COMPOSITION UNDERSTANDING COMPOSITION OF AUTOMOBILE INTERIOR

专利摘要:
composed of automobile interiors. the present invention relates to a composition having a flow rate mfr <sym> (230ºc), measured according to iso 1133 in the range of 15 to 30 g / 10 min. said composition comprises a heterophasic propylene copolymer (h- pp1), a high melt flow polypropylene (hmf-pp), a styrenic block copolymer (sbc) and a mineral filler (f), where (a) the heterophasic propylene copolymer (h-pp1) has a of cold soluble xylene (xcs) measured according to iso 6427 in the range of 22.0 to 50.0% by weight and comprises (a1) a polypropylene matrix (m1) and (a2) an elastomeric copolymer (e1) that comprises units derived from propylene and ethylene and / or <244> -olefin c <sym> ac <sym>, (b) the melting flow rate mfr <sym> (230ºc) measured according to iso 1133 of high polypropylene fusion flow (hmf-pp) is higher than the mfr <sym> fusion flow rate (230ºc) measured according to iso 1133 of the heterophasic propylene copolymer (h-pp1), and (c) the polypropylene high melt flow (hmf-pp) has the melt flow rate mfr <sym> (230ºc) measured according to iso 1133 of at least 40.0 g / 10 min.
公开号:BR112012026586B1
申请号:R112012026586-5
申请日:2011-04-15
公开日:2020-03-10
发明作者:Klaus Lederer；Erwin Kastner
申请人:Borealis Ag；
IPC主号:

专利说明:

Descriptive Report of the Invention Patent for "COMPOSITION UNDERSTANDING COMPOSITE OF CAR INTERIOR".
[001] The present invention relates to a new propylene composition suitable for the automobile industry.
[002] Polypropylene is now the polymer of choice for auto parts such as bumpers, door panels, and instrument panels. In particular, heterophasic propylene copolymers (HECO) are suitable when they combine rigidity with good impact behavior. Hypophasic propylene copolymers (HECO) are well known in the art. Such heterophasic propylene copolymers (HECO) comprise a matrix that is a propylene homopolymer or a random propylene copolymer in which an elastomeric copolymer is dispersed. Thus, the polypropylene matrix contains inclusions (finely) dispersed not being part of the matrix and said inclusions contain the elastomeric copolymer. The term inclusion indicates 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, such as electron microscopy or scanning force microscopy.
[003] Even though the heterophasic propylene copolymers on the market achieve a very good balance between rigidity and impact, the profile requirements for such systems become increasingly demanding. For example, today the automotive industry requires polymer materials with very high impact performance and total flexible breakdown behavior by maintaining rigidity at a very high level.
[004] However, such demanding properties cannot be fulfilled by classic heterophasic propylene copolymers. [005] Consequently, the aim of the present invention is to provide a polymeric composition that exhibits an impact behavior of at least 5.0 kJ / m2 (bevelled Izod at -30 ° C), a total flexible failure behavior in the test high speed multiaxial impact as well as a stiffness (flexural modulus) of at least 1750 MPa. In addition, the polymeric composition must have a very high melt flow rate and preferably a higher scratch resistance.
[006] The finding of the present invention is that a composition must be provided comprising a heterophasic propylene copolymer, a high melt flow component, a styrenic block copolymer, and a mineral filler preferably having a high aspect ratio.
[007] Consequently, the present invention is directed to a composition having an MFR2 melt index (230 ° C) measured according to ISO 1133 in the range of 15 to 30 g / 10 min, said composition comprises a heterophasic propylene copolymer ( H-PP1), a polypropylene with a high fluidity index (HMF-PP), a styrenic block copolymer (SBC) and a mineral filler (F), in which (a) the heterophasic propylene copolymer (H-PP1) presents a cold soluble xylene content (XCS) measured according to ISO 6427 in the range of 22.0 to 50.0% by weight and comprises (a1) a polypropylene matrix (M1) and (a2) an elastomeric copolymer (E1 ) comprising units derived from - propylene and - ethylene and / or α-olefin C4 to C12, the flow rate MFR2 (230 ° C) measured according to ISO 1133 of the polypropylene with high flow rate (HMF-PP ) is higher than the MFR2 fluidity index (230 ° C) measured according to ISO 1133 of the heterophasic propylene copolymer (H-PP1), and (c) polypropylene with high flow rate (HMF-PP) has the flow rate MFR2 (230 ° C) measured according to ISO 1133 of at least 40.0 g / 10 min.
[008] Preferably the composition additionally comprises a high density polyethylene (HDPE).
[009] More precisely, the present invention is directed to a composition presenting a fluidity index MFR2 (230 ° C) measured according to ISO 1133 in the range of 15 to 30 g / 10 min, said composition comprises - 20 to 40% by weight, preferably 25 to 35% by weight, of a heterophasic polypropylene (H-PP1), - 17 to 38% by weight, preferably 22 to 30% by weight, of a polypropylene with a high flow rate ( HMF-PP), - 7 to 25% by weight, preferably 12 to 20% by weight, of a styrenic block copolymer (SBC) - optionally from 2 to 10% by weight, more preferably from 3 to 7% by weight weight of a high density polyethylene (HDPE), and - 15 to 30% by weight, preferably 15 to 25% by weight, of a mineral filler (F), based on the composition, more preferably based on the components H-PP1, HMF-PP, SBC, HDPE and F, where (a) the heterophasic propylene copolymer (H-PP1) has a cold soluble xylene content (XCS) measured according to ISO 6427 in the range of 22 , 0 to 50.0% by weight and comprises (a1) a polypropylene matrix (M1) and (a2) an elastomeric copolymer (E1) comprising units derived from - propylene and - ethylene and / or α-olefin C4 at C12, the MFR2 fluidity index (230 ° C) measured according to ISO 1133 of the high fluidity polypropylene (HMF-PP) is higher than the MFR2 fluidity index (230 ° C) measured according to ISO 1133 of the heterophasic propylene copolymer (H-PP1), and (c) polypropylene with a high fluidity index (HMF-PP) shows the MFR2 fluidity index (230 ° C) measured according to ISO 1133 of at least 40 , 0 g / 10 min.
[0010] It is evident from the phraseology used for the different polymers (H-PP1, HMF-PP, SBC and HDPE) according to the present invention that must (chemically) differ from each other.
[0011] The expression "heterophasic" indicates that an elasomeric copolymer is (finely) dispersed in a matrix. In other words, the elastomeric copolymer forms inclusions in the matrix. Thus the matrix contains inclusions (finely) dispersed that are not part of the matrix and said inclusions contain the elastomeric copolymer. The term "inclusion" according to this invention should preferably indicate that the matrix and the inclusion form different phases within the heterophasic propylene copolymer, said inclusions are, for example, visible through high resolution microscopy, such as electron microscopy or microscopy sweep force. The final composition is probably of a complex structure. Probably the matrix of heterophasic propylene copolymers forms a continuous phase which is the matrix of the composition in which the elastomeric copolymer, the styrenic block copolymer (SBC), and optionally high density polyethylene (HDPE) form together or individually inclusions dispersed in it.
[0012] Additionally, the inclusions of the final composition may also contain the mineral filler (F); however, preferably, the mineral filler (F) forms separate inclusions within the matrix.
[0013] In another embodiment the matrix contains inclusions (finely) dispersed that are not part of the matrix and said inclusions contain the elastomeric copolymer and the styrenic block copolymer (SBC). In such a case the styrenic block copolymer (SBC) can preferably form on its partly (finely dispersed) inclusions within the elastomeric copolymer.
[0014] In addition, the composition according to the present invention preferably comprises the heterophasic propylene copolymer (H-PP1), the high fluidity polypropylene (HMF-PP), the styrenic block copolymer (SBC), and optionally high density polypropylene (HDPE) as the only polymeric components within the composition. In other words, the present invention may contain other additives, such as mineral filler (F), but no other polymer in an amount greater than 8% by weight, more preferably greater than 5% by weight, such as greater than 3% by weight, based on the total composition. An additional polymer that can be present in such low amounts is a polyethylene which is a reaction by-product obtained by preparing heterophasic propylene copolymers (see in detail below) or a polyethylene from standard pigment mixtures.
[0015] It was surprisingly found that the composition according to this invention has an extremely high impact combined with the total flexible breakdown behavior in the high speed multiaxial impact test at very low temperatures. In addition, the composition shows very high stiffness and outstanding scratch resistance (see the example section).
[0016] The present invention will now be described in more detail.
[0017] A requirement is that the final 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 lower flow tendency than small molecules. An increase in molecular weight means a decrease in the MFR value. The fluidity index (MFR) is measured in g / 10 min of the polymer discharged through a matrix defined under specific conditions of temperature and pressure and the measure of the viscosity of the polymer which, in turn, for each type of polymer is mainly influenced for its molecular weight, but also for its degree of branching. The flow rate measured under a load of 2.16 kg at 230 ° C (ISO 1133) is indicated as MFR2 (230 ° C). Consequently, it is noted that in the present invention the composition has a melt flow index MFR2 (230 ° C) in a range of 15.0 to 30.0 g / 10 min, preferably from 17.0 to 28.0 g / 10 min.
