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    • 专利摘要:
    COMPOSITION OF REINFORCED POLYPROPYLENE WITH HIGH FLOW FIBER. The present invention relates to a fiber-reinforced composition comprising a heterophasic propylene copolymer, a propylene homopolymer and / or a propylene copolymer, and fibers with an average diameter of 12.0 μm or less, wherein the propylene copolymer comprises no more than 2.0% by weight of C2 to C10 (alpha) -olefins other than propylene, the propylene homopolymer and the propylene copolymer have an MFR2 (230 ° C) fluidity index of at least 100 g / 10 min, and the composition has an MFR2 (230 ° C) melt index of at least 10 g / 10 min.
    公开号:BR112014024333B1
    申请号:R112014024333-6
    申请日:2013-03-27
    公开日:2020-12-22
    发明作者:Erwin Kastner；Jochen Kastl；Markus Hemmeter
    申请人:Borealis Ag；
    IPC主号:
    专利说明:

    [001] The present invention relates to a fiber-reinforced composition, as well as articles formed from it.
    [002] Polypropylene is a material used in a wide variety of technical fields and reinforced polypropylenes have, in particular, gained relevance in areas that were previously exclusive to non-polymeric materials, in particular metals. A particular example of reinforced polypropylenes are glass fiber reinforced polypropylenes. Such materials allow an adaptation of the properties of the composition by selecting the type of polypropylene, the amount of glass fiber and sometimes selecting the type of coupling agent used. Likewise, currently glass fiber reinforced polypropylene is a well accepted material for applications that require high rigidity, resistance to heat variation and resistance to both impact and dynamic fracture on the load (examples include automotive components with a load function) in the engine compartment, support parts for polymeric body panels, washing machine and dishwasher components). However, a disadvantage of commercially available fiber-reinforced material is its limitation on fluidity and processability. The fact that there is a clear negative correlation between the glass fiber content (usually ranging from 10 to 40% by weight) and fluidity (MFR) makes the formation of a thin wall or delicate parts difficult or impossible.
    [003] There is a need in the art to increase fluidity from the variation of the polymer material without sacrificing mechanical performance, especially impact resistance. In addition, there is a need in the art of reducing weight and complexity. The essential requirements are, first, to have sufficient fluidity to ensure adequate filling and, therefore, make complex parts viable and, second, to ensure the filling content as low as possible to obtain the greatest possible lightness potential. In order to obtain less weight in the final application, foaming via physical and chemical foaming becomes increasingly important.
    [004] Because of legal requirements for reducing carbon emissions and the need for economical engines, it is of special interest in the automotive industry to validate all types of lightweight potentials. Potential fields of interest include replacing “high density materials” with lighter sources or reducing the weight of the relevant part. One approach is to use chemical or physical foam. For the successful foaming of relevant applications, such as instrumental carriers, protections, structural carriers, in addition to foam reactivity, it is desired to have good fluidity of the used plastics in order to match the thin wall fill and have low levels of stress in the part to allow a suitable and constant foam construction and the filling of the necessary wall thicknesses.
    [005] EP 1 357 144 B1 describes the combination of a propylene homopolymer with a heterophasic propylene copolymer or two different heterophasic propylene copolymers as a matrix for glass fiber reinforced material (5 to 50% by weight of content of fiber). The polymer component A (a homopolymer or a propylene copolymer) has a melt index (MFR2) above 10 g / 10 min, while the polymer component B (a heterophasic copolymer) has a melt index (MFR2) of 0, 1 to 2.0 g / l0 min. The total fluidity index (MFR2) of the examples is 1.3 to 6.5 g / 10 min, with mechanics significantly worse at the highest fluidity indexes.
    [006] EP 0 206 034 A1 describes polyolefin compositions comprising an inorganic fibrous fill (3 to 25% by weight). The matrix for fibrous filling is a combination of a homopolymer or a copolymer of propylene and a polyethylene with fluidity index (MFR2) of more than 10 g / 10 min with said fluidity index (MFR2) being 0.1 to 50 times the fluidity index (MFR2) of the polypropylene component. The total fluidity with respect to the fluidity index (MFR2) of the examples can be estimated from the components as being between 1 and 4 g / 10 min.
    [007] US 5,382,459 covers glass fiber reinforced polypropylene compositions consisting essentially of a heterophasic copolymer, a polypropylene modified by carboxylic acid (as a compatibilizer) and fiberglass. Target applications are injection-molded wheel caps of high gloss and strength. Neither the total fluidity index (MFR2) nor the hardness are quantified.
    [008] WO 2008/07415 A1 refers to compositions filled with polyolefins containing from 15 to 55% by weight of polypropylene (bimodal mixture with two components having fluidity indexes (MFR2) of more than 500 g / 10 min and 0 , 1 to 30 g / 10 min, respectively, optionally with compatibilizer at 0.5 to 15% by weight), from 4 to 25% by weight of elastomer polymer and from 20 to 80% by weight of filler. Examples that include glass fibers (50% by weight) have a total fluidity index (MFR2) of 3.6 to 7.8 g / 10 min with Charpy (IS 179 1eU, +23 ° C) ranging from 61 to 82 kJ / m2e resistance module from 9,700 to 13,100 MPa. However, the fluidity of the compositions is still not satisfactory.
    [009] Thus, the object of the present invention is to provide a fiber-reinforced composition with excellent fluidity and a superior balance of mechanical properties, such as flexion module, impact resistance and elongation at break.
    [010] The discovery of the present invention is that the reinforced fibrous material embedded in a polymer composition, which includes a low viscous polypropylene and a heterophasic polypropylene, is a fiber material having a diameter of 12.0 µm or less.
    [011] Therefore, the present invention is directed to a fiber-reinforced composition comprising: (a) a heterophasic propylene cup (HECO), (b) a propylene homopolymer (H-PP1) and / or a propylene propylene cup ( C-PP1), and (c) fibers (F) with an average diameter of 12.0 μm or less, where (i) the propylene cup (C-PP1) comprises no more than 2.0% by weight of C2 to C10 α-o1efins other than propylene, (ii) the propylene homopolymer (H-PP1) and the propylene cup (C-PP1) have an MFR2 fluidity index (230 ° C) measured according to ISO 1133 of at least 50 g / 10 min, and (iii) the fiber-reinforced composition has an MFR2 melt index (230 ° C) measured according to ISO 1133 of at least 10 g / 10 min.
    [012] In a preferred embodiment, the fibers (F) have an average diameter of 11.5 μm or less, more preferably 11.0 μm or less, even more preferably 10.5 μm or less, such as 8, 0 to 12.0 μm, 9.0 to 11.5 μm, or 10.0 to 11.0 μm.
    [013] Preferably, the fibers (F) have an aspect ratio of 150 to 450, more preferably 200 to 400 and even more preferably 250 to 350. The aspect ratio is the relationship between length and diameter of the fibers.
    [014] In a preferred embodiment according to the present invention, the heterophasic propylene copolymer (HECO) of the fiber-reinforced composition includes a polypropylene (M-PP) matrix, wherein preferably the polypropylene (M- PP) is a propylene homopolymer (H-PP2), and dispersed therein an elastomer copolymer (E1) that includes units derived from: (a) propylene and (b) ethylene and / or C4 to C20 α-olefin.
    [015] The polypropylene (M-PP) matrix of the heterophasic propylene copolymer (HECO) included in the fiber-reinforced composition according to the present invention has a lower melt index MFR2 (230 ° C) measured according to ISO 1133 than the propylene homopolymer (H-PP1) or the propylene copolymer (C-PP1).
    [016] In a preferred embodiment, the fiber-reinforced composition according to the present invention includes (c) 10.0 to 50.0% by weight, preferably from 20 to 40% by weight and even more preferable from 25 to 35% by weight of the heterophasic propylene copolymer (HECO), (d) 20.0 to 70.0% by weight, preferably from 25 to 65% by weight, more preferably from 30 to 60% by weight of propylene homopolymer (H-PPI), propylene copolymer (C-PPI), or the mixture of propylene homopolymer (H-PPI) and propylene copolymer (C-PPI), and (c) 5.0 to 50.0 % by weight of fibers (F), preferably from 10 to 45% by weight, more preferably from 15 to 40% by weight, even more preferably from 15 to 25% by weight, such as 20% by weight, based on weight total fiber-reinforced composition.
    [017] Preferably, the heterophasic propylene copolymer (HECO) included in the fiber reinforced composition according to the present invention has: (e) a content of cold xylene soluble (XCS) measured according to ISO 6427 (23 ° C) of not more than 35% by weight, preferably not more than 32% by weight, such as 25 to 32% by weight and / or (f) an MFR2 flow rate (23 ° C) measured according to with ISO 1133 of more than 15 g / 10 min, preferably more than 16 g / 10 min, such as from 16 to 20 g / 10 min and / or (g) a different total content of C2 to C10 α-olefins of propylene from 10 to 30% by weight, preferably from 15 to 25% by weight, more preferably from 27 to 31% by weight.
