic propylene polymer, and
    [00100] wherein the heterophasic propylene copolymer is preferably a propylene reactor grade copolymer.
    [00101] Preferred embodiments of this heterophasic propylene copolymer apply as defined herein for the second heterophasic propylene copolymer of the polyolefin composition according to the invention.
    [00102] In yet another aspect, the present invention relates to the use of a combination of the two heterophasic propylene copolymers mentioned above in a compound still containing an inorganic filler such as talc and an ethylene-α-olefin copolymer elastomer and in effective amounts to allow the manufacture of molded automotive parts having an average tiger stripe rating, as defined in the specification, of at least 6. Rheological behavior
    [00103] The present inventors have found that the rheological behavior of a heterophasic polyolefin composition can be used as an indication of the sensitivity to tiger stripes.
    [00104] To this extent, the present inventors measured the rheological behavior using an Advanced Instruments Rheometric Expansion System (ARES) from TA Instruments with two parallel plates of 25 mm in diameter, operating at 200 ° C and applying a frequency scan of 100 to 0.1 rad per second.
    [00105] Then the first derivative of imaginary viscosity (eta ") was plotted (vertically, that is, Y axis) versus the real viscosity (eta ') horizontally, that is, X axis in order to form a" curve viscosity ".
    [00106] Based on the experiments carried out by the inventors it was discovered that a regime can be defined in which the tiger stripe performance is good.
    [00107] More particularly, the present inventors have discovered that if a viscosity curve of a heterophasic polyolefin composition is above the curve represented by the formula: Y = -5.55556e-4 * X + 0.61111 (Y and X representing eta 'and eta' respectively) The performance of the tiger stripe is good.
    [00108] Likewise if a viscosity curve of a heterophasic polyolefin composition is below the curve presented by the formula: Y = -0.00142 * X + 0.63333 The performance of the tiger stripe is good.
    [00109] In the area between these two curves the tiger stripe performance is usually poor.
    As such, the present invention relates to polyolefin compositions comprising a first and second propylene copolymer as defined herein, wherein the amounts of the first and second heterophasic propylene copolymer are selected such that the viscosity curve of the combination it is not in the area between the two curves as defined above. Measuring methods
    Performance of tiger stripe / flow marks
    [00111] Samples of the polyolefin composition were injection molded into two types of test specimens in the form of a ruler using the feeding system and the mold as illustrated in Figure 1. Details of the two types of the molds are illustrated in Figures 2 and 3. The two types of molds are called a fan gate (Figure 2) and a pin-point gate (Figure 3).
    [00112] Figure 1 illustrates the feeding system and the mold. The fused polyolefin composition is extruded through a nozzle 1 having an upper end having a diameter of 4 mm and a lower end having a diameter of 7 mm. The lower end of the nozzle 1 merges with a rectangular mold channel.
    [00113] Figure 2 illustrates a "fan-gate" mold. Along the length of the mold, the width changes from about 6.5 mm to 30 mm and the thickness changes from about 3 mm to 2 mm. After the fan-shaped part, an elongated part is still 30 mm wide and 3 mm thick. The rectangular part is about 43 mm in length. The fan-shaped part of the mold is about 25 mm in length.
    [00114] Figure 3 illustrates a "pin-gate" mold. The pin-point gate is identical to the fan gate in Figure 2 except that the rectangular part comprises a portion having a width of 1.2 mm over a length of about 6 mm
    [00115] The melting temperature during injection molding is adjusted to 240 ° C and the mold is kept at room temperature. Three different thread speeds are used according to the following conditions. Injection conditions

    [00116] Specimens having a smooth side and a textured side were manufactured.
    [00117] After molding each specimen is visually observed for the occurrence of tiger stripes on its smooth side and on its textured side. The surface quality was assessed on a scale of 1 to 10, 10 being the best performance.

    [00118] The average tiger stripe rating is defined as the numerical average of the individual tiger stripe ratings for each of the test specimens manufactured at low, medium and high speeds, manufactured with pin-gate and fan-gate and measured on the smooth surface and the textured surface. Consequently, the average tiger stripe rating as defined here is the average of 12 individual tiger stripe measurements. Experiments
    [00119] A total of 38 experiments were carried out, numbered as E1 to E38 in tables 1 to 7 below.