[0018] In addition, to obtain the desired melt flow properties of the composition, a polymer with a very high melt flow rate must be present. Accordingly, the composition of the invention comprises a high melt flow propylene copolymer (HMF-PP) having an MFR2 melt index (230 ° C) of at least 40 g / 10 min, preferably an MFR2 melt index (230 ° C) in the range of 40.0 to 1000.0 g / 10 min, more preferably in the range of 60.0 to 500.0 g / 10 min, even more preferably in the range of 70 to 200 g / 10 min. In a preferred embodiment the high flow rate propylene copolymer (HMF-PP) is not degraded. In a specific embodiment the propylene copolymer with high melt index (HMF-PP) is a heterophasic propylene copolymer (H-PP1) as defined below.
[0019] In addition, the propylene copolymer with a high fluidity index (HMF-P) differs, inter alia, from the heterophasic propylene copolymer (H-PP1) in its melt flow behavior. Therefore, another requirement according to this invention is that the flow rate MFR2 (230 ° C) of the propylene copolymer with high flow rate (HMF-PP) is higher than the flow rate MFR2 (230 ° C ) of the heterophasic propylene copolymer (H-PP1). More specifically, it is observed that the MFR2 fluidity index (230 ° C) of the high fluidity propylene cup-polymer (HMF-PP) is at least 30 g / 10 min, more preferably at least 50 g / 10 min, higher than the flow rate MFR2 (230 ° C) of the heterophasic propylene copolymer (H-PP1). Consequently, it is observed in particular that the ratio of the MFR2 fluidity index (230 ° C) of the heterophasic propylene copolymer (H-PP1) to the MFR2 fluidity index (230 ° C) of the high propylene copolymer fluidity (HMF-PP) [MFR (H-PP1) / MFR (HMF-PP)] is in the range of 1: 4 to 1:80, more preferably in the range of 1: 5 to 1:50).
[0020] The heterophasic propylene copolymer (H-PP1) is a typical material used in this technical field. Consequently, the heterophasic propylene cup-polymer (H-PP1) preferably has an MFR2 melt index (230 ° C) in the range of 3.0 to 30.0 g / 10 min, more preferably in the range of 7.0 to 20.0 g / 10 min, even more preferably in the range of 9.0 to 15.0 g / 10 min.
[0021] As mentioned above, the heterophasic propylene copolymer (H-PP1) according to the present invention comprises (a) a polypropylene matrix (M1) and (b) an elastomeric copolymer (E1) comprising units derived from - propylene and - ethylene and / or α-olefin C4 to C12.
[0022] Preferably the propylene content in the heterophasic propylene copolymer (H-PP1) is 75.0 to 92.0% by weight, more preferably 80.0 to 90.0% by weight, based on the copolymer of total heterophasic propylene (H-PP1), more preferably based on the amount of the polymer components of the heterophasic propylene copolymer (H-PP1), even more preferably based on the amount of the matrix (M1) and the elastomeric copolymer (E1) together. The remaining part constitutes comonomers other than propylene (ethylene and / or α-olefin C4 to C12), preferably constitutes ethylene.
[0023] As defined herein a heterophasic propylene copolymer (H-PP1) comprises as polymer components only the polypropylene matrix (M1) and the elastomeric copolymer (E1). In other words, the heterophasic propylene copolymer (H-PP1) may still contain additives, but no other polymer in an amount greater than 5% by weight, more preferably greater than 3% by weight, such as greater than 1% by weight, based on the total heterophasic propylene copolymer (H-PP1), more preferably based on the polymers present in the heterophasic propylene copolymer (H-PP1). An additional polymer that may be present in low amounts is a polyethylene which is a reaction product obtained by preparing the heterophasic propylene copolymer (H-PP1). Consequently, it is in particular observed that a heterophasic propylene copolymer (H-PP1) as defined in the present invention contains only a polypropylene matrix (M1), an elastomeric copolymer (E1) and optionally a polyethylene in quantities as mentioned in this paragraph.
[0024] In addition, throughout the present invention the cold insoluble xylene fraction (XCI) of the heterophasic propylene copolymer (H-PP1) represents the matrix (M1) and optionally polyethylene, while the soluble xylene fraction a cold (XCS) represents the elastomeric part of the heterophasic propylene copolymer (H-PP1), that is, the elastomeric copolymer (E1).
[0025] Thus, the matrix content (M1), that is, the content of cold insoluble xylene (XCI), in the heterophasic propylene copolymer (H-PP1) is preferably in the range of 50.0 to 78.0 % by weight, more preferably in the range of 55.0 to 75.0% by weight. In the case where polyethylene is present in the heterophasic propylene copolymer (H-PP1), the values for the matrix content (M1), but not for the cold insoluble xylene content (XCI), may be slightly decreased.
[0026] On the other hand, the content of elastomeric copolymer (E1), that is, the content of cold soluble xylene (XCS), in the heterophasic propylene copolymer (H-PP1) is preferably in the range of 22.0 to 50.0% by weight, more preferably in the range of 25.0 to 45.0% by weight.
The polypropylene matrix (M1) is preferably a random propylene copolymer (R1) or a propylene homopolymer (H1), the latter being especially preferred.
[0028] Consequently, the comonomer content of the polypropylene matrix (M1) is equal to or below 1.0% by weight, even more preferably not more than 0.8% by weight, even more preferably not more than 0 , 5% by weight, such as not more than 0.2% by weight.
[0029] As mentioned above, the polypropylene (M1) matrix is preferably a propylene (H1) homopolymer.
The term propylene homopolymer used in the present invention refers to a polypropylene that consists substantially, that is, of more than 99.7% by weight, even more preferably at least 99.8% by weight, of units propylene. In a preferred embodiment, only the propylene units in the propylene homopolymer are detectable. The comonomer content can be determined with FT infrared spectroscopy, as described below in the examples.
[0031] In the case the polypropylene matrix (M1) is a random propylene copolymer (R1), it is observed that the random propylene copolymer (R1) comprises the copolymerizable monomers with propylene, for example, comonomers such as ethylene and / or C4 to C12 α-olefins, in particular ethylene and / or C4 to C12 α-olefins, for example, 1-butene and / or 1-hexene. Preferably, the random propylene copolymer (R1) according to this invention comprises, especially consists of, monomers copolymerizable with propylene from the group consisting of ethylene, 1-butene and 1-hexene. More specifically, the random propylene copolymer (R1) of this invention comprises - in addition to propylene - units derived from ethylene and / or 1-butene. In a preferred embodiment the random propylene copolymer (R1) comprises units derived from ethylene and propylene alone.
[0032] Additionally, it is noted that the random propylene copolymer (R1) preferably has a comonomer content in the range of more than 0.3 to 1.0% by weight, more preferably in the range of more than 0, 3 to 0.8% by weight, even more preferably in the range of 0.3 to 0.7% by weight.
[0033] The term "random" indicates that the comonomers in the random propylene copolymer (R1) and (R2) are randomly distributed within the propylene copolymers. The term random is understood according to IUPAC (Glossary of basic terms in polymer science; IUPAC recommendations 1996).
[0034] The polypropylene matrix (M1) of the heterophasic propylene copolymer (H-PP1), preferably the polypropylene matrix (M1) being the propylene homopolymer (H1), can be multimodal or bimodal taking into account the molecular weight .
[0035] The term "multimodal" or "bimodal" used throughout the present invention 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 a function of their molecular weight, and / or ■ the shape of their comonomer content distribution curve, which is the graph of the comonomer content as a function of the molecular weight of the polymer fractions.
[0036] As will be explained below, heterophasic propylene copolymers as well as their individual components (matrix and elastomeric copolymer) can be produced by mixing different types of polymer, that is, of different molecular weight and / or comonomer content . However, it is preferable that the heterophasic propylene copolymers as well as their individual components (matrix and elastomeric copolymer) are produced in a process of sequential steps, using reactors of series configuration and operating under different reaction conditions. As a consequence, each fraction prepared in a specific reactor will have its own molecular weight distribution and / or distribution of comonomer content.
[0037] It is also observed that the polypropylene (M1) matrix of the heterophasic propylene copolymer (H-PP1) shows a moderate melting flow MFR2 (230 ° C). As mentioned above, the flow rate MFR2 (230 ° C) of the polypropylene matrix (M1) matches the flow rate MFR2 (230 ° C) of the cold insoluble xylene fraction (XCI) of the heterophasic propylene copolymer (H -PP1). Thus, it is preferable that the cold insoluble xylene fraction (XCI) of the heterophasic propylene copolymer (H-PP1) has an MFR2 fluidity index (230 ° C), measured according to ISO 1133 from 20.0 to 150.0 g / 10 min, more preferably from 25.0 to 90.0 g / 10 min, even more preferably from 30.0 - 75.0 g / 10 min.
[0038] Preferably, the polypropylene (M1) matrix is isotactic. Thus it is observed that the polypropylene matrix (M1) has a quite high quinquevalent concentration, that is, higher than 80%, more preferably higher than 85%, even more preferably higher than 90%, even more preferably higher than 92%, even more preferably higher than 93%, as higher than 95%.
[0039] The second component of the heterophasic propylene copolymer (H-PP1) is the elastomeric copolymer (E1).