    [018] In a preferred embodiment, the propylene polymer (H-PP1 or C-PP1) included in the fiber-reinforced composition according to the present invention is a propylene homopolymer (H-PPI). More preferably, said propylene homopolymer has an MFR2 melt index (230 ° C) measured according to ISO 1133 in the range of 50 to 150 g / 10 min, more preferably from 55 to 140 g / 10 min, even more preferably from 60 to 130 g / 10 min.
    [019] In a preferred embodiment, the present invention relates to a fiber-reinforced composition as defined above, wherein the fibers (F) are selected from a group consisting of glass fibers, metal fibers, ceramic fibers and graphite fibers, and are preferably selected from glass fibers.
    [020] It was discovered, with surprise, that the fiber-reinforced composition has very good fluidity and foaming capacity as well as other properties, such as stiffness and impact, at the desired levels. In particular, the flexural modulus, the impact of Charpy, and the elongation at break meet the requirements established, for example, by the automobile industry and the tool industry. The material, according to the present invention, typically passes the so-called “airbag” development test, which requires foaming ability, strength of the material that allows the airbag to pass through it, and stiffness that does not lead to fragility.
    [021] The present invention will now be described in more detail. Preferred embodiments, according to the present invention, can be taken from the appended claims.
    [022] It is apparent, because of the nomenclature used for the different polymers (HECO, M-PP, H-PP1, C-PP1, and E1) according to the present invention, that they must (chemically) vary from each other . The present invention is further characterized by the fact that none of the HECO polymers employed (and their individual components) is branched. In other words, the HECO polymers, (and their individual components), H-PP1, C-PP1, and E1 have a branching index of at least 0.90, more preferably at least 0.95, such as 1 , 00. The branching index is defined as g '= [IV] br / [IV] lin, where g' is the branching index, [IV] br is the intrinsic viscosity of the branched polypropylene and [IV] lin is the intrinsic viscosity of linear polypropylene that has the same average molecular weight (within a range of + 10%) as branched polypropylene. However, a low g 'value is an indicator of high branched polymer. In other words, if the value of g 'decreases, the branching of the polypropylene increases. References are made in this context to Zimm and W.H. Stockmeyer, J. Chem. Phys. 17, 1301 (1949). This document is incorporated herein by reference.
    [023] The term “heterophasic” indicates that the elastomeric copolymer (E1) is preferable (finely) dispersed at least in the polypropylene (M-PP) matrix of the heterophasic propylene copolymer (HECO). In other words, the elastomeric copolymer (E1) forms inclusions in the polypropylene matrix (M-PP). Thus, the polypropylene matrix (M-PP) contains (finely) dispersed inclusions that are not part of the matrix and said inclusions contain elastomeric copolymer (E1). The term "inclusion", according to this invention, should preferably indicate that the matrix and the inclusion form different phases within the heterophasic propylene copolymer (HECO), said inclusions are, for example, visible by high resolution microscopy, as electron microscopy or scanning force microscopy. The final fiber-reinforced composition is probably of a complex structure. Probably, the polypropylene matrix (M-PP) together with the propylene homopolymer (H-PP1) and / or the propylene copolymer (C-PP1) form a continuous phase with the fiber-reinforced composition matrix, in which the elastomeric copolymer (E1) forms inclusions dispersed there.
    [024] Additionally, the inclusions of the final fiber-reinforced composition may also contain the fibers (F); however, the fibers (F) are preferably dispersed individually as separate inclusions in the final matrix of the fiber-reinforced composition.
    [025] Furthermore, it is desired that the fiber-reinforced composition has a very high flow rate. The fluidity index depends mainly on the average molecular weight. This is due to the fact that long molecules give the material a tendency to flow more slowly than short molecules. An increase in molecular weight means a decrease in the MFR value. The fluidity index (MFR) is measured in g / 10min of the polymer discharged by a matrix defined under specific temperature and pressure conditions and the measure of the polymer viscosity which, in turn, for each type of polymer is mainly influenced by its molecular weight and also by its degree of branching. The flow rate measured under a load of 2.16 kg at 230 ° C (ISO 1133) is considered as MFR2 (230 ° C). Likewise, it is preferable that, in the present invention, the fiber-reinforced composition has an MFR2 (230 ° C) of at least 10 g / 10min, more preferably at least 11 g / 10min, such as 11 to 13 g / 10min. In this way, it is appreciated to have the final fluidity index MFR2 (230 ° C) of the fiber composition reinforced in a range of 10 to 100 g / 10min, more preferably from 10.5 to 80 g / 10min, more preferably from 11 to 60 g / 10min.
    [026] As stated above, the heterophasic propylene copolymer (HECO) includes: (a) a polypropylene matrix (M-PP) and (b) an elastomeric copolymer (E1) including units derived from: - propylene and - ethylene and / or C4 to C20 α-olefin.
    [027] In addition, the heterophasic propylene copolymer (HECO) comprises as components of the polymer only the polypropylene matrix (M-PP) and the elastomeric copolymer (E1). In other words, the heterophasic propylene copolymer (HECO) may contain more additives, but not another polymer in an amount exceeding 5% by weight, more preferably exceeding 3% by weight, as exceeding 1% by weight, based on the total of heterophasic propylene copolymer (HECO), more preferably based on the polymers present in the heterophasic propylene copolymer (HECO). An additional polymer that may be present in low quantities is a polyethylene which is a reaction product obtained by preparing the heterophasic propylene copolymer (HECO). Likewise, it is particularly appreciated that the heterophasic propylene copolymer (HECO) as defined in the present invention contains only a polypropylene matrix (M-PP), an elastomeric copolymer (E1) and optionally a polyethylene in amounts mentioned in this paragraph. Still, in the present invention, the fraction of insoluble in cold xylene (XCI) of the heterophasic propylene copolymer (HECO) represents the polypropylene matrix (M-PP) and optionally - if present - the polyethylene of the heterophasic propylene copolymer (HECO) ), while the fraction of soluble in cold xylene (XCS) represents the elastomeric part of the heterophasic polypropylene (H-PP1), that is, the elastomeric copolymer (E1).
    [028] On the other hand, the content of the polypropylene matrix (M-PP), that is, the content of insoluble in cold xylene (XCI), in the heterophasic propylene copolymer (HECO) is preferably at least 65% by weight , more preferably at least 67% by weight, and even more preferable at least 69% by weight. Although it is appreciated that the content of the polypropylene matrix (M-PP), that is, the content of insoluble in cold xylene (XCI) is preferably in the range of 65 to 75% by weight, more preferably in the range of 66 to 72 % by weight. If polyethylene is present in the heterophasic propylene copolymer (HECO), the values for the content of the polypropylene matrix (M-PP), but not for the content of insoluble in cold xylene (XCI), may be slightly decreased.
    [029] As explained above, a heterophasic propylene copolymer (HECO) constitutes a polypropylene matrix (MPP) in which the elastomeric copolymer is dispersed.
    [030] As will be explained in detail below, the polypropylene matrix (M-PP), the propylene homopolymer (H-PP1), the propylene copolymer (C-PP1) and the elastomeric copolymer (E1) can be unimodal or multimodal, as bimodal in view of the molecular weight distribution and / or the distribution of the comonomer content.
    [031] Thus, the expression “multimodal” and “bimodal” used here refers to the polymer modality, that is, - the shape of its molecular weight distribution curve, which is the graph of the molecular weight fraction as a function of its molecular weight, and / or - the shape of its comonomer content distribution curve, which is the graph of the comonomer content as a function of the molecular weight of the polymer fractions.
    [032] As will be explained below, the polypropylene matrix (M-PP), the propylene homopolymer (H-PP1), the propylene copolymer (C-PP1) and the elastomeric copolymer (E1), if they are multimodal characteristics or bimodal, can be produced by mixing different types of polymer, that is, different molecular weights and / or comonomer content. However, in such a case it is preferable that the polymer components of the polypropylene matrix (M-PP), the propylene homopolymer (H-PP1), the propylene copolymer (C-PP1) and / or the elastomeric copolymer (E1 ) are produced in a gradual process, using reactors configured in series and operated under different reaction conditions. As a consequence, each fraction prepared in a specific reactor will have its own molecular weight distribution and / or comonomer content distribution.
    [033] When the distribution curves (molecular weight or comonomer content) of these fractions are superimposed to obtain the molecular weight distribution curve or the comonomer content distribution curve of the final polymer, these curves can show two or more maximum or at least distinctly widened when compared to the individual fractions curves. Such a polymer, produced in two or more stages in series, is called bimodal or multimodal, depending on the number of stages.