    [00120] In the experiments the following materials were used:
    [00121] All heterophasic copolymers are reactor grade materials, that is, they are unsubstituted or not viscorreduced categories. PP612MK10: Commercially available impact propylene copolymer from SABIC having an MFI of 33 g / 10 min, a C2 / C3 rubber content of about 18% by weight and a rubber phase C2 content of about 54% in weight. PP513MNK10: Commercially available impact propylene copolymer from SABIC having an MFI of 70 g / 10 min, a C2 / C3 rubber content of about 18% by weight and a rubber phase C2 content of about 54% in weight. BG A0: Heterophasic propylene copolymer having a propylene homopolymer matrix phase and a dispersed C2 / C3 copolymer phase and having: Rubber content (C2 / C3 copolymer) 20% by weight MFI_matrix 70 g / 10 min MFI_dispersed 3, 5 g / 10 min C2 content in rubber 55% by weight global MFI 38 g / 10 min BG A1 Heterophasic propylene copolymer having a propylene homopolymer matrix phase and a dispersed C2 / C3 copolymer phase and having: rubber (C2 / C3 copolymer) 20% by weight MFI_matrix 75.0 g / 10 min MFI_dispersed 3.0 g / 10 min C2 content in rubber 40% by weight MFI global 39 g / 10 min BG A2 Heterophasic propylene copolymer having a propylene homopolymer matrix phase and a dispersed C2 / C3 copolymer phase having: Rubber content (C2 / C3 copolymer) 20% by weight MFI_matrix 75.0 g / 10 min MFI_dispersed 3.0 g / 10 min Content of C2 in rubber 55% by weight global MFI 40 g / 10 min BG B0 Heterophasic propylene copolymer having a homopolymer matrix phase of propylene and a dispersed phase of C2 / C3 copolymer and having: Rubber content (C2 / C3 copolymer) 30% by weight MFI_ matrix 70 g / 10 min MFI_dispersed 0.2 g / 10 min C2 content in rubber 58% by weight MFI overall 12 g / 10 min BG B1 Heterophasic propylene copolymer having a propylene homopolymer matrix phase and a dispersed C2 / C3 copolymer phase and having: Rubber content (C2 / C3 copolymer) 30% by weight MFI_matrix 75.0 g / 10 min MFI_dispersed 0.20 g / 10 min C2 content in rubber 60% by weight global MFI 12 g / 10 min BG B2 Heterophasic propylene copolymer having a propylene homopolymer matrix phase and a dispersed C2 copolymer phase / C3 and having: Rubber content (C2 / C3 copolymer) 30% by weight MFI_matrix 75.0 g / 10 min MFI_dispersed 0.15 g / 10 min C2 content by rubber 35% by weight MFI global 12 g / 10 min Talco_1 Steamic OOSD, commercially available from Imersys Talc. Talc_2 HTP Ultra 5c, commercially available from Imifabi Talc Talc_3 Luzenac HAR T84, commercially available from Imersys Talc Talc_4 HTP 05, commercially available from Imifabi Talc Engage 8200 Polyolefin elastomer commercially available from Dow, having a density of 0.870 g / cm3 and an MFI 5 g / 10 min (ASTM D1238, 2.16 kg, 230 ° C) Engage XLT8677 Commercially available polyolefin elastomer from Dow, having a density of 0.870 g / cm3 and an MFI of 0.5 g / 10 min (ASTM D1238, 2.16 kg, 230 ° C) Tafmer DF740 Ethylene-based elastomer, commercially available from Mitsui Chemicals, having a density of 0.870 g / cm3 and an MFI of 6.7 g / 10 min (ASTM D1238, 2, 16 kg, 230 ° C) Tafmer DF605 Elastomer based on ethylene, commercially available from Mitsui Chemicals, having a density of 0.861 g / cm3 and an MFI of 0.9 g / 10 min (ASTM D1238, 2.16 kg, 230 ° C) Other usual additives for compounds, such as stabilizers, antioxidants and the like.
    [00122] Examples E1 to E6 provide a comparison between heterophasic propylene copolymers when used as a single heterophasic propylene copolymer in a compound still containing talc and ethylene α-olefin elastomer (Engage 8200).
    [00123] Examples E7 to E14 show compositions according to the invention based on a combination of the first and second heterophasic copolymers as defined here. It is observed that compositions based on BG B2 show good results in terms not only of the tiger stripe performance, but also in terms of the impact on a more or less similar level of stiffness (flexural module being indicative for stiffness)
    [00124] Table 3 shows the individual tiger stripe measurements for examples E1 to E14.