[0040] The elastomeric copolymer (E1) preferably comprises units derived from (i) propylene and (ii) ethylene and / or at least another α-olefin C4 to C12, such as α-olefin C4 to C10, more preferably units derived from (i) propylene and (ii) ethylene and at least selected α-olefin form the group consisting of 1-butene, 1-pentene, 1-hexene, 1-heptene and 1-octene. The elastomeric copolymer (E1) can additionally contain units derived from a conjugated diene, such as butadiene, or an unconjugated diene, however, it is said that the elastomeric copolymer (E1) consists of units derived from (i) propylene and ( ii) ethylene and / or only C4 to C12 α-olefins. 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 dihydroocymene, 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-cyclohexene and 1-isopropenyl-4- (4-butenyl) -cyclohexane. Fused multi-ring and bridged ring alicyclic dienes are also suitable, including tetrahydroindene, methyltetrahydroindene, dicyclopentadiene, (2,2,1) hep-ta-2,5-diene, 2-methyl bicycloeptadiene, and alkenyl, alkylidene, cycloalkenyl and cycloalkylidene norbornenes, such as 5-methylene-2-norbornene, 5-isopropylidene norbornene, 5- (4-cyclopentenyl) -2-norbornene and 5-cyclohexylidene-2-norbornene. Preferred unconjugated dienes are 5-ethylidene-2-norbornene, 1,4-hexadiene and dicyclo-pentadiene.
[0041] Consequently, the elastomeric copolymer (E1) comprises at least the units derived from propylene and ethylene and can comprise other units derived from another α-olefin as defined in the previous paragraph. However, it is particularly preferred that the elastomeric copolymer (E1) comprises only the units derived from propylene and ethylene and optionally a conjugated diene, such as butadiene, or an unconjugated diene as defined in the previous paragraph, such as 1,4-hexadiene. Thus, a non-conjugated ethylene propylene diene monomeric polymer (EPDM1) and / or an ethylene propylene rubber (EPR1) as an elastomeric copolymer (E1) is especially preferred, the latter most preferred.
[0042] As the polypropylene matrix (M1) the elasto-metallic copolymer (E1) can be unimodal or multimodal, in the same way as bimodal, the latter being the preferred one. Regarding the definition of unimodal and multimodal, as bimodal, it refers to the definition above. [0043] In the present invention the content of pro-pilen-derived units in the elastomeric copolymer (EP1) equals the detectable propylene content in the cold soluble xylene fraction (XCS). Consequently, the detectable propylene in the cold soluble xylene fraction (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 cold soluble xylene fraction (XCS), comprises from 25.0 to 50.0% by weight, more preferably from 30, 0 to 45.0% by weight, of units derived from ethylene and / or at least one other C4 to C12 α-olefin. Preferably, the elastomeric copolymer (E1) is a non-conjugated ethylene propylene diene monomeric polymer (EPDM1) or an ethylene propylene rubber (EPR1), the latter especially preferred, with a propylene and / or ethylene content as defined herein paragraph.
[0044] Another preferred requirement of the present invention is that the intrinsic viscosity (IV) of the cold soluble xylene fraction (XCS) of the heterophasic propylene copolymer (H-PP1) is relatively high. Very high values of intrinsic viscosity (IV) improve impact resistance. Consequently, it is observed that the intrinsic viscosity of the cold soluble xylene fraction (XCS) of the heterophasic propylene copolymer (H-PP1) is above 2.0 dL / g, more preferably at least 2.3 dL / g. On the other hand, the intrinsic viscosity (IV) must not be too high, otherwise the flowable capacity is reduced. Thus, the intrinsic viscosity of the cold soluble xylene fraction (XCS) of the heterophasic propylene copolymer (H-PP1) is preferably in the range of 2.0 to 4.5 dL / g, more preferably in the range of 2.3 to 4.1 dL / g. Intrinsic viscosity is measured according to ISO 1628 in decal at 135 ° C.
[0045] Preferably the heterophasic propylene copolymer (H-PP1) is α-nucleated. Examples of suitable α-nucleating agents are inorganic additives such as talc, silica or kaolin, salts of monocarboxylic or polycarboxylic acids, for example, sodium benzoate or aluminum tert-butylbenzoate, dibenzylidenosorbitol or its derivatives substituted by C1-C8 alkyl such as methyldibenzyl-denossorbitol, ethyldibenzylidenosorbitol or dimethyldibenzylidenosorbitol or salts of phosphoric acid diesters, eg 2,2'-methylenebis (4,6, -di-tert-butylphenyl) sodium phosphate or nonitol derivatives such as 1,2, 3-trideoxy-4,6: 5,7-bis-O [(4-propylphenyl) -methylene] -nonitol.
[0046] Preferred α-nucleating agents are selected from the group consisting of (i) salts of monocarboxylic acids and polycarboxylic acids, for example, sodium benzoate or aluminum tert-butylbenzoate, and (ii) dibenzylidenosorbitol (eg example: 1,3: 2,4 dibenzyl-denosorbitol) and C-Cs-substituted dibenzylidenosorbitol derivatives, such as methyldibenzylidenosorbitol, ethyldibenzylidenosor-bitol or dimethyldibenzylidenosorbitol (eg 1,3: 2,4 di (methylbenzylidene) sorbitol) , nonitol, 1,2,3, -trideoxy-4,6: 5,7-bis-O - [(4-propylphenyl) methylene] -nonitol, and (iii) diester salts of phosphoric acid, for example, 2 , 2'-methylenebis (4, 6, -di-tert-butylphenyl) sodium phosphate or aluminum-hydroxy-bis [2,2'-methylene-bis (4,6-di-t-butylphenyl) phosphate], and (iv) vinylcycloalkane polymer and vinylalkane polymer. [0047] The nucleating agent content of the heterophasic propylene copolymer (H-PP1) is preferably up to 5% by weight.
[0048] Such additives are generally commercially available and are described, for example, in Gachter / Muller, Plastics Additives Handbook, 4th Edition, Hansa Publishers, Munich, 1993. [0049] In a preferred embodiment, the copolymer of heterophasic propylene (H-PP1) of the present invention contains from 0.1 to 1% by weight, preferably from 0.15 to 0.25% by weight, of a nucleating agent, in particular salts of phosphoric acid diesters , for example, 2,2'-methylenebis (4, 6, -di-tert-butylphenyl) sodium phosphate or aluminum-hydroxy-bis [2,2'-methylene-bis (4,6-di-t-butylphenyl) )phosphate]. In another preferred embodiment the heterophasic propylene copolymer (H-PP1) is nucleated BNT as mentioned below.
[0050] As mentioned above as another polymer component, a polypropylene with a high fluidity index (HMF-PP) must be present. Preferably, said high flow rate polypropylene (HMF-PP) is a heterophasic propylene copolymer (H-PP2). So in what follows, the heterophasic propylene copolymer (H-PP2) is defined in more detail.
[0051] Regarding the MFR2 fusion flow rate (230 ° C) of the heterophasic propylene copolymer (H-PP2), it refers to the information provided for the polypropylene with high flow rate (HMF-PP).
[0052] Furthermore, the heterophasic propylene copolymer (H-PP2) according to this invention comprises (a) a polypropylene matrix (M2) and (b) an elastomeric copolymer (E2) comprising units derived from - propylene and - ethylene and / or α-olefin C4 to C12.
[0053] Preferably, the propylene content in the heterophasic propylene copolymer (H-PP2) is 85.0 to 96.0% by weight, more preferably from 88.0 to 94.0% by weight, based on total heterophasic propylene copolymer (H-PP2), more preferably based on the amount of the polymer components of the heterophasic propylene copolymer (H-PP2), even more preferably based on the amount of the matrix (M2) and the elastomeric copolymer (E2 ) together. The remaining part constitutes comonomers other than propylene (ethylene and / or α-olefin C4 to C12), preferably constitutes ethylene.
[0054] With reference to the definition of a heterophasic polypropylene, see the information provided when discussing the heterophasic propylene copolymer (H-PP1). Consequently, the heterophasic propylene copolymer (H-PP2) comprises only the polypropylene matrix (M2) and the elastomeric copolymer (E2) as polymer components. In other words, the heterophasic propylene copolymer (H-PP2) may contain other additives, but no other polymer in an amount greater than 5% by weight, more preferably greater than 3% by weight, such as greater than 1% by weight , based on the total heterophasic propylene copolymer (H-PP2), more preferably based on the polymers present in the heterophasic propylene copolymer (H-PP2). An additional polymer that can be present in such low amounts is a polyethylene which is a product of the reaction obtained by preparing the heterophasic propylene copolymer (H-PP2). Consequently, it is in particular observed that a heterophasic propylene copolymer (H-PP2) as defined in the present invention, contains only a polypropylene matrix (M2), an elastomeric copolymer (E2) and optionally a polyethylene in quantities as mentioned in this paragraph. In addition, throughout the present invention, the cold insoluble xylene fraction (XCI) of the heterophasic propylene copolymer (H-PP2) represents the matrix (M2) and optionally polyethylene, while the cold soluble xylene fraction ( XCS) represents the elastomeric part of the heterophasic propylene copolymer (H-PP2), that is, the elastomeric copolymer (E2).
[0055] In this way, the matrix content (M2), that is, the content of cold insoluble xylene (XCI), in the heterophasic propylene copolymer (H-PP2) is preferably in the range of 80.0 to 93.0 % by weight, more preferably in the range of 82.0 to 91.0% by weight, as from 83.0 to 89.0% by weight. In the case where polyethylene is present in the heterophasic propylene copolymer (H-PP2), the values for the matrix content (M2), but not for the cold insoluble xylene content (XCI), may be slightly decreased.