    [034] The polypropylene matrix (M-PP) can be a propylene homopolymer (H-PP1) or a propylene copolymer (C-PP1).
    [035] In any case, it is preferable that the propylene matrix (M-PP) is a propylene homopolymer (H-PP1).
    [036] The term propylene homopolymer as used in the present invention refers to a polypropylene that consists substantially, for example, of more than 99.5% by weight, even more preferably at least 99.7% by weight, as with minus 99.8% by weight of propylene units. In a preferable embodiment, only the propylene units in the propylene homopolymer are detectable. The comonomer content can be determined with FT infrared spectroscopy, as described in the examples below.
    [037] Furthermore, in the case of the polypropylene matrix (M-PP) being of a multimodal character, such as bimodal, in particular multimodal, as bimodal, from the point of view of the content of comonomers, it is desired that the individual fractions be present in quantities that influence the material properties. Likewise, it is desired that each of these fractions be present in the amount of 10% by weight based on the polymer matrix (M-PP). Thus, in the case of a bimodal system, in particular from the point of view of comonomer content, the distribution of two fractions is basically 50:50. Thus, in one embodiment, the polypropylene matrix (M-PP) comprises two fractions that differ in their comonomer content, such as ethylene content, in which the first fraction is present from 40 to 60% by weight and the second fraction of 60 to 40% by weight.
    [038] The difference in comonomer content between the two fractions is defined in a preferred mode mode in the following paragraph.
    [039] The polypropylene matrix (M-PP) can be produced in a polymerization stage carried out in one or more polymerization reactors. It is desired that the polypropylene matrix (M-PP) is produced by carrying out polymerization in two or more different polymerization reactors (for example, mass reactors and / or gas phase reactors; as mass reactors, closed circuit reactors are preferred) to generate polymers of different desired molecular weight distributions or monomer formation in the different polymerization reactors.
    [040] Preferably, the polypropylene (M-PP) matrix is isostatic. Likewise, it is appreciated that the polypropylene matrix (M-PP) has a rather high concentration of pentants, for example, higher than 90 mol%, more preferably higher than 92 mol%, even more preferably higher than 93 mol% and still preferably higher than 95 mol%, as higher than 99 mol%.
    [041] Still, it is preferable that the polypropylene matrix (M-PP) has a very high flow rate. Thus, it is preferable, in the present invention, that the polypropylene matrix (M-PP), for example, the fraction of insoluble in cold xylene (XCI) of the heterophasic propylene copolymer (HECO), has a fluidity index MFR2 (230 ° C) in a range of 70.0 to 500.0 g / 10 min, more preferably from 75.0 to 400.0 g / 10 min.
    [042] Additionally, it is desired that the polypropylene matrix (M-PP) not only have a very high flow rate MFR2 (230 ° C), but also a fraction of soluble in cold xylene (XCS). Thus, it is preferable that the polypropylene (M) matrix fills in the equation: MFR / XCS> 30, preferably MFR / XCS> 40, more preferably MFR / XCS> 50 where “MFR” is MFR2 (230 ° C) [ g / 10 min] of the polypropylene matrix (M-PP) measured according to ISO 1133, and “XCS” is the amount of the fraction of cold xylene soluble (XCS) [% by weight] of the polypropylene matrix ( M-PP) measured according to ISO 6427 (23 ° C).
    [043] Preferably, the cold xylene-soluble fraction (XCS) of the polypropylene matrix measured according to ISO 6427 (23 ° C) is at least 1.0% by weight. Even more preferable, the polypropylene matrix (M-PP) has a fraction of cold xylene soluble (XCS) of no more than 3.5% by weight, preferably more than 3.0% by weight, as not more than 2.6% by weight. Although a preferred range of 1.0 to 3.5% by weight, more preferable from 1.0 to 3.0% by weight, even more preferable from 1.2 to 2.6% by weight.
    [044] Preferably, the propylene content in the heterophasic propylene copolymer (HECO) is 75 to 95% by weight, more preferably 80 to 94% by weight, based on the total of heterophasic propylene copolymer (HECO), more preferably based on the amount of polymer components in the heterophasic propylene copolymer (HECO), even more preferred based on the amount of the polypropylene matrix (M-PP) and the elastomeric copolymer (E1) together. The remainder comprises the comonomers, preferably ethylene. Thus, in a preferred embodiment, the comonomer content, for example, the content of C2 to C10 α-olefin instead of propylene, is from 5 to 25% by weight, more preferably from 6 to 20% by weight.
    [045] The second component of the heterophasic propylene copolymer (HECO) is the elastomeric copolymer (E1).
    [046] The constitution of the elastomeric copolymer (E1) preferably includes units derived from (i) propylene and (ii) ethylene and / or at least another C4 to C20 α-olefin, more preferably units derived from (i) propylene and ( ii) ethylene and at least one other α-oleophin selected from the group that includes 1-butene, 1-pentene, 1-hexene, 1-heptene and 1-octane. The elastomeric copolymer (E1) can additionally contain units derived from an unconjugated diene, however it is preferable that the elastomeric copolymer (E1) consists of units derived from (i) propylene and (ii) ethylene and / or C4 to C20 α-olefins only. Suitable unconjugated dienes, if used, include straight and branched chain acyclic dienes, such as 1,4-hexadiene, 1,5-hexadiene, 1,6-octadiene, 5-methyl-1,4-hexadiene, 3,7 -dimethyl-1,6-octadiene, 3,7-dimethyl-1,7 octadiene and the mixed isomers of dihydromyrcene and dihydro-ocimene, and single ring alicyclic dienes, such as 1,4-cyclohexadiene, 1,5- cyclooctadiene, 1,5-cyclododecadiene, 4-vinyl cyclohexene, 1-allyl-4-isopropylidene cyclohexane, 3-allyl cyclopentene, 4-cyclohexane and 1-isopropenyl-4- (4-butenyl) cyclohexane. Bridged ring dienes and multi-ring alicyclic fused are also suitable including tetrahydroindene, methyltetrahydroindene, dicyclopentadiene, bicyclo (2,2,1) hepta-2,5-diene, 2-methyl bicycloheptadiene and alkenyl, alkylidene, cycloalkenyl and noralkene cycloalkylidene , such as 5-methylene-2-norbonene, 5-isopropylidene norbonene, 5- (4-cyclopentenyl) -2-norbonene and 5-cyclohexylidene-2-norbonene. Preferred unconjugated dienes are 5-ethylidene-2-norbonene, 1,4-hexadiene and dicyclopentadiene.
    [047] In this way, the elastomeric copolymer (E1) includes at least units derivable from propylene and ethylene and can include other units derived from another α-oleophine, as defined in the previous paragraph. Therefore, it is particularly preferred that the elastomeric copolymer (E1) includes only units derived from propylene and ethylene and optionally an unconjugated diene as defined in the previous paragraph, such as 1,4-hexadiene. Although a propylene ethylene polymer not conjugated to a diene and / or propylene ethylene rubber (EPR1) as an elastomeric copolymer (E1), it is especially preferred, the latter is most preferred.
    [048] Like the polypropylene matrix (M-PP), the elastomeric copolymer (E1) can be both unimodal and multimodal, as well as bimodal. With regard to the definition of unimodal and multimodal, as bimodal, it concerns the definition above.
    [049] In the present invention, the content of the propylene-derived units in the elastomeric copolymer (E1) matches the content of the propylene detectable in the fraction of cold xylene soluble (XCS). Likewise the detectable propylene in the fraction of soluble in cold xylene (XCS) ranges from 50.0 to 75.0% by weight, more preferably from 55.0 to 70.0% by weight. Thus, in a specific embodiment, the elastomeric copolymer (E1), that is, the fraction of soluble in cold xylene (XCS) includes from 25.0 to 50.0% by weight, more preferably from 30.0 to 45.0% by weight of ethylene derivative units. Preferably, the elastomeric copolymer (E1) is a monomeric diene polymer not conjugated to ethylene propylene (EPDM1) or an ethylene propylene rubber (EPR1), the latter especially preferred, with a propylene and / or ethylene content as defined herein paragraph.
    [050] Another preferred requirement of the present invention is that the intrinsic viscosity (IV) of the cold xylene soluble fraction (XCS) of the heterophasic propylene copolymer (HECO) is very low. Very high values of intrinsic viscosity improve the ductility of the heterophasic system. Likewise, it is desired that the intrinsic viscosity of the cold xylene soluble fraction (XCS) of the heterophasic propylene copolymer (HECO) is below 3.0 dl / g, more preferably below 2.8 dl / g, and even more preferable below 2.5 dl / g. Even more preferable, the intrinsic viscosity of the cold xylene-soluble fraction of the heterophasic propylene copolymer (HECO) is in the range of 1.5 to 3.0 dl / g, more preferably in the range of 1.7 to 2, 8 dl / g, even more preferably 1.8 to 2.6 dl / g. The intrinsic viscosity is measured according to ISO 1628 in decal at 135 ° C.