    [00125] Examples E15 to E20 provide another comparison between heterophasic propylene copolymers when used as a single heterophasic propylene copolymer in a compound still containing talc and ethylene-α-olefin elastomer (Engage 8200).
    [00126] Examples E21 to E24 show compositions according to the invention based on a combination of the first and second heterophasic copolymers as defined herein. It is observed that compositions based on BG B2 show good results in terms not only of tiger stripe performance, but also in terms of impact on a more or less similar level of stiffness (flexural module being indicative for stiffness)
    [00127] Examples E25 to E27 show the results of a variation in the type of ethylene-α-olefin copolymer elastomer. Tiger stripe performance is largely unaffected.
    [00128] Examples E28 and E29 show the effect of the talc type. The talc type mainly appears to affect stiffness, but no significant effect on tiger stripe performance has been observed.
    [00129] Table 6 shows the individual tiger stripe measurements for examples E15 to E29.
    [00130] Examples E30 to E38 further contain compositions according to the invention. From Table 7 it can be seen that the inventive polyolefin compositions not only have good tiger stripe performance, but also show good flow (melt flow index), acceptable rigidity and impact properties, but in particular good values of scratch resistance.










    权利要求:
    Claims (14)
    [0001]
    1. Polyolefin composition characterized by the fact that it comprises a first heterophasic propylene copolymer and a second heterophasic propylene copolymer, wherein the first heterophasic propylene copolymer comprises: from 70 to 90% by weight of a first polypropylene having an index of melt flow of 55 to 85 g / 10 min as measured according to ISO 1133 (2.16 kg and 230 ° C), from 10 to 30% by weight of a first ethylene-α-olefin copolymer having an index of melting flow of 2.5 to 5.0 g / 10 min according to ISO 1133 (2.16 kg and 230 ° C), the respective amounts of the first polypropylene and first ethylene-α-olefin polymer being based on the weight of the first heterophasic propylene polymer, wherein the first ethylene-α-olefin copolymer is an ethylene-propylene copolymer having an ethylene content of 50 to 58% by weight, based on the weight of the ethylene-propylene copolymer, and in which the second heterophasic propylene copolymer comprises: from 60 to 85% by weight of a second polypropylene having a melt flow index of 50 to 100 g / 10 min as measured according to ISO 1133 (2.16 kg, 230 ° C), from 15 to 40% by weight of a second ethylene copolymer -α-olefin having a melt flow index of 0.050 to 0.30 g / 10 min according to ISO 1133 (2.16 kg and 230 ° C), the respective amounts of the second polypropylene and second ethylene-α copolymer -olefin being based on the weight of the second heterophasic propylene copolymer, wherein the second ethylene-α-olefin copolymer is an ethylene-propylene copolymer having an ethylene content of 30 to 50% by weight, based on the weight of the copolymer ethylene-propylene, wherein a weight ratio of said first and second heterophasic propylene copolymer is 1 to 10.
    [0002]
    2. Polyolefin composition according to claim 1, characterized in that the first and / or second heterophasic propylene copolymer is / are reactor grade propylene copolymer (s), preferably in which both the first and the second heterophasic propylene copolymers are reactor grade propylene copolymers.
    [0003]
    3. Polyolefin composition according to claim 1 or 2, characterized in that the second ethylene-α-olefin copolymer is an ethylene-propylene copolymer having an ethylene content of 35 to 40% by weight based on weight of the ethylene-propylene copolymer.
    [0004]
    Polyolefin composition according to any one of claims 1 to 3, characterized in that the first and / or second polypropylene is / are a propylene homopolymer or a propylene-α-olefin copolymer containing at least 97% in propylene weight, based on the weight of the first and / or second polypropylene.
    [0005]
    Polyolefin composition according to any one of claims 1 to 4, characterized in that one or both of the first and second heterophasic propylene copolymer is / are non-viscored reduction copolymer (s).
    [0006]
    A compound characterized in that it comprises the polyolefin composition, as defined in any one of claims 1 to 5, and from 1 to 30% by weight, preferably from 5% by weight to 25% by weight, more preferably from 5% by weight to 15% by weight of an inorganic filler such as talc, based on the weight of the compound.