[0056] On the other hand, the content of elastomeric copolymer (E2), that is, the content of cold soluble xylene (XCS), in the heterophasic propylene copolymer (H-PP2) is preferably in the range of 7.0 to 20, 0% by weight, more preferably in the range of 9.0 to 18.0% by weight, such as 11.0 to 17.0% by weight.
Consequently, the content of elastomeric copolymer (E2), that is, the content of cold soluble xylene (XCS), in the heterophasic propylene copolymer (H-PP2) is quite low in comparison to the content of elastomeric copolymer ( E2), that is, the content of cold soluble xylene (XCS), in the heterophasic propylene copolymer (H-PP1). Thus, it is observed that the amount of cold soluble xylene content (XCS) of the heterophasic polypropylene (H-PP1) measured according to ISO 6427 is higher, preferably at least 8.0% in higher weight, more preferably at least 11.0% higher by weight, compared to the cold soluble xylene content (XCS) of the heterophasic polypropylene (H-PP2) measured according to ISO 6427. Consequently, it is observed that the following formula (I ), preferably (Ia), XCS (H-PP1)> 1.5 x XCS (H-PP2) (I) XCS (H-PP1)> 1.7 x XCS (H-PP2) (Ia) is satisfied in that XCS (H-PP1) is the soluble xylene content measured according to ISO 6427 supplied in weight percent of the heterophasic polypropylene (H-PP1), and XCS (H-PP2) is the soluble xylene content measured according to ISO 6427 supplied in weight percent of heterophasic polypropylene (H-PP2).
[0058] Furthermore, the polypropylene matrix (M2) is preferably a random propylene copolymer (R2), or a propylene homopolymer (H2), the latter being especially preferred.
[0059] Consequently, the comonomer content of the polypropylene matrix (M2) is equal to or below 1.0% by weight, even more preferably not more than 0.8% by weight, even more preferably not more than than 0.5% by weight, such as not more than 0.2% by weight.
[0060] As mentioned above, the polypropylene (M2) matrix is preferably a propylene (H2) homopolymer.
[0061] In the case the polypropylene matrix (M2) is a random propylene copolymer (R2), it is observed that the random propylene copolymer (R2) comprises the monomers copolymerizable with propylene, for example, comonomers such as ethylene and / or C4 to C12 α-olefins, in particular ethylene and / or C4 to Cs α-olefins, for example, 1-butene and / or 1-hexene. Preferably the random propylene copolymer (R2) according to this invention comprises, especially consists, the copolymerizable monomers with propylene from the group consisting of ethylene, 1-butene and 1-hexene. More specifically, the random propylene (R2) copolymer of this invention comprises - in addition to propylene - units derived from ethylene and / or 1-butene. In a preferred embodiment the random propylene copolymer (R2) comprises units derived from ethylene and propylene alone.
[0062] Additionally, it is noted that the random propylene copolymer (R2) preferably has a comonomer content in the range of more than 0.3 to 1.0% by weight, more preferably in the range of more than 0 .3 to 0.8% by weight, even more preferable in the range of 0.3 to 0.7% by weight.
[0063] The polypropylene matrix (M2) of the heterophasic propylene copolymer (H-PP2), preferably the polypropylene matrix (M2) being the propylene homopolymer (H2), can be multimodal or bimodal in view of the molecular weight.
[0064] Also and preferably the polypropylene (M2) matrix has a very high fluidity index. As mentioned above, when talking about the flow rate of the matrix of a heterophasic polypropylene, the flow rate of the cold insoluble xylene fraction (XCI) of said heterophasic polypropylene is proposed. Thus, the MFR2 fluidity index (230 ° C) measured according to ISO 1133 of the cold insoluble xylene fraction (XCI) of the heterophasic polypropylene (H-PP1) is preferably lower, more preferably at least 80 g / 10 min lower, even more preferably at least 100 g / 10 min lower, compared to the fluidity index MFR2 (230 ° C) measured according to ISO 1133 of the cold insoluble xylene fraction (XCI) of heterophasic polypropylene ( H-PP2).
Consequently, it is stated that in the present invention the polypropylene matrix (M2), that is, the cold insoluble xylene fraction (XCI) of the heterophasic propylene copolymer (H-PP2), has an MFR2 (230 ° C ) in a range of 100.0 to 1500.0 g / 10 min, more preferably from 120.0 to 800.0 g / 10 min, even more preferably from 150.0 to 500.0 g / 10 min.
[0066] Preferably the polypropylene (M2) matrix is isotactic. In this way it is observed that the polypropylene matrix (M2) has a quite high quinquevalent concentration, that is, higher than 80%, more preferably higher than 85%, even more preferably higher than 90%, still more preferably higher than 92%, even more preferably higher than 93%, such as higher than 95%.
[0067] The second component of the heterophasic propylene copolymer (H-PP2) is the elastomeric copolymer (E2).
[0068] The elastomeric copolymer (E2) preferably comprises units derived from (i) propylene and (ii) ethylene and / or at least another α-olefin C4 to C12, such as α-olefin C4 to C10 , more preferably (i) propylene and (ii) ethylene derivatives and at least one other selected α-olefin form the group consisting of 1-butene, 1-pentene, 1-hexene, 1-heptene and 1-octene. The elastomeric copolymer (E2) can additionally contain units derived from a conjugated diene, such as butadiene, or an unconjugated diene, however, it is said that the elastomeric copolymer consists of units derived from (i) propylene and (ii) ethylene and / or only C4 to C12 α-olefins. 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 dihydroocymene, 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-cyclohexene and 1-isopropenyl-4- (4-butenyl) -cyclohexane. Fused multi-ring and bridged ring alicyclic dienes are also suitable, including tetrahydroindene, methyltetrahydroindene, dicyclopentadiene, (2,2,1) hep-ta-2,5-diene, 2-methyl bicycloeptadiene, and alkenyl, alkylidene, cycloalkenyl and cycloalkylidene norbornenes, such as 5-methylene-2-norbornene, 5-isopropylidene norbornene, 5- (4-cyclopentenyl) -2-norborene and 5-cyclohexyleneidene-2-norbornene. Preferred unconjugated dienes are 5-ethylidene-2-norbornene, 1,4-hexadiene and dicyclopentadiene.
Consequently, the elastomeric copolymer (E2) comprises at least the units derived from propylene and ethylene and can comprise other units derived from another α-olefin as defined in the previous paragraph. However, it is particularly preferred that the elastomeric copolymer (E21) comprises only the units derived from propylene and ethylene and optionally a conjugated diene, such as butadiene, or an unconjugated diene as defined in the previous paragraph, such as 1,4-hexadiene . Thus, a monomeric ethylene propylene non-conjugated diene polymer (EPDM2) and / or an ethylene propylene rubber (EPR2) as an elastomeric copolymer (E2) is especially preferred, the latter most preferred.
[0070] Like the polypropylene matrix (M2) the elastomeric copolymer (E1) can be unimodal or multimodal, in the same way as bimodal. With regard to the definition of unimodal and multimodal, such as bimodal, it refers to the definition above.
[0071] In the present invention the content of propylene-derived units in the elastomeric copolymer (E2) equals the detectable propylene content in the cold soluble xylene fraction (XCS). Consequently, the detectable propylene in the cold soluble xylene fraction (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 (E2), that is, the cold soluble xylene fraction (XCS), comprises from 25.0 to 50.0% by weight, more preferably from 30.0 to 45.0% by weight of units derived from ethylene and / or C4 to C12. Preferably the elastomeric copolymer (E2) is a non-conjugated ethylene propylene diene monomeric polymer (EPDM2) or an ethylene propylene rubber (EPR2), the latter especially preferred, with a content of propylene and / or ethylene as defined in this paragraph.
[0072] To achieve a good balance between the rigidity and flexibility the intrinsic viscosity of the cold soluble xylene fraction (XCS) of the two heterophasic polypropylenes will preferably differ. Thus it is observed that the intrinsic viscosity (IV) measured according to ISO 1268-1 (decalin) of the fraction of cold soluble xylene (XCS) of the heterophasic propylene copolymer (H-PP1) is higher compared to the viscosity intrinsic (IV) measured according to ISO 1268-1 (decalin) of the cold soluble xylene fraction (XCS) of the heterophasic propylene copolymer (H-PP2).
[0073] It is therefore preferable that the intrinsic viscosity (IV) of the cold soluble xylene fraction (XCS) of the heterophasic propylene copolymer (H-PP2) is quite low. Very high values of intrinsic viscosity improve the flexibility of the heterophasic system. Thus, it is observed that the intrinsic viscosity of the cold soluble xylene fraction (XCS) of the heterophasic propylene copolymer (H-PP2) is below 2.8 dL / g, more preferably below 2.5 dL / g, even more preferably below 2.0 dL / g. Even more preferable, the intrinsic viscosity of the cold soluble xylene fraction (XCS) of the heterophasic propylene copolymer (H-PP2) is in the range of 1.7 to 3.0 dL / g, more preferably in the range of 1.8 to 2.7 dL / g. Intrinsic viscosity is measured according to ISO 1628 in decal at 135 ° C. [0074] Another essential requirement of the present invention is the presence of a styrenic block copolymer (SBC). Preferably, the styrenic block copolymer (SBC) can be a styrene-ethylene / butylene-stirene block copolymer (SEBS) and / or a hydrogenated styrene-vinyl isoprene block rubber (SIS). It is especially preferable that the styrenic block copolymer (SBC) is a styrene-ethylene / butylene-stirene block copolymer (SEBS).