    [051] Additionally, it is desired that the fluidity index (230 ° C) measured according to ISO 1133 of the heterophasic propylene copolymer (HECO) and / or the polypropylene matrix (M-PP) is lower than the index fluidity MFR2 (230 ° C) measured according to ISO 1133 of the propylene homopolymer (H-PP1) and the propylene copolymer (C-PP1).
    [052] Likewise, it is particularly desirable that the ratio of the MFR2 flow rate (230 ° C) of the heterophasic propylene copolymer (HECO) to the MFR2 flow rate (230 ° C) of the propylene homopolymer (H-PP1) ) and the propylene copolymer (C-PP1) [(MFR (HECO) / MFR (H-PP1)) or [(MFR (HECO) / MFR (C-PP1))] is in the range 1: 4 to 1 : 50, more preferably in the range of 1: 6 to 1:40). But not only the flow rate MFR2 (230 ° C) of the heterophasic system, but this must differentiate from the flow rate MFR2 (230 ° C) of the propylene homopolymer (H-PP1) and the propylene copolymer (C-PP1), respectively, but preferably also the flow rate MFR2 (230 ° C) of part of the matrix of the respective heterophasic system will differ from the flow rate MFR2 (230 ° C) of the propylene homopolymer (HPP1) and the propylene copolymer (C- PP1), respectively. The heterophasic propylene copolymer (HECO) is presented by a fraction of soluble in cold xylene (XCS) and a fraction of insoluble in cold xylene (XCI). In the present patent application, the fraction of insoluble in cold xylene (XCI) of the heterophasic propylene copolymer (HECO) is essentially identical to the matrix of said heterophasic propylene copolymer (HECO).
    [053] Likewise, when we talk about the flow rate of the polypropylene matrix (M-PP) of the heterophasic propylene copolymer (HECO), the flow rate of the fraction of insoluble in cold xylene (XCI) of said copolymer heterophasic propylene (HECO) is comprised. Thus, the MFR2 fluidity index (230 ° C) measured according to ISO 1133 of the cold xylene insoluble fraction (XCI) of the heterophasic propylene copolymer (HECO) is lower, preferably at least lower than 50 g / 10 min, more preferably lower than at least 55 g / 10 min, even more preferably at least lower than 60 g / 10 min, compared to the fluidity index MFR2 (230 ° C) measured according to ISO 1133 propylene homopolymer (H-PP) and propylene copolymer (C-PP), respectively.
    [054] The propylene homopolymer (H-PP1) is preferably an isostatic propylene homopolymer. In this way, it is appreciated that the polypropylene matrix (H-PP1) has a very high pentant concentration, for example, higher than 90 mol%, more preferably higher than 92 mol%, even more preferably higher than than 93 mol%, and even more preferably higher than 95 mol%, as more than 99 mol%.
    [055] Preferably the propylene homopolymer (H-PP1) has a melting temperature Tm measured according to ISO 11357-3 of at least 145 ° C, more preferably of at least 150 ° C.
    [056] In addition, the propylene homopolymer (H-PP) has a very low cold xylene soluble (XCS) content, for example, below 4.5% by weight, more preferably below 4.0% by weight, even more preferable below 3.7% by weight. While it is appreciated that the content of cold xylene soluble (XCS) is in a range of 0.5 to 4.5% by weight, more preferably in a range of 1.0 to 4.0% by weight, even more preferable in a range of 1.5 to 3.7% by weight, such as 2.0 to 3.5% by weight.
    [057] The propylene copolymer (C-PP1) preferably consists of units derived from propylene and ethylene and / or at least one C4 to C20 α-olefin, preferably at least one α-olefin selected from the group consisting of ethylene, 1 -butene, 1-pentene, 1-hexene and 1-octene, more preferably ethylene and / or 1-butene, even more preferably ethylene.
    [058] Thus, the propylene copolymer (C-PP) can comprise units derived from propylene, ethylene and optionally at least another C4 to C10 α-olefin. In a specific aspect of the present invention, the propylene copolymer (C-PP1) contains units derived from propylene, ethylene and optionally at least one other α-olefin selected from the group consisting of C4 α-olefin, C5 α-olefin, C6 α- olefin, C7 α-olefin, C8 α-olefin, C9 α-olefin and C10 α-olefin. More preferably, the propylene copolymer (C-PP) contains units derived from propylene, ethylene and optionally at least one other α-olefin selected from the group consisting of 1-butene, 1-pentene, 1-hexene, 1-heptene, 1- octene, 1-nonene and 1-decene, where 1-butene and 1-hexene are preferable. It is particularly preferable that the propylene copolymer (C-PP1) consists of units derived from propylene and ethylene. Preferably, the propylene derivative units constitute the main part of the propylene copolymer (C-PP1), for example, at least 95.0% by weight, preferably at least 97.0% by weight, more preferably at least 98.0% % by weight, even more preferable from 95.0 to 99.5% by weight, even more preferable from 97.0 to 99.5% by weight, even more preferably from 98.0 to 99.2% by weight. The number of units derived from C2 to C20 α-olefins in addition to propylene in the propylene copolymer (C-PP1) is in the range of 0.5 to 5.0% by weight, more preferably from 0.5 to 3.0% by weight, even more preferable from 0.8 to 2.0% by weight. It is particularly appreciated that the amount of ethylene in the propylene copolymer (C-PP1), in particular, in the case that the propylene copolymer consists only of units derived from propylene and ethylene, is in a range of 0.5 to 5.0 % by weight, preferably from 0.8 to 2.0% by weight.
    [059] In addition, it is desired that the content of soluble in cold xylene (XCS) of the propylene copolymer (C-PP1) be slightly lower. Thus, the propylene copolymer (C-PP1) preferably has the fraction of soluble in cold xylene (XCS) measured according to ISO 6427 (23 ° C) of not more than 14.0% by weight, more preferable of not more than 13.0% by weight, even more preferable not more than 12.0% by weight, as not more than 11.5% by weight. Although the preferred range is from 1.0 to 14.0% by weight, more preferred from 1.0 to 13.0% by weight, even more preferred from 1.2 to 11.0% by weight.
    [060] Preferably, the propylene copolymer (C-PP1) is isostatic. Likewise, it is appreciated that the propylene copolymer has a desired high concentration of pentant, for example, higher than 95 mol%, more preferably higher than 97 mol%, even more preferably higher than 98 mol% .
    [061] Furthermore, it is appreciated that units derived from C2 to C20 α-olefin in addition to propylene within the propylene copolymer (C-PP1) are randomly distributed. Randomness indicates the number of isolated comonomer units (C-PP1), for example, those that have no other comonomer units in proximity, compared to the total amount of comonomers in the polymer chain. In a preferred embodiment, the randomness of the propylene copolymer (C-PP1) is at least 30%, more preferable at least 50%, even more preferable at least 60%, and even more preferable at least 65%.
    [062] Additionally, it is appreciated that the propylene copolymer (C-PP1) has a melting temperature Tm measured according to ISO 11357-3 of at least 140 ° C, preferably at least 145 ° C, more preferable at least 150 ° C. Likewise, the melting temperature varies preferably from 140 to 164 ° C, more preferable variations from 150 to 160 ° C.
    [063] Especially good results are obtained in the case of the fiber-reinforced composition additionally containing an elastomer (E2). In this case, it is appreciated that the elastomer (E2) is (chemically) different from the elastomeric copolymer (E1).
    [064] The elastomer (E2), according to this invention, is preferably polyethylene, in particular a linear low density polyethylene (LLDPE). Thus, the elastomer (E2), that is, linear low density polyethylene (LLDPE) has a density measured according to ISO 1183-187 in a range of 820 to 905 kg / m3, more preferably in the range of 840 to 900 kg / m3, even more preferably in the range of 850 to 890 kg / m3, as in the range of 860 to 885 kg / m3.
    [065] Also, the elastomer (E2), that is, the linear low density polyethylene (LLDPE), is characterized by a specific fluidity index, namely by an MFR2 fluidity index (190 ° C) measured according to ISO 1133 in the range of 0.5 to 50.0 g / 10 min, more preferably in the range of 1.0 to 35.0 g / 10 min.
    [066] Preferably, the elastomer (E2), that is, the linear low density polyethylene (LLDPE), is a copolymer containing mostly derivable ethylene units. Likewise, it is appreciated that the elastomer (E2), that is, the linear low density polyethylene (LLDEP), comprises at least 50.0% by weight of derivable ethylene units, more preferably at least 55.0% by weight of ethylene-derived units. Thus, it is appreciated that the elastomer (E2), that is, linear low density polyethylene (LLDPE), comprises from 50.0 to 70.0% by weight, more preferably from 55.0 to 65% by weight, from derivative units of ethylene. The comonomers present in the elastomer (E2), that is, linear low density polyethylene (LLDPE), are C4 to C20 α-olefins, such as 1-butene, 1-hexene and 1-octene, the latter being especially preferred. Likewise, in a specific embodiment, the elastomer (E2), that is, the linear low density polyethylene (LLDPE), is a polymer of ethylene-1-octene or a polymer of ethylene-1-hexene, with the quantities given in this paragraph.