    [0007]
    A compound according to claim 6, characterized in that it further comprises from 1 to 25% by weight, based on the weight of the compound, of an ethylene-α-olefin copolymer elastomer, preferably selected from of one or more of an ethylene-butene copolymer elastomer, an ethylene-hexene copolymer elastomer, and an ethylene-octene copolymer elastomer, even more preferably selected from one or more of a metallocene copolymer elastomer -ethylene-octene, and a metallocene-ethylene-butene copolymer elastomer.
    [0008]
    8. Compound according to claim 6 or 7, characterized by the fact that it has an average tiger stripe rating, as defined in the specification, of at least 6.0.
    [0009]
    Use of the polyolefin composition, as defined in any one of claims 1 to 5, or the compound, as defined in any one of claims 6 to 8, characterized by the fact that it is for the manufacture of interior or exterior automotive parts.
    [0010]
    10. Use of the compound, as defined in any of claims 6 to 8, characterized by the fact that it is in an injection molding process to reduce tiger streaks.
    [0011]
    11. Molded article characterized by the fact that it comprises the polyolefin composition as defined in any one of claims 1 to 5, or the compound as defined in any one of claims 6 to 8.
    [0012]
    12. Hypophasic propylene copolymer characterized by the fact that it comprises: from 70 to 90% by weight of a first polypropylene having a melt flow index of 55 to 85 g / 10 min as measured according to ISO 1133 (2.16 kg and 230 ° C), where the first polypropylene is a propylene homopolymer or a propylene α-olefin copolymer containing at least 97% by weight of propylene, based on the weight of the first polypropylene from 10 to 30% by weight of a first ethylene-α-olefin copolymer having a melt flow index of 2.5 to 5.0 g / 10 min according to ISO 1133 (2.16 kg and 230 ° C), where the first ethylene copolymer -α-olefin is an ethylene-propylene copolymer having an ethylene content of 50 to 58% by weight, based on the weight of the ethylene-propylene copolymer. the respective amounts of the first polypropylene and first ethylene-α-olefin polymer, being based on the weight of the first heterophasic propylene polymer, and wherein the heterophasic propylene copolymer is preferably a propylene reactor grade copolymer.
    [0013]
    13. Hypophasic propylene copolymer characterized by the fact that it comprises: from 60 to 85% by weight of a second polypropylene having a melt flow index of 50 to 100 g / 10 min as measured according to ISO 1133 (2.16 kg and 230 ° C), wherein the second polypropylene is a propylene homopolymer or a propylene α-olefin copolymer containing at least 97% by weight of propylene, based on the weight of the second polypropylene from 15 to 40% by weight of a second ethylene-α-olefin copolymer having a melt flow index of 0.050 to 0.30 g / 10 min according to ISO 1133 (2.16 kg and 230 ° C), in which the second ethylene-α copolymer -olefin is an ethylene-propylene copolymer having an ethylene content of 30 to 50% by weight, preferably 35 to 40% by weight based on the weight of the ethylene-propylene copolymer, the respective amounts of the second polypropylene and second copolymer of ethylene-α-olefin being based on the weight of the second heterophasic propylene copolymer, and in which pref Heterophasically propylene copolymer is a propylene reactor grade copolymer.
    [0014]
    Use of a combination of a first amount of heterophasic propylene copolymer as defined in claim 12, and a second amount of heterophasic propylene copolymer as defined in claim 13, in a compound further containing an inorganic filler, such as talc and an ethylene-α-olefin copolymer elastomer characterized by the fact that it is for the manufacture of molded automotive parts having an average tiger stripe rating, as defined in the specification, of at least 6.5.
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    同族专利:
    公开号 | 公开日
    EP3083819B1|2019-01-30|
    US10047218B2|2018-08-14|
    WO2015091151A1|2015-06-25|
    US20170002188A1|2017-01-05|
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    EP3083819A1|2016-10-26|
    CN105849178A|2016-08-10|
    MX2016008034A|2017-03-03|
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    法律状态:
    2019-12-24| B06U| Preliminary requirement: requests with searches performed by other patent offices: procedure suspended [chapter 6.21 patent gazette]|
    2020-11-17| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|
    2021-01-05| B16A| Patent or certificate of addition of invention granted [chapter 16.1 patent gazette]|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 10/12/2014, OBSERVADAS AS CONDICOES LEGAIS. |
    优先权:
    申请号 | 申请日 | 专利标题
    EP13199158.0|2013-12-20|
    EP13199158|2013-12-20|
    PCT/EP2014/077205|WO2015091151A1|2013-12-20|2014-12-10|Polyolefin composition|
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