Consequently, it is observed that the styrenic block copolymer (SBC), preferably the styrene-ethylene / butylene-styrene block copolymer (SEBS) and / or the hydrogenated styrene-vinyl isoprene block rubber (SIS) , has a styrene content equal to or below 25% by weight, more preferably equal to or below 20% by weight, even more preferably equal to or below 18% by weight. On the other hand, the styrene content in the styrenic block copolymer (SBC), preferably the styrene-ethylene / butylene-styrene block copolymer (SEBS) and / or the hydrogenated styrene-vinyl isoprene block rubber ( SIS) must not fall below 10% by weight. Thus, a preferred range is 10 to 25% by weight, more preferable from 11 to 20% by weight and even more preferable from 12 to 18% by weight.
[0076] Furthermore, it is noted that the styrenic block copolymer (SBC), preferably the styrene-ethylene / butylene-styrene block copolymer (SEBS) and / or the hydrogenated styrene-vinyl isoprene block rubber (SIS) ), has an MFR fluidity index (230 ° C / 5.0 kg) of at least 8.0 g / 10 min, more preferably at least 15.0 g / 10 min, even more preferably at least 20, 0 g / 10 min. On the other hand, the flow MFR melting rate (230 ° C / 5.0 kg) of the styrenic block copolymer (SBC), preferably the styrene-ethylene / butylene-styrene block copolymer (SEBS) and / or the hydrogenated styrene-vinyl isoprene block rubber (SIS), should not be more than 30.0 g / 10min. Consequently, a preferred fluidity index MFR (230 ° C / 5.0 kg) is in the range of 8.0 to 30.0 g / 10min, more preferable from 15.0 to 28.0 g / 10 min, even more preferably from 18.0 to 25.0 g / 10 min.
[0077] Furthermore, the styrenic block copolymer (SBC), preferably the styrene-ethylene / butylene-styrene block copolymer (SEBS) and / or the hydrogenated styrene-vinyl isoprene block rubber (SIS), can be defined for its density. Thus, it is observed that the styrenic block copolymer (SBC), preferably the styrene-ethylene / butylene-styrene block copolymer (SEBS) and / or the hydrogenated styrene-vinyl isoprene block rubber (SIS) , has a density equal to or below 0.910 g / cm3, more preferably equal to or below 0.900 g / cm3.
[0078] Optionally, as an additional polymer component in the present composition is a high density polyethylene (HDPE).
[0079] By high density polyethylene (HDPE) according to this invention, it means a polyethylene with a density measured according to ISO 1183-187 of at least 940 kg / m3, more preferably at least 955 kg / m3, still more preferably in the range of 940 to 975 kg / m3, even more preferably in the range of 958 to 968 kg / m3, such as from 960 to 966 kg / m3.
[0080] Preferably high-density polyethylene (HDPE) has an MFR2 (190 ° C) melt index of 6.0 to 15 g / 10 min, more preferably 7.0 to 10.0 g / 10 min, as such as 7.5 to 9.0 g / 10 min.
[0081] Finally, the present composition must comprise a mineral filler (F), preferably an anisotropic mineral filler (F). Consequently, the mineral filler is preferably selected from the group consisting of talc, mica and volastonite. Most preferably the mineral filler (F) is talc.
[0082] Especially good results are achievable in the case where the mineral charge (F) has a particle size distribution d95 in the range of 1 to 20 pm, more preferably in the range of 5 to 15 pm. Typically, the mineral filler (F) has a surface area measured according to the BET method commonly known with N2 gas as an adsorbable analysis of more than 5 m2 / g, more preferably of more than 10 m2 / g, even more preferably more than 12 m2 / g, even more preferably in the range of 5 to 25 m2 / g, such as from 10 to 20 m2 / g.
[0083] The present composition may contain additives other than the mineral filler (F). For example, it is observed that the composition comprises acid decontaminants (AS), antioxidants (AO), nucleating agents (NA), light hindered amine stabilizers (HALS), glidants (SA), and pigments. Preferably, the amount of additives excluding the mineral filler (F) should not exceed 7% by weight, more preferably it should not exceed 5% by weight, as well as not more than 3.5% by weight, within the present composition.
[0084] In what follows the preferred additives are listed.
[0085] A preferred acid decontaminant (AS) is Ca-stearate.
[0086] As antioxidants (AO), preferably the feinolic antioxidant (AO) and / or phosphorus antioxidant must be present in the composition of the invention.
[0087] More preferably the phenolic antioxidant is selected from the group consisting of [0088] pentaerythrityl-tetrakis (3- (3,5-di-tert-butyl-4-hydroxyphenyl) pro-pioneer (CAS No. 6683-19- 8; 1178 g / mol), [0089] octadecyl 3- (3 ', 5'-di-tert-butyl-4-hydroxyphenyl) propionate (CAS No. 2082-79-3; 531 g / mol) [0090] bis (3,3-bis (3'-tert-butyl-4'-hydroxyphenyl) butonic acid) glycolester (CAS No. 32509-66-3; 794 g / mol), [0091] 3,3'- Bis (3,5-di-tert-butyl-4-hydroxyphenyl) -N, N'-hexamethylenedipropionamide (CAS No. 23128-74-7; 637 g / mol), [0092] 3,9-bis (1, 1-dimethyl-2- (beta- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy) ethyl) -2,4,8,10-tetraoxaspiro [5.5] undecane (CAS No. 90498-90- 1,741 g / mol), [0093] 1,6-hexanediyl-bis (3,5-bis (1,1-dimethylethyl) -4-hydroxybenzene) propanoate) (CAS No. 35074-77-2; 639 g / mol ), [0094] triethylene glycol-bis- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate (CAS No. 36443-68-2; 587 g / mol), [0095] a mixture of esters linear and branched C13 to C15 alkyls s of 3- (3 ', 5'-di-t-butyl-4'-hydroxyphenyl) propionic acid (CAS no. 171090-93-0; 485 g / mol), and [0096] straight and branched C7-C9 alkyl esters 3,5-bis (1,1-dimethylethyl) -4-hydroxy-, benzenepropanoic acid (CAS No. 12564361-0; 399 g / mol), [0097] The most preferred phenolic antioxidant is pentaerythrityl-tetrakis (3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate (CAS No. 6683-19-8; 1178 g / mol ).
[0098] The preferred phosphorous antioxidant is selected from the group consisting of [0099] tris- (2,4-di-tert-butylphenyl) phosphite (CAS No. 31570-04-4; 647 g / mol), [00100] tetrakis - (2,4-di-tert-butylphenyl) -4,4'-biphenylen-di-phosphonite (CAS No. 38613-77-3; 991 g / mol), [00101] bis- (2,4-di -tert-butylphenyl) -pentaerythrityl-di-phosphite (CAS No. 26741-53-7; 604 g / mol), [00102] di-stearyl-pentaerythrityl-di-phosphite (CAS No. 3806-34-6; Mw 733 g / mol), [00103] tris-nonylphenyl phosphite (CAS No. 26523-78-4; 689 g / mol), [00104] bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythrityl- di-phosphite (CAS No. 80693-00-1; 633 g / mol), [00105] 2,2'-methylenebis (4,6-di-tert-butylphenyl) octyl-phosphite (CAS No. 126050-54- 2. 583 g / mol), [00106] 1, 1,3-tris (2-methyl-4-ditridecyl phosphite-5-tert-butylphenyl) butane (CAS No. 68958-97-4; 1831 g / mol) , [00107] 4,4'-butylidenobis (3-methyl-6-tert-butylphenyl-di-tridecyl) phosphite (CAS No. 13003-12-8; 1240 g / mol), [00108] bis- (2, 4-dicumylphenyl) pentaerythritol diphosphite (CAS No. 15486243-8; 852 g / mol), [00109] bis (2-methyl-4,6-bis (1,1-dmethylethyl) phenyl) phosphoric acid ethyl ester (CAS no. 145650-60-8; 514 g / mol), [00110] 2,2 ', 2' '- n triethyl-trisyl (3,3', 5,5'-tetra-tert-butyl-1,1,1-biphenyl-2,2 '-diyl) phosphite) (CAS No. 80410-33-9; 1465 g / mol) [00111] 2,4,6-Tisyl (tert-butyl) phenyl-2-butyl-2-ethyl-1,3 -propandiolphosphite (CAS No. 161717-32-4, 450 g / mol), [00112] 2,2'-Ethyliden-bis (4,6-di-tert-butylphenyl) fluorphosphonite (CAS No. 118337-09-0 ; 487 g / mol), [00113] 6- (3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propoxy) -2,4,8,10-tetra-tert-butyldibenz [d, f ] [1.3.2] dioxafosfepine (CAS No. 203255-81-6; 660 g / mol), [00114] tetrakis- (2,4-di-tert-butyl-5-methylphenyl) -4,4'-bipheni len-diphosphite (CAS No. 147192-62-9; 1092 g / mol), and [00115] 1,3-bis- (diphenylphosphino) -2,2-dimethylpropane (CAS No. 80326- 98-3; 440.5 g / mol).