    [067] Another essential component of the present fiber-reinforced composition is fibers (F). Preferably, the fibers (F) are selected from a group consisting of glass fibers, metal fibers, ceramic fibers and graphite fibers. Glass fibers are especially preferred. Glass fibers can be cut glass fibers or long glass fibers, although preference is given to the use of cut glass fibers, also known as short fibers or cut yarns.
    [068] As indicated above, fibers (F) have an average diameter of 12.0 μm or less.
    [069] In a preferred embodiment, the fibers (F) have an average diameter of 11.5 μm or less, more preferably 11.0 μm or less, even more preferably 10.5 μm or less, such as 8 , 0 to 12.0 μm, from 9.0 to 11.5 μm, or from 10.0 to 11.0 μm.
    [070] In general, glass fibers can have a length of 1.0 to 50 mm. The cut or long fiber used in fiber-reinforced compositions has a preferred length of 1.0 to 10.0 mm, more preferably 1.0 to 7.0 mm, and / or a diameter of 8 to less than 12 μm, more preferably from 9 to 11.5 μm.
    [071] The fiber-reinforced composition may contain a compatibilizer (C).
    [072] The compatibilizer (C) preferably contains a modified (functionalized) polymer and optionally a low molecular weight compound having reactive polar groups. Modified α-oleophin polymers, in particular propylene homopolymers and copolymers, such as ethylene and propylene copolymers with one another or with other α-oleophins, are more preferred because they are highly compatible with the polymers of the fiber-reinforced composition. Modified polyethylene can also be used.
    [073] In the case of the structure, the modified polymers are preferably selected from graft or block copolymers.
    [074] In this context, preference is given to modified polymers containing groups derived from polar components, in particular selected from a group containing acid anhydrides, carboxylic acids, carboxylic acid derivatives, primary and secondary amines, hydroxyl compounds, oxazoline and epoxides , and also ionic components.
    [075] Specific examples of said polar components are unsaturated cyclic anhydrides and their aliphatic diesters, and derivatives of diacids. Particularly, maleic anhydride and compounds selected from C1 to C10 linear and branched dialkyl maleates, C1 to C10 linear and branched dialkyl smokers, itaconic anhydride, C1 to C10 linear and branched dialkyl esters, can be used maleic acid, fumaric acid, itaconic acid and mixtures thereof.
    [076] Particular preference is given to the use of the propylene polymer grafted with maleic anhydride as the modified polymer, that is, the compatibilizer (C).
    [077] The modified polymer, for example, the compatibilizer (C), can be produced in a simple way by reactive extrusion of the polymer, for example, with maleic anhydride in the presence of free radical generators (such as organic peroxides), such as shown, for example, in EP 0 572 028.
    [078] Preferred amounts of groups derived from polar compounds in the modified polymer, i.e., the compatibilizer (C), are 0.5 to 3% by weight.
    [079] Preferred values of the flow rate MFR2 (230 ° C) for the modified polymer, for example, for the compatibilizer (C), are from 1.0 to 500 g / 10 min.
    [080] The present composition may additionally contain other typical additives useful, for example, in the automotive sector, such as carbon black, other pigments, antioxidants, UV stabilizers, nucleating agents, antistatic agents and glidants, in amounts usual in the art .
    [081] All components used in the preparation of the present fiber-reinforced composition are known. Thus, their preparation is also well known. For example, the heterophasic polypropylene (HECO) according to this invention is preferably produced in a multi-stage process known in the art, where the polypropylene matrix (M-PP) is produced in at least one suspension reactor and one subsequently elastomeric copolymer (E1) is produced in at least one gas phase reactor.
    [082] Then, the polymerization system may contain one or more conventional stirred suspension reactors and / or one or more gas phase reactors. Preferably, the reactors used are selected from a group of closed loop and gas phase reactors and, in particular, the process employs at least one closed loop reactor and one gas phase reactor. It is also possible to use several reactors of each type, for example, one closed circuit and two or three gas phase reactors, or two closed circuit and one or two gas phase reactors, in series.
    [083] Preferably, the process also comprises a prepolymerization with the chosen catalyst system, as described in detail below, composed of the Ziegler-Natta procatalyst, the external donor and the co-catalyst.
    [084] In a preferred embodiment, prepolymerization is done as a bulk polymerization of mass in liquid propylene, that is, the liquid phase is composed mainly of propylene, with a smaller amount of other reagents and optionally components aggregates dissolved in it.
    [085] The prepolymerization reaction is typically carried out at a temperature of 0 to 50 ° C, preferably 10 to 45 ° C, and even more preferably 15 to 40 ° C.
    [086] The pressure in the prepolymerization reactor is not critical, but it must be high enough to maintain the reaction of the mixture in the liquid phase. Therefore, the pressure can be from 20 to 100 bar (2,000 to 10,000 kPa), for example, from 30 to 70 bar (3,000 to 7,000 kPa).
    [087] The catalyst components must all be introduced in the prepolymerization phase. However, where the solid catalyst component (i) and co-catalyst (ii) can be added separately, it is possible that only a part of the co-catalyst is added during the prepolymerization phase and the remaining parts in subsequent phases. In these cases too, the introduction of co-catalyst in the prepolymerization phase is such that it will be possible to obtain a sufficient polymerization reaction.
    [088] It is also possible to add other components to the prepolymerization phase. Therefore, hydrogen can be added in the prepolymerization phase to control the molecular weight of the prepolymer, as is known in the art. In addition, antistatic additives can be used to prevent particles from adhering to each other or to the reactor walls.
    [089] Precise control of polymerization conditions and reaction parameters is within the skill of the art.
    [090] A suspension reactor refers to any reactor, such as a single or continuous batch agitated tank reactor or closed circuit reactor, operating in bulk or slurry and in which the polymer is in the form of particles. "Bulk" means polymerization in a reaction medium comprising at least 60% by weight of monomer. According to a preferred embodiment the suspension reactor comprises a mass loop reactor.
    [091] “Gas-phase reactor” means any mechanical mixing reactor or fluidized bed. Preferably, the gas phase reactor comprises a mechanically stirred fluidized bed reactor with gas velocities of at least 0.2 m / s.
    [092] The particularly preferred embodiment for the preparation of the heterophasic polypropylene (HECO) of the invention comprises carrying out polymerization in a process comprising either a combination of a closed circuit and one or two gas phase reactors or a combination of two closed circuit and one or two gas phase reactors.
    [093] A multi-stage process is a gaseous-phase slurry process, as developed by Borealis and known as Borstar® technology. In this regard, reference is made to documents EP 0 887 379 A1, WO 92112182, WO 2004/000899, WO 20041111095, WO 99/24478, WO 99/24479 and WO 00/68315. They are hereby incorporated by reference.
    [094] Another suitable gaseous-phase slurry process is Basell's Spheripol® process.
    [095] Preferably, the heterophasic polypropylene composition according to the present invention is produced through a special Ziegler-Natta procatalyst, in combination with a special external donor, as described in detail below, preferably in the Spheripol®or Borstar® process -PP.
    [096] A preferred multi-stage process can therefore comprise the steps of: - producing a polypropylene matrix in the presence of the chosen catalyst system, as, for example, described in detail below, comprising the special Ziegler- Natta (i), an external donor (iii) and the co-catalyst (ii) in a first suspension reactor and optionally in a second suspension reactor, both suspension reactors using the same polymerization conditions, - transfer of product from suspension reactor for at least one first gas phase reactor, such as a gas phase reactor or a first and second gas phase reactor connected in series, - production of an elastomeric copolymer in the presence of the polypropylene matrix and in the presence of catalyst system in at least in said at least first gas-phase reactor, - recovery of the polymer product for further processing.
    [097] With respect to the above gas-phase slurry process, the following general information can be provided with respect to the process conditions.
    [098] The temperature is preferably 40 to 110 ° C, between 50 and 100 ° C, in particular between 60 and 90 ° C, with a pressure in the range of 20 to 80 bar (2,000 to 8,000 kPa), preferably 30 at 60 bar (3,000 to 6,000 kPa), with the option of adding hydrogen in order to control the molecular weight in a manner known per se.
    [099] The slurry polymerization reaction product, which is preferably carried out in a closed loop reactor, is then transferred to the subsequent gas phase reactor (s), where the temperature is preferably in a range from 50 to 130 ° C, even more preferably from 60 to 100 ° C, at a pressure in the range of 5 to 50 bar (500 to 5,000 kPa), preferably from 8 to 35 bar (800 to 3,500 kPa), again with option of adding hydrogen in order to control the molecular weight in a manner known per se.
    [100] The average residence time may vary in the reactor zones identified above. In one embodiment, the average residence time in the suspension reactor, for example, a closed circuit reactor, is in the range of 0.5 to 5 hours, for example, 0.5 to 2 hours, while the time The average residence time in the gas-phase reactor is usually 1 to 8 hours.
    [101] If desired, polymerization can be carried out in a known manner under supercritical conditions in the suspension reactor, preferably closed loop, and / or as a condensed mode in the gas phase reactor.
    [102] According to the invention, heterophasic polypropylene (HECO) is preferably obtained through a multi-stage polymerization process, as described above, in the presence of a catalyst system comprising as component (i) a Ziegler-Natta procatalyst which contains a transesterification product of a short-chain alcohol and a phthalic ester.
    [103] The procatalyst used according to the invention is prepared by: a) reacting an adduct solidified by emulsion or crystallized by spraying MgCl2 and a C1-C2 alcohol with TiC4 b) reacting the product from step a) with a dialkyl phthalate of the formula (I): wherein R1'and R2're independently present at least one C5 alkyl under conditions in which a transesterification between said C1 to C2 alcohol and said dialkylphthalate of formula (1) occurs to form the internal donor c ) washing the product from step b) or d) optionally reacting the product from step c) with more TiC4.
    [104] The procatalyst is produced as defined, for example, in patent applications WO 87/07620, WO 92/19653, WO 92/19658 and EP 0491 566. The content of these documents is included here by reference.
    [105] First, a MgCl2 adduct and a C1-C2 alcohol of the formula MgCl2 * nROH, where R is methyl or ethyl and n is 1 to 6, is formed. Ethanol is preferably used as alcohol.
    [106] The adduct, which is first melted and then crystallized by spraying or solidified by emulsion, is used as a catalyst carrier.
    [107] In the next step, the spray crystallized or emulsion solidified formula MgCl2 * nROH, where R is methyl or ethyl, preferably ethyl and n is 1 to 6, is in contact with TiCl4 to form a titanized carrier, followed by by the steps of: - adding to the titanized carrier (i) a dialkylphthalate of formula (I) with R1'and R2 'being independently at least one C5-alkyl, such as at least one C8-alkyl, or preferably (ii) a dialkylphthalate of formula (I) with R1'and R2 'being the same and being at least one C5-alkyl, such as at least one C8-alkyl, or more preferably (iii) a dialkylphthalate of formula (I) selected from the group that consists of propylhexyl phthalate (PrHP), dioctyl phthalate (DOP), diiso-decyl phthalate (DIDP) and ditridecyl phthalate (DTDP), even more preferably the dialkyl phthalate of the formula (I) is a dioctyl phthalate (DOP), as di-iso-octyl phthalate diethylhexyl phthalate, in particular diethylhexyl phthalate, to form a first - subjecting said first product to suitable transesterification conditions, that is, at a temperature above 100 ° C, preferably between 100 to 150 ° C, more preferably between 130 to 150 ° C, such that said methanol or ethanol is transesterified with said ester groups of said dialkyl phthalate of formula (1) to preferably form at least 80 mol%, more preferably 90 mol%, and more preferably 95 mol%, of a dialkyl phthalate of formula (II) with R1 and R2 being methyl or ethyl, preferably ethyl, the dialkyl phthalate of formula (II) being the internal donor and - recovery of said transesterification product as the pro-catalyst composition (component (i)).
    [108] The adduct of the formula MgCl2 * nROH, where R is methyl or ethyl and n is 1 to 6, is, in a preferred embodiment, melted and then the melt is preferably injected by a gas in a cooled solvent or by a cooled gas, whereby the adduct is crystallized in a morphologically advantageous form, as for example described in WO 87/07620. This crystallized adduct is preferably used as the catalyst carrier and reacted to the pro-catalyst useful in the present invention, as described in WO 92/19658 and WO 92/19653.
    [109] As the catalyst residue is removed by extraction, an adduct from the titanized carrier and the internal donor are obtained, in which the group resulting from the ester alcohol has changed.
    [110] If sufficient titanium remains in the carrier, it will act as an active element in the pro-catalyst.
    [111] Otherwise, titanization is repeated after the above treatment, in order to ensure sufficient titanium concentration and therefore activity.
    [112] Preferably the pro-catalyst used according to the invention contains a maximum of 2.5% by weight of titanium, preferably 2.2% by weight at most, and more preferably 2.0% by weight at most. Its donor content is preferably between 4 to 12% by weight and more preferably between 6 and 10% by weight.
    [113] More preferably, the pro-catalyst used according to the invention was produced using ethanol as the alcohol and dioctyl phthalate (DOP) as the dialkyl of formula (I), obtaining diethyl phthalate (DEP) as the internal donor compound. .
    [114] Even more preferably, the catalyst used according to the invention is Borealis BHC01P catalyst (prepared according to WO 92/19653, as disclosed in WO 99/24479; especially with the use of dioctyl phthalate as dialkylphthalate of the formula (I) according to WO 92/19658) or the Polytrack 8502 catalyst, commercially available from Grace.
    [115] In another embodiment, the Ziegler-Natta pro-catalyst can be modified by polymerizing a vinyl compound in the presence of the catalyst system, comprising the special Ziegler-Natta pro-catalyst, an external donor and a co-catalyst, whose vinyl compound has the formula: CH2 = CH-CHR3R4 where R3 and R4 together form a 5- or 6-membered saturated ring, unsaturated or aromatic or, comprising from 1 to 4 carbon atoms, and the modified catalyst is used for the preparation of the heterophasic propylene composition according to this invention. The polymerized vinyl compound can act as a nucleating agent. This modification is particularly used for the preparation of heterophasic polypropylene (H-PP1).
    [116] With regard to the modification of catalyst, reference is made to international patent applications WO 99/24478, WO 99/24479 and particularly WO 00/68315, incorporated herein by reference with respect to the reaction conditions relating to modification of the catalyst, as well as with respect to the polymerization reaction.
    [117] For the production of the heterophasic polypropylenes according to the invention, the catalyst system used preferably comprises, in addition to the special Ziegler-Natta procatalyst, an organometallic co-catalyst as component (ii).
    [118] Likewise, it is preferable to select the co-catalyst from the group consisting of trialkylaluminium, such as triethylaluminium (TEA), dialkyl aluminum chloride and alkyl aluminum sesquichloride.
    [119] The component (iii) of the catalyst system used is an external donor represented by the formula (III): Si (OCH3) 2R25 (III) in which R5 represents a branched alkyl group having 3 to 12 carbon atoms, preferably a branched alkyl group having 3 to 6 carbon atoms, or a cycloalkyl having 4 to 12 carbon atoms, preferably a cycloalkyl having 5 to 8 carbon atoms.
    [120] It is particularly preferred that R5 be selected from the group consisting of iso-propyl, iso-butyl, iso-pentyl, tert-butyl, tert-amyl, neopentyl, cyclopentyl, cyclohexyl, methylcyclopentyl and cycloheptyl.
    [121] More preferably, the external donor is dicyclopentyl dimethoxy silane [Si (OCH3) 2 (cyclopentyl) 2] or diisopropyl dimethoxy silane [Si (OCH3) 2 (CH (CH3) 2) 2].
    [122] The additives as mentioned above are added after the heterophasic polypropylenes, which are collected from the final reactor in the reactor series. Preferably, these additives are mixed in the heterophasic polypropylene (HECO) at or during the extrusion process in a one-stage combination process. Alternatively, a main batch can be formulated, in which the heterostatic polypropylene (HECO) is first mixed with only some of the additives.
    [123] Propylene homopolymer (H-PPl) and propylene copolymer (C-PPl), respectively, as defined in the present invention, can be prepared by propylene polymerization, in a fluidized bed reactor, for example , a closed circuit reactor, optionally together with at least one other C2 to C20 α-olefin (comonomers), in the presence of a polymerization catalyst to produce at least a part of the propylene homopolymer (H-PPl) or the copolymer of propylene (C-PPl), respectively. In case only part of the propylene homopolymer (H-PPI) or propylene copolymer (C-PPI) is produced, this part is subsequently transferred to a gas phase reactor, where the propylene in the phase reactor gas is reacted in order to produce an additional part in the presence of the reaction product of the first stage. In the second stage, other C2 to C20 α-olefin (s) (comonomers) can also be fed, if necessary. This reaction sequence provides a mixture of the parts reactor (i) and (ii) that constitutes the propylene homopolymer (H-PPI) or the propylene copolymer (C-PPI). It is clear that it is possible by the present invention that the first reaction is carried out in a gas-phase reactor, while the second polymerization reaction is carried out in a suspension reactor, for example, a closed circuit reactor. In addition, it is also possible to reverse the order of the producing parts (i) and (ii), which was described above in the order of the first producing part (i) and then the producing part (ii). The aforementioned process, which comprises at least two polymerization phases, is advantageous, in view of the fact that it provides reaction steps that allow the preparation of a desired reactor mixture. The polymerization steps can be adjusted, for example, by selecting the appropriate form of monomer feed, comonomer feed, hydrogen feed, temperature and pressure in order to properly adjust the properties of the obtained polymerization products. It is in particular possible to obtain a multimodality, preferably bimodality, of the propylene homopolymer (H-PPI) or of the propylene copolymer (C-PPI), in relation to the comonomer distribution, such as ethylene, as well as with respect to molecular weights and MFR2 values (230 ° C) during said multi-stage polymerization procedures. However, propylene homopolymer (H-PPI) and propylene copolymer (C-PPI), respectively, can also be produced in a reactor, such as a closed loop reactor, a method that is preferred.