[00116] The most preferred phosphorous antioxidant is tris- (2,4-di-tert-butylphenyl) phosphite (CAS No. 31570-04-4; 647 g / mol).
[00117] Light hindered amine stabilizers (HALS) are known in the art. Preferably such light hindered amine stabilizers are 2,6-alkyl-piperidine derivatives, in particular 2,2,6,6-tetramethyl-piperidine derivatives.
[00118] Consequently the light hindered amine stabilizer is preferably selected from the group consisting of [00119] bis- (2,2,6,6-tetramethyl-4-piperidyl) sebacate (CAS No. 5282907-9; 481 g / mol ), [00120] bis- (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate (CAS No. 41556-26-7; 509 g / mol), [00121] tetrakis tetracarboxylate (2, 2,6,6-tetramethyl-4-piperidyl) - 1.2.3.4-butane (CAS No. 64022-61-3; 792 g / mol), [00122] tetrakis tetracarboxylate (1,2,2,6,6 -pentamethyl-4-piperidyl) -1,2,3,4-butane (CAS No. 91788-83-9; 847 g / mol), [00123] 1,2,3-tris (1,2,2, 6,6-pentamethyl-4-piperidyl) -4-tridecyl butane- 1.2.3.4- tetracarboxylate (CAS No. 84696-72-0; 900 g / mol), [00124] 1,2,3-tris (2, 2,6,6-tetramethyl-4-piperidyl) -4-tridecyl butane- 1,2,3,4-tetracarboxylate (CAS No. 84696-71-9; 900 g / mol), [00125] N, N ' -bisformyl-N, N'-bis- (2,2,6,6-tetramethyl-4-piperidinyl) -hexamethylenediamine (CAS No. 124172-53-8; 450 g / mol), [00126] l, 3, 5-triazine-2,4,6-triamine, NsNM, 2-ethanediilbis [N- [3 - [[4,6- bis [butyl ( 1,2,2,6,6-pentamethyl-4-piperidinyl) amino] -1, 3,5-triazin-2-yl] amino] propyl] -N ', N "-dibutyl-N', N" - bis (1,2,2,6,6-pentamethyl-4-piperidinyl) - (CAS no. 106990-43-6; 2286 g / mol), and [00127] bis- (1-octyloxy-2,2,6,6-tetramethyl-4-piperidinyl) sebacate (CAS No. 129757-67-1; 737 g / mol).
[00128] In the case where a nucleating agent (NA) is used it is preferably an α-nucleating agent. Even more preferable, the present invention is free of β-nucleation agents. According to the present invention, the nucleating agent (NA) is understood as a different nucleating agent for the mineral filler (F). Consequently, the nucleating agent (NA) is preferably selected from the group consisting of (i) salts of monocarboxylic acids and polycarboxylic acids, for example, sodium benzoate or aluminum tert-butylbenzoate, and (ii) dibenzylidenosorbitol (eg example: 1,3: 2,4 dibenzyl-denossorbitol) and C1-C8-substituted dibenzylidenosorbitol derivatives, such as methyldibenzylidenosorbitol, ethyldibenzylidene sorbitol or dimethyldibenzylidenosorbitol (eg 1,3: 2,4 di (methylbenzylidene) sorbitol, , 1,2,3, -trideoxy-4,6: 5,7-bis-O - [(4-propylphenyl) methylene] -nonitol, and (iii) salts of phosphoric acid diesters, for example, 2.2 aluminum '-methylenobis (4,6, -di-tert-butylphenyl) phosphate or hydroxy-bis [2,2'-methylene-bis (4,6-di-t-butylphenyl) phosphate], and (iv ) vinylcycloalkane polymer and vinylalkane polymer. [00129] It is especially preferred that the nucleating agent (NA) is 2,2'-methylene-bis (4,6, -di-tert-butylphenyl) phosphate.
[00130] A preferred glidant is, for example, a fatty acid amide. Preferably the amount of fatty acid carbon atoms is preferably in the range of carbon atoms C10 to C25.
[00131] Consequently, the sliding agent (SA) is preferably selected from the group consisting of [00132] Cis-13-docosomal amide (CAS No. 112-84-5; 337.6 g / mol), [00133] cis-9.10 octadecenoamide (CAS No. 301-02-0; 281.5 g / mol) [00134] octadecanoylamide (CAS No. 124-26-5; 283.5 g / mol), [00135] beenamide ( CAS No. 3061-75-4; 339.5 g / mol), [00136] N, N'-ethylene-bis-stearamide (CAS No. 110-30-5; 588 g / mol), [00137] N -octadecyl-13-docosenamide (CAS No. 10094-45-8; 590 g / mol), and [00138] oleylpalmitamide (CAS No. 16260-09-6; 503 g / mol).
[00139] Especially suitable is cis-13-docosanoic amide (CAS No. 112-84-5; 337.6 g / mol) and / or cis-9-octadecenamide (CAS No. 30102-0; 281.5 g / mol) mol).
[00140] All components used for the preparation of the present composition are known. In this way, its preparation is also well known. For example, the heterophasic polypropylenes according to this invention are preferably produced by a multistage process known in the art, wherein the matrix is produced at least in a slurry reactor and subsequently the elastomeric copolymer is produced at least in a gas phase reactor.
[00141] Thus, the polymerization system may comprise one or more conventional agitated slurry reactors and / or one or more gas phase reactors. Preferably, the reactors used are selected from the group of closed loop and gas phase reactors and, in particular, the process employs at least one closed loop reactor and at least one gas phase reactor. It is also possible to use several reactors of each type, for example, a closed loop reactor and two or three gas phase reactors, or two closed loop reactors and one or two gas phase reactors, in series.
[00142] Preferably the process also comprises prepolymerization with the selected catalyst system, as described in detail below, comprising the Ziegler-Natta pro-catalyst, the external donor and the co-catalyst.
[00143] In a preferred embodiment, prepolymerization is conducted as the polymerization of bulky slurry into liquid propylene, i.e. the liquid phase mainly comprises propylene, with a smaller amount of other reagents and optionally inert components dissolved in it .
[00144] The prepolymerization reaction is typically conducted at a temperature of 0 to 50 ° C, preferably 10 to 45 ° C, and more preferably 15 to 40 ° C.
[00145] The pressure in the prepolymerization reactor is not critical, but it must be high enough to maintain the reaction mixture in the liquid phase. Thus, the pressure can be from 20 to 100 bar, for example, from 30 to 70 bar.
[00146] The catalyst components are preferably all those introduced in the prepolymerization step. However, where the solid catalyst component (i) and co-catalyst (ii) can be fed separately, it is possible that only a part of the co-catalyst is introduced in the prepolymerization stage and the remainder in the subsequent polymerization. Also in such cases it is necessary to introduce only the co-catalyst in the prepolymerization stage in which a sufficient polymerization reaction is obtained therein.
[00147] It is also possible to add other components in the prepolymerization stage. Thus, hydrogen can be added in the prepolymerization stage to control the molecular weight of the prepolymer as is known in the art. In addition, anti-static additive can be used to prevent particles from adhering to each other or to the reactor walls.
[00148] Precise control of prepolymerization conditions and reaction parameters is within the skill of the technique.
[00149] A slurry reactor means any reactor, such as a continuous or simple batch stirred tank reactor or closed loop reactor, which operates in volume or slurry and in which the polymer is formed in particulate form. "By volume" means polymerization in the reaction medium that comprises at least 60% by weight of monomer. According to a preferred embodiment, the slurry reactor comprises a closed loop reactor by volume.
[00150] "Gas phase reactor" means any mechanically mixed or fluid bed reactor. Preferably the gas phase reactor comprises a mechanically agitated fluid bed reactor with gas velocities of at least 0.2 m / sec.
[00151] The particularly preferred embodiment for the preparation of the heterophasic polypropylenes of the invention comprises carrying out polymerization in a process comprising a combination of a closed loop reactor and one or two gas phase reactors, or a combination of two reactors closed circuit and one or two gas phase reactors.
[00152] A preferred multistage process is a gaseous-phase slurry process, such as that developed by Borealis and known as Borstar® technology. In this regard, reference is made to EP 0 887 379 A1, WO 92/12182, WO 2004/000899, WO 2004/111095, WO 99/24478, WO 99/24479 and WO 00/68315. They are hereby incorporated by reference.
[00153] Another suitable slurry-gas phase process is Basell's Sferipol® process.
[00154] Preferably, the heterophasic polypropylene composition according to this invention is produced using a special Ziegler-Natta pro-catalyst in combination with a special external donor, as described below in detail, preferably in the Sferipol® process or in the Borstar®-PP process.
[00155] A preferred multistage process can therefore comprise the steps of: - producing a polypropylene matrix in the presence of the selected catalyst system, for example, described in detail below, comprising the special Ziegler-Natta pro-catalyst (i), an external donor (iii) and the co-catalyst (ii) in a first slurry reactor and optionally in a second slurry reactor, both slurry reactors using the same polymerization conditions, - transfer the slurry reactor product into at least one first gas phase reactor, such as a gas phase reactor or a first and second gas phase reactor connected in series, - producing an elastomeric copolymer in the presence of the matrix of polypropylene and in the presence of the catalyst system in said at least first gas phase reactor, - recovering the polymer product for further processing.
[00156] With respect to the preferable slurry-gas phase process mentioned above, the following general information can be provided in relation to the process conditions.