    [124] Such a process (one reactor or several reactors in sequence) can be carried out using any suitable catalyst for the preparation of the propylene homopolymer (H-PP1) and the propylene copolymer (C-PP1), respectively. Preferably, the process as discussed above is carried out using a Ziegler-Natta catalyst, in particular a high-performance Ziegler-Natta (so-called fourth and fifth generation types to differentiate from the so-called second generation Ziegler-Natta catalysts) low profit). A Ziegler-Natta catalyst, suitable for use according to the present invention comprises a catalyst component, a cocatalyst component and at least one electron donor (internal and / or external electron donor, preferably at least one donor external). Preferably, the catalyst component is an Mg-Ti based catalyst component and, typically, the co-catalyst is an Al-alkyl based compound. Suitable catalysts are, in particular, disclosed in US 5,234,879, WO 92/19658 and WO 99/33843.
    [125] Preferred external donors are known silane-based donors, such as dicyclopentyl dimethoxy silane or cyclohexyl methyldimethoxy silane.
    [126] One embodiment of a process for the propylene homopolymer (H-PP1) or the propylene copolymer (C-PP1), as discussed above, is a closed-loop process or a closed-loop process gas phase, as developed by Borealis, known as Borstar® technology, described, for example, in EP 0 887 379 A1 and WO 92/12182.
    [127] With respect to the aforementioned preferred closed-loop process, or a gaseous closed-loop process, the following general information can be provided with respect to the process conditions.
    [128] Temperature from 40 to 110 ° C, preferably between 60 and 100 ° C, in particular between 80 and 90 ° C, with a pressure ranging from 20 to 80 bar (2,000 to 8,000 kPa), preferably 30 to 60 bar (3,000 to 6,000 kPa), with the option of adding hydrogen in order to control the molecular weight. The suspension polymerization reaction product, which is preferably carried out in a closed loop reactor, is then transferred to the reactor in the subsequent gas phase (in the case of the suspension gas process), where the temperature is preferably 50 to 130 ° C, more preferably from 80 to 100 ° C, at a pressure ranging from 5 to 50 bar (500 to 5,000 kPa), preferably from 15 to 35 bar (1,500 to 3,500 kPa), again with the option of add hydrogen in order to control the molecular weight.
    [129] The residence time may vary in the reactor zones identified above. In embodiments, the residence time in the suspension reaction, for example, the closed loop reactor, is in the range of 0.5 to 5 hours, for example, 0.5 to 2 hours, while the residence time in the gas phase reactor it will generally be from 1 to 8 hours.
    [130] The properties of the propylene homopolymer (H-PP1) or the propylene copolymer (C-PP1), produced with the process described above, can be adjusted and controlled with the process conditions, as known to the skilled person, by example, by one or more of the following process parameters: temperature, hydrogen feed, comonomer feed, propylene feed, catalyst, type and quantity of external donors, divided between two or more components of a multimodal polymer.
    [131] The elastomer (E2), that is, linear low density polyethylene (LLDPE), can be manufactured in a suspension reactor using a single site catalyst, for example, metallocene catalyst. Suitable metallocenes and ways of preparing them are within the knowledge and skills of a qualified person in the field. Reference is made to EP 0260130, WO 97/28170, WO 98/46616, WO 98/49208, WO 99/12981, WO 99/19335, EP 0 836 608, WO 98/56831, WO 00/34341, EP 0423101 and EP 0 537130. Especially preferred, the elastomer (E2), that is, the linear low density polyethylene (LLDPE), is made using a hafnium metallocene like a bis (n-butylcyclopentadienyl) hafnium or bis (n-butylcyclopentadienyl) chloride ) hafnium dibenzyl. Other potential catalysts are described in WO 97/28170 and WO 00/40620.
    [132] For suspension reactors, the reaction temperature will generally be 60 to 110 ° C (for example, 85 to 110 ° C), the reactor pressure will generally be 5 to 80 bar (5,000 to 8,000 kPa) ( for example, from 50 to 65 bar (5,000 to 6,500 kPa), and the dwell time will generally be 0.3 to 5 hours (for example, 0.5 to 2 hours). The diluent used will generally be an aliphatic hydrocarbon with a boiling point between -70 to +100 ° C. In these reactors, polymerization can, if desired, be carried out under supercritical conditions. Preferably, the polymer is produced in a closed loop reactor where ethylene is polymerized in the presence of the polymerization catalyst, as indicated above, and a chain transfer agent such as hydrogen. The inert diluent is typically an aliphatic hydrocarbon, preferably isobutane or propane. The elastomer (E2) can contain several standard polymeric additives, such as antioxidants, UV stabilizers and polymer processing agents.
    [133] To mix the individual components of the present fiber-reinforced composition, the conventional composition or mixing apparatus, such as the Banbury mixer, two-roller rubber mill, Buss co-kneader or a twin screw extruder can be used. Preferably, mixing is carried out in the co-rotating twin screw extruder. The polymer materials recovered from the extrusion machine are generally in the form of pellets. These pellets are preferably further processed, for example, injection molded to generate articles and products of the fiber-reinforced composition of the invention.
    [134] The present invention also relates to automobile articles comprising fiber-reinforced composition as defined above.
    [135] In addition, the present invention also relates to the use of the fiber-reinforced composition as defined above for automotive articles.
    [136] Furthermore, the present invention also relates to a process for preparing the fiber-reinforced composition according to any one of the preceding claims 1 to 8, comprising the steps of adding: (a) the heterophasic propylene copolymer (HECO), (b) the propylene homopolymer (H-PPI), the propylene copolymer (C-PPI), or the mixture of the propylene homopolymer (H-PPI) and the propylene copolymer (C-PPI), and (c) the fibers (F) to an extruder and extrude it obtaining said fiber-reinforced composition.
    [137] The fiber-reinforced composition according to the invention can be pelleted and composed using any of the varieties of formulation and mixing methods well known and commonly used in the resin compositing art.
    [138] The fiber-reinforced composition of the present composition can be used for the production of molded articles, preferably injection-molded articles. Even more preferred is the use for the production of washing machine or dishwasher parts, as well as automotive articles, especially for interiors of automobiles and exteriors, such as instrument carriers, shrouds, structural carriers, bumpers, side moldings, steps auxiliaries, body panels, spoilers, interior panels, interior finishes and the like.
    [139] The present invention also provides articles, such as injection molded articles or foamed articles, comprising the fiber-reinforced composition of the invention. Thus, the present invention is especially aimed at parts of washing machines or dishwashers, as well as automotive articles, especially for car interiors and exteriors, such as bumpers, side friezes, auxiliary steps, body panels, spoilers, panels , interior finishes and the like, comprising the polypropylene composition of the invention.
    [140] According to a preferred embodiment, the article is a foam article comprising the fiber-reinforced composition described above.
    [141] Examples of such foamed articles for automotive applications are instrument carriers, shrouds, or structural carriers.
    [142] Suitable methods of preparing foamed articles by chemical or physical foaming are generally known to the skilled person.
    [143] The present invention will now be described in more detail by the examples presented below. EXAMPLES 1. Measurement Definitions / Methods
    [144] The following definitions of the terms and methods of determination apply to the general description of the invention above, as well as the examples below, unless otherwise defined. Quantification of polypropylene isotacticity by 13C NMR spectroscopy.
    [145] Isotacticity is determined by quantitative 13C nuclear magnetic resonance (NMR) spectroscopy, after base assignment, for example in: V. Busico and R. Cipullo, Progress in Polymer Science, 2001, 26, 443- 533. Experimental parameters are adjusted to ensure quantitative measurement of spectra for this specific task, for example, in: S. Berger and S. Braun, 200 and More NMR Experiments: A Practical Course, 2004, Wiley-VCR, Weinheim. Quantities are calculated using simple corrected ratios of the signal members of representative locations in a manner known in the art. Isotacticity is determined at the pentant level, that is, mmmm fraction of the pentant distribution.