[00157] The temperature is preferably 40 to 110 ° C, preferably between 50 and 100 ° C, in particular between 60 and 90 ° C, with a pressure in the range of 20 to 80 bar, preferably 30 to 60 bar, with the option of adding hydrogen in order to control the molecular weight in a manner known per se.
[00158] The slurry polymerization reaction product, which is preferably carried out in a closed loop reactor, is then transferred to the subsequent gas phase reactor, where the temperature is preferably within the range of 50 to 130 ° C, more preferably from 60 to 100 ° C, at a pressure in the range of 5 to 50 bar, preferably from 8 to 35 bar, again with the option of adding hydrogen in order to control the molecular weight in a known manner per se.
[00159] The average residence time may vary in the reactor zones identified above. In one embodiment, the average residence time in the slurry reactor, for example, a closed loop reactor, is in the range of from 0.5 to 5 hours, for example, from 0.5 to 2 hours, while that the average residence time in the gas phase reactor will generally be 1 to 8 hours.
[00160] If desired, polymerization can be carried out in a known manner under supercritical conditions in the slurry, preferably the closed loop reactor, and / or as a condensed mode in the gas phase reactor.
[00161] According to the invention, heterophasic polypropylenes are preferably obtained by a multi-stage polymerization process, as described above, in the presence of a catalyst system comprising as component (i) a Ziegler-Natta pro-catalyst which contains a product from the transesterification of a lower alcohol and a phthalic ester.
[00162] The pro-catalyst used according to the invention is prepared by a) reaction of an adduct crystallized by spraying or solidified by emulsion of MgCl2 and a C1-C2 alcohol with TiCU b) reaction of the stage product a) a dialkylphthalate of formula (I) in which R1 'and R2' are independently at least one C5 alkyl under conditions where a transesterification between said C1 to C2 alcohol and said dialkyl phthalate of formula (I) occurs to form the internal donor c) washing the product 3 stage b) or d) optionally the reaction of the product from step c) with additional TiCl4.
[00163] The pro-catalyst is produced as defined, for example, in patent applications WO 87/07620, WO 92/19653, WO 92/19658 and EP 0 491 566. The content of these documents is included by reference.
[00164] Firstly, an adduct of MgCb and a C1-C2 alcohol of the formula MgCl2 * nROH, where R is methyl or ethyl and n is 1 to 6, are formed. Ethanol is preferably used as alcohol.
[00165] The adduct, which is first melted and then crystallized by spraying or solidified by emulsion, is used as a catalyst carrier.
[00166] In the next step the adduct crystallized by spraying or solidified by emulsion of the formula MgCl2 * nROH, in which R is methyl or ethyl, preferably ethyl, and n is 1 to 6, is in contact with TiCl4, to form a carrier submitted to titanium, followed by the steps of • adding to said bearer submitted to titanium (i) a dialkylphthalate of formula (I) with R1 'and R2' being independently at least one C5 alkyl, such as at least one Cs alkyl, or preferably ( ii) a dedialkyl phthalate of formula (I) with R1 'and R2' being the same and being at least one C5 alkyl, such as at least one Cs alkyl, or more preferably (iii) a dialkyl phthalate of formula (I) selected from the group that consists of propylexyl phthalate (PrHP), dioctyl phthalate (DOP), diiso-decyl phthalate (DIDP), and ditridecyl phthalate (DTDP), even more preferably the dialkyl phthalate of formula (I) is a dioctyl phthalate (DOP), as diisopropylate or diethylexyl phthalate, in particular diethylexyl talate, to form a first product, • subject said first product to the appropriate trans-esterification conditions, that is, at a temperature above 100 ° C, preferably between 100 to 150 ° C, more preferably between 130 to 150 ° C such that methanol or ethanol is transesterified with said ester groups of said dialkylphthalate of formula (I) to preferably form at least 80 mol%, more preferably 90 mol%, most 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 • recovering this transesterification product as the pro-catalyst composition (component (i)).
[00167] The adduct of the formula MgCl2 * nROH, where R is methyl or ethyl and n is 1 to 6, is in a preferred molten embodiment and then the melt is preferably injected by a gas in a cooled solvent or a gas cooled, whereby the adduct is crystallized in a morphologically advantageous form, as, for example, described in WO 87/07620.
[00168] This crystallized adduct is preferably used as the catalyst carrier and reacted with the pro-catalyst useful in the present invention as described in WO 92/19658 and WO 92/19653.
[00169] When the catalyst residue is removed by extraction, an adduct from the carrier subjected to titanium and from the internal donor is obtained, in which the group that originates from the ester alcohol has been changed.
[00170] In the event that sufficient titanium remains in the operator, it will act as an active element of the pro-catalyst.
[00171] Otherwise, titanization is repeated after the above treatment in order to guarantee a sufficient titanium concentration and thus the activity.
[00172] Preferably the pro-catalyst used according to the invention contains a maximum of 2.5% by weight of titanium, preferably a maximum of 2.2% by weight, and most preferably 2.0% by weight of maximum. Its donor content is preferably between 4 to 12% by weight and more preferably between 6 and 10% by weight.
[00173] More preferably the pro-catalyst used according to the invention was produced using ethanol as the alcohol and dioctyl phthalate (DOP) as the dialkyl phthalate of formula (I), producing diethyl phthalate (DEP) as the donor compound. internal.
[00174] Even more preferably, the catalyst used according to the invention is Borealis BC-1 catalyst (prepared according to WO 92/19653 as disclosed in WO 99/24479; especially with the use of dioctyl phthalate as dialkylphthalate of formula (I) according to WO 92/19658) or Politrack 8502 catalyst, commercially available from Grace.
[00175] In another embodiment, the Zie-gler-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 cocatalyst, whose vinyl compound has the formula: CH2 = CH-CHR3R4 in which R3 and R4 together form a 5- or 6-membered saturated, unsaturated or aromatic ring or independently represent an alkyl group comprising 1 to 4 carbon atoms, and the modified catalyst is used for the preparation of the heterophasic polypropylene composition according to this invention. The polymerized vinyl compound can act as an α-nucleating agent. This modification is in particular used for the preparation of heterophasic polypropylene (H-PP1).
[00176] With regard to the modification of the catalyst, reference is made to international applications WO 99/24478, WO 99/24479 and particularly WO 00/68315, incorporated herein by reference in relation to the reaction conditions regarding the modification of the catalyst as well as in relation to the polymerization reaction.
[00177] For the production of heterophasic polypropylenes according to the invention, the catalyst system used preferably comprises, in addition to the special Ziegler-Natta pro-catalyst, an organometallic co-catalyst, as component (ii).
Consequently 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.
[00179] 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 from 3 to 12 carbon atoms, of 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.
[00180] It is particularly preferable that R5 is selected from the group consisting of iso-propyl, iso-butyl, iso-pentyl, tert-butyl, tert-amyl, neopentyl, cyclopentyl, cyclohexyl, methylcyclopentyl and cycloeptyl.
[00181] More preferably, the external donor is dicyclopentyl dimethoxy silane [Si (OCH3) 2 (cyclo-pentyl) 2] or diisopropyl dimethoxy silane [Si (OCH3) 2 (CH (CH3) 2) 2].
[00182] For mixing the individual components of the present composition, a conventional combining or mixing mechanism, for example, a Banbury mixer, a 2-roller rubber mill, Buss co-mixer or a double helix extruder, can be used . The polymeric materials recovered from the extruder are generally in the form of granules. These granules are then preferably further processed, for example, through injection molding to generate articles and products of the inventive composition.
[00183] Consequently, the present invention is also directed to a process for the preparation of the present composition, comprising the steps of adding heterophasic polypropylene (H-PP1), polypropylene with a high fluidity index (HMF-PP), of the copolymer in styrenic block (SBC), mineral filler (F), and optionally other additives to an extruder (as mentioned above) and its extrusion thus obtaining this composition.
[00184] The composition according to the invention can be granulated and combined using any of the variety of well-known mixing and mixing methods commonly used in the resin composition technique.
[00185] The composition of the present invention is preferably used for the production of automobile articles, such as automobile molded articles, preferably automobile injection molded articles. Even more preferable is the use for the production of interiors and exteriors of vehicles, such as bumpers, side trim, stirrup auxiliaries, body panels, airfoils, instrument panels, interior finishes and more.
[00186] The current invention also provides (automotive) articles, such as injection molded articles, comprising at least 60% by weight, more preferably at least 80% by weight, even more preferably at least 95% by weight, likewise which consisting of the polypropylene composition of the invention. Consequently, the present invention is especially directed at automobile articles, especially for interiors and exteriors of vehicles, such as bumpers, side trim, stirrup auxiliaries, body panels, airfoils, instrument panels, and interior finishes and more , comprising at least 60% by weight, more preferably at least 80% by weight, even more preferably at least 95% by weight, in the same way as consisting of the polypropylene composition of the invention.
[00187] The present invention will now be described in more detail through the examples provided below.
EXAMPLES 1. Measurement Definitions / Methods [00188] The following definitions of terms and methods of determination apply to the general description above of the invention as well as to the examples below, unless otherwise defined.