    [146] Numerical average molecular weight (Mn), weighted average molecular weight (Mw) and molecular weight distribution (MWD) are determined by size exclusion chromatography (SEC) using a Waters Alliance GPCV 2000 instrument with an in-line viscometer. The oven temperature is 140 ° C. Trichlorobenzene is used as a solvent (ISO 16014).
    [147] Density is measured according to ISO 1183-187. Sample preparation is done by compression molding according to ISO 1872-2: 2007.
    [148] Melting temperature Tm is measured according to ISO 11357-3
    [149] MFR2 (230 ° C) is measured according to ISO 1133 (230 ° C, 2.16 kg of load).
    [150] MFR2 (190 ° C) is measured according to ISO 1133 (190 ° C, 2.16 kg of load).
    [151] Quantification of comonomer content by FTIR spectroscopy
    [152] Comonomer content is determined by quantitative Fourier transform infrared spectroscopy (FTIR) after basic assignment calibrated using quantitative 13C nuclear magnetic resonance (NMR) in a manner well known in the art. Thin films are pressed to a thickness between 100-500 μm and spectra recorded in the transmission mode.
    [153] Specifically, the ethylene content of a polypropylene-co-ethylene copolymer is determined using the corrected baseline of the quantitative bands found at 720-722 and 730-733 cm-1. Quantitative results are obtained based on the reference to the film thickness.
    [154] Intrinsic viscosity is measured according to DIN ISO 1628/1, October 1999 (in Decalin at 135 ° C).
    [155] Voltage module; Elongation at break; Yield stress are measured according to ISO 527-2 (crosshead speed = 50 mm / min, 23 ° C), using injection molded samples, as described in EN ISO 1873-2 (dog bone shape, 4 mm ).
    [156] Flexural modulus: The flexural modulus was determined in flexion at 3 points in accordance with ISO 178 in injection molded samples of 80 x 10 x 4 mm, prepared in accordance with ISO 294-1: 1996.
    [157] Charpy impact test: Charpy (notched) impact resistance (Charpy NIS / IS) is measured according to ISO 179 2C / DIN 53453, at 23 ° C and -20 ° C, using test species of injection molded bar 80 x 10 x 4 mm3 prepared according to ISO 294-1: 1996.
    [158] Cold xylenes soluble (XCS,% by weight): xylene soluble content (XCS) is determined at 23 ° C according to ISO 6427.
    [159] Average fiber diameter:
    [160] Determined according to ISO 1888: 2006 (E), Method B, microscope magnification 1000. 2. Examples
    [161] The following invention example IE1 and comparative examples CE1 and CE2 were prepared.

    [162] PP1 is the commercial product HJ120UB from Borealis AG, which is a homopolymer with an MFR2 (230 ° C) of 75 g / l0min and a density of 905 kg / m3.
    [163] HECO is the commercial product EF015AE from Borealis AG with an MFR2 (230 ° C) of 18 g / l0 min, and a total comonomer content (C2) of 20% by weight, and a soluble content in xylene at cold (XCS) of 29% by weight.
    [164] Fiber 1 is the commercial product ECS 03 T-480H from Nippon Electrics Glass Co., Ltd., with a filament diameter of 10.5 μm and a wire length of 3 mm.
    [165] PP2 is the commercial product HD601CF from Borealis AG, which is a homopolymer with an MFR2 (230 ° C) of 8 g / l0min.
    [166] PP3 is the commercial product HC101BF from Borealis AG, which is a homopolymer with an MFR2 (230 ° C) of 3.2 g / l0 min.
    [167] Fiber 2 is the commercial product of NEG ECS 03T- 480 / R which has a filament diameter of 13 μm.
    [168] PP-4 is the commercial product HG265FB from Borealis AG which is a homopolymer with an MFR2 (230 ° C) of 26 g / 10 min.
    [169] PP-5 is the commercial product HK060AE from Borealis AG which is a homopolymer with an MFR2 (230 ° C) of 125 g / l0 min.
    [170] Fiber 3 is the commercial product EC13 4.5 MM 968 with a filament diameter of 13 μm.

    [171] The material according to the inventive example combines high fluidity, which is relevant for the processing of auto parts, with greater rigidity and impact resistance. The material of the invention can also be foamed to provide an improved foam structure.
    权利要求:
    Claims (10)
    [0001]
    1. Fiber reinforced composition characterized by the fact that it comprises: (a) a heterophasic propylene copolymer (HECO), (b) a propylene homopolymer (H-PP1) and / or a propylene copolymer (C-PP1), and (c) fibers (F) with an average diameter of 12.0 μm or less and an aspect ratio of 150 to 450, in which (i) the propylene copolymer (C-PP1) comprises no more than 2.0 % by weight of C2 to C10 α-olefins other than propylene, (ii) the propylene homopolymer (H-PP1) and the propylene copolymer (C-PP1) have a flow rate MFR2 (230 ° C) measured according to with ISO 1133 of at least 50 g / 10 min, and (iii) the fiber-reinforced composition has an MFR2 melt index (230 ° C) measured according to ISO 1133 of at least 10 g / 10 min.
    [0002]
    2. Fiber reinforced composition according to claim 1, characterized by the fact that the heterophasic propylene copolymer (HECO) comprises a polypropylene matrix (M-PP), preferably the polypropylene matrix (M-PP) is a propylene homopolymer (H-PP2), and dispersed therein an elastomeric copolymer (E1) comprising units derived from: - propylene and - ethylene and / or C4 to C20 α-olefin.
    [0003]
    3. Fiber-reinforced composition according to claim 2, characterized by the fact that the polypropylene matrix (M-PP) has a lower flow rate MFR2 (230 ° C), measured according to ISO 1133, than the propylene homopolymer (H-PP1) or the propylene copolymer (C-PP1).
    [0004]
    4. Fiber-reinforced composition according to any one of the preceding claims, characterized by the fact that the composition comprises: (a) 10.0 to 50.0% by weight of the propylene heterophasic copolymer (HECO), (b) 20.0 to 70.0% by weight of the propylene homopolymer (H-PP1), the propylene copolymer (C-PP1), or the mixture of the propylene homopolymer (H-PP1) and the propylene copolymer (C- PP1), and (c) 5.0 to 50.0% by weight of fibers (F), based on the total weight of the fiber-reinforced composition.
    [0005]
    5. Fiber reinforced composition according to any one of the preceding claims, characterized by the fact that the heterophasic propylene copolymer (HECO) has: (a) a content of cold xylene soluble (XCS) measured according to ISO 6427 (at 23 ° C) of not more than 35% by weight, and / or (b) a fluidity index of MFR2 (230 ° C) measured according to ISO 1133 of more than 15 g / 10 min, and / or (c) a C2 to C10 total α-olefin content different from the propylene content of 10 to 30% by weight.
    [0006]
    6. Fiber-reinforced composition according to any one of the preceding claims, characterized by the fact that the propylene homopolymer (H-PPI) has a fluidity index MFR2 (230 ° C) measured according to ISO 1133 in the range from 50 to 150 g / 10min, both are very well defined in the specification.
    [0007]
    7. Fiber reinforced composition according to any of the preceding claims, characterized by the fact that the fibers (F) are selected from the group consisting of glass fibers, metallic fibers, ceramic fibers and graphite fibers.
    [0008]
    8. Automotive article characterized by the fact that it comprises the fiber-reinforced composition as defined in any of the preceding claims.
    [0009]
    9. Foam article, characterized by the fact that it comprises the fiber-reinforced composition as defined in any one of claims 1 to 7.
    [0010]
    10. Process for the preparation of the fiber-reinforced composition as defined in any of claims 1 to 7, characterized by the fact that it comprises the steps of adding: (a) the heterophasic propylene copolymer (HECO), (b) the homopolymer of propylene (H-PP1), the propylene copolymer (C-PP1) or the mixture of propylene homopolymer (H-PP1) and the propylene copolymer (C-PP1), and (c) the fibers (F) to a extruder and extrude it obtaining the said fiber-reinforced composition.
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    法律状态:
    2018-03-27| B06F| Objections, documents and/or translations needed after an examination request according art. 34 industrial property law|
    2020-02-27| B06U| Preliminary requirement: requests with searches performed by other patent offices: suspension of the patent application procedure|
    2020-11-17| B09A| Decision: intention to grant|
    2020-12-22| B16A| Patent or certificate of addition of invention granted|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 27/03/2013, OBSERVADAS AS CONDICOES LEGAIS. |
    优先权:
    申请号 | 申请日 | 专利标题
    EP12163221.0|2012-04-04|
    EP12163221|2012-04-04|
    PCT/EP2013/056578|WO2013149915A1|2012-04-04|2013-03-27|High-flow fiber reinforced polypropylene composition|
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