[00189] Quantification of isotactic capacity in polypropylene by 13C NMR spectroscopy
[00190] Isotactic capacity is determined by quantitative 13C nuclear magnetic resonance (NMR) spectroscopy after the basic designation, for example, in: V. Busico and R. Cipullo, Progress in Polymer Science, 2001, 26, 443-533 . The experimental parameters are adjusted to ensure the measurement of the quantitative spectra for this specific task, for example, in: S. Berger and S. Braun, 200 and More NMR Experiments: A Practical Course, 2004, Wiley-VCH, Weinheim. Quantities are calculated using simple proportions corrected for the signal integrals of representative sites in a manner known in the art. Isotactic capacity is determined at the quinquevalent level, that is, the mmmm fraction of the quinquevalent distribution.
[00191] The density is measured according to ISO 1183-187. Sample preparation is done by compression molding according to ISO 1872-2: 2007.
[00192] MFR2 (230 ° C) is measured according to ISO 1133 (230 ° C, 2.16 kg load).
[00193] MFR (230 ° C / 5 kg) is measured according to ISO 1133 (230 ° C, 5 kg load).
[00194] MFR2 (190 ° C) is measured according to ISO 1133 (190 ° C, 2.16 kg load).
[00195] Quantification of the comonomer content by FTIR spectroscopy
[00196] The comonomer content is determined by quantitative Fourier Transformed Infrared Spectroscopy (FTIR) after the basic designation calibrated using quantitative 13C nuclear magnetic resonance (NMR) spectroscopy in a manner well known in the art. The thin films are compressed to a thickness between 100 to 500 pm and the spectra recorded in transmission mode.
[00197] Specifically, the ethylene content of a polypropylene-co-ethylene copolymer is determined using the peak area corrected by the basic value of the quantitative ranges observed in 720 to 722 and 730 to 733 cnr1. Quantitative results are obtained based on the reference for the film thickness.
[00198] The intrinsic viscosity is measured according to DIN ISO 1628/1, October 1999 (in decalin at 135 ° C).
[00199] Traction Module; Elongation at break; Production Stress, are measured according to ISO 527-2 (upper transverse speed = 50 mm / min, 23 ° C) using injection molded specimens as described in EN ISO 1873-2 (dog bone shape, 4 mm thickness ).
[00200] Flexion Module: The flexure module was determined in the curvature of three points according to ISO 178 on the injection molded specimens of 80 x 10 x 4 mm prepared according to ISO 294-1: 1996.
[00201] The beveled Izod Impact is determined according to ISO 180 / 1A at 23 ° C, and at -30 ° C through the use of injection molded test specimens as described in EN ISSO 1873-2 (80 x 10 x 4 mm).
[00202] Cold xylene soluble (XCS,% by weight): The content of xylene soluble (XCS) is determined at 23 ° C according to ISO 6427.
Styrene content [00203] The styrene content is measured by Fourier transform infrared spectroscopy (FTIR). A thin film of 300 pm thickness is prepared from the granulated material by means of hot compression (190 ° C, 100 bar, 1 minute). For example, two films are prepared. The film samples thus prepared are measured by a Perkin Elmer IR-Spectrophotometer System 2000FTIR. The peak at 1602 cnr1 (Phenyl Absorption) is integrated and evaluated using an internally established calibration curve. The arithmetic mean of two measurements is given as a result.
[00204] Calibration: Various polypropylene compounds consisting of PP and an elastomer containing styrene (of known styrene content) are prepared and measured according to the method described above.
[00205] The d95 particle size is calculated from the particle size distribution as determined by laser diffraction according to ISO 13320-1: 1999.
[00206] The surface area is determined as the BET surface according to ISO 787-11 with nitrogen (N2).
Scratch resistance [00207] To determine the scratch resistance a Cross Hatch Cut-ter Model 420p, manufactured by Erichsen, was used.
[00208] For the tests, plates 70 x 70 x 4 mm in size were cut from a molded granulated plate (grain parameters: average grain size = 1 mm, grain depth = 0.12 mm, collinity = 6 °) of size 140 x 200 x 4 mm. The minimum period between specimen injection molding and risk testing was 7 days. [00209] For testing the specimens must be fixed in an appropriate mechanism as described above. The streaks are applied with a force of 10 N using a cylindrical metal pen, with a ball-shaped tip (radius = 0.5 mm ± 0.01). A cutting speed of 1000 mm / min is used.
[00210] A minimum of 20 risks parallel to each other are created on a 10 N load with a distance of 2 mm. The application of the risks is repeated perpendicularly to each other, so that the result is a screen of risks. The direction of risk must be unidirectional. [00211] The scratch resistance is reported as the difference in the intensity of the AL light of the non-streaked areas from the streaked areas. AL values can be measured using a spectrophotometer that meets the requirements according to DIN 5033.
[00212] The measured values of AL must be below a maximum of 1.5.
[00213] A detailed test description of the test method can be found in the article "Evaluation of scratch resistance in multiphase PP blends" by Thomas Koch and Doris Machl, published in POLYMER TESTING 26 (2007), p. 927-936.
[00214] Linear thermal expansion coefficient: The linear thermal expansion coefficient (CLTE) was determined in accordance with ISO 11359-2: 1999 on the 10 mm long pieces cut from the same injection molded specimens as used for determining the bending module. The measurement was carried out in a temperature range of -30 to + 80 ° C at a heating rate of 1 ° C / min.
[00215] Turbidity measured according to DIN 75201. 2. Examples Table 1: [00216] The used heterophasic polypropylenes (HECO) "HECO 1" is the commercial product EF209AE from Borealis "HECO 2" is the commercial product EG250AI from Borealis " HECO 3 "is the commercial product EE050AE from Borealis" HECO 4 "(HMF-PP) is the commercial product BJ356MO from Borealis" Carga "is the commercial product JETFINE 3CA from Luzenac Table 2: Compositions [00217] The rest at 100% in weight are additives, such as antioxidants "SEBS" is the commercial copolymer product of commercial ethylene butylene styrene Kraton G 1657 from Kraton Polymers LLC with a styrene content of about 13.0% by weight and a fluidity index MFR (230 ° C / 5 kg) of 22 g / 10 min, "HDPE" is the commercial high-density polyethylene product MG 9641 from Borealis AG featuring an MFR2 (190 °) of 8 g / 10 min and a density of 964 kg / m3, "Talc" is the commercial HAR T84 talc from Luzenac, "Carbon black" is the standard commercial blend " Plasblak PE4103 "from Cabot," AO1 "is the commercial phenolic antioxidant Irganox 1010 from Ciba," AO2 "is the commercial phosphorus antioxidant Irgafos 168 from Ciba," NA "is the commercial α-nucleating agent of 2,2'-methylenebis (4,6, -di-tert-butylphenyl) sodium phosphate (NA11) from Ciba, "ESA" is Croda's commercial 13-dococenamide, "Oleamide" is Croda's commercial 9-octadecenamide, "HALS" is the stabilizer light commercial hindered amine (HALS) Cytec 3808 from Cytec.

权利要求:
Claims (15)
[1]
1. Composition, characterized by the fact that it comprises a fluidity index MFR2 (230 ° C), measured according to ISO 1133, in the range of 15 to 30 g / 10 min, said composition comprising: 25 to 40% by weight of a heterophasic propylene copolymer (H-PP1), 22 to 30% by weight of a high fluidity polypropylene (HMF-PP), 7 to 25% weight of a styrenic block copolymer (SBC), and 15 to 25% by weight of a mineral filler (F), with (a) the heterophasic propylene copolymer (H-PP1) having a cold soluble xylene content (XCS) measured according to ISO 6427 in the range of 22.0 at 50.0% by weight and comprises (a1) a polypropylene matrix (M1) and (a2) an elastomeric copolymer (E1) comprising units derived from - propylene, e - ethylene and / or α-olefin C4 to C12, (b) the MFR2 fluidity index (230 ° C), measured according to ISO 1133, of the polypropylene with high fluidity index (HMF-PP), is higher than the MFR2 fluidity index (230 ° C), measured from according to ISO 1133, of the heterophasic propylene copolymer (H-PP1), and (c) polypropylene with a high fluidity index (HMF-PP) has an MFR2 fluidity index (230 ° C), measured according to ISO 1133, at least 60.0 to 1000.0 g / 10 min.
[2]
2. Composition according to claim 1, characterized by the fact that the heterophasic propylene copolymer (H-PP1) has a fluidity index MFR2 (230 ° C), measured according to ISO 1133, in the range of 3, 0 to 30.0 g / 10 min.
[3]
3. Composition according to claim 1 or 2, characterized by the fact that the heterophasic propylene copolymer (H-PP1) has: (a) a total propylene content of 75.0 to 92.0% by weight and / or (b) a propylene content in the cold soluble xylene (XCS) fraction of 50.0 to 75.0% by weight.
[4]
4. Composition according to any one of claims 1 to 3, characterized by the fact that: (a) the intrinsic viscosity (IV), measured according to ISO 1268-1 (decalin), of the cold soluble xylene fraction (XCS) of the heterophasic propylene copolymer (H-PP1), is above 2.0 dL / g and / or (b) and the fluidity index MFR2 (230 ° C), measured according to ISO 1133, of the fraction of cold insoluble xylene (XCI) of the heterophasic propylene copolymer (H-PP1), is in the range of 20.0 to 150.0 g / 10 min.
[5]
Composition according to any one of claims 1 to 4, characterized by the fact that polypropylene with a high flow rate (HMF-PP) is not degraded.
[6]
6. Composition according to any one of claims 1 to 5, characterized by the fact that polypropylene with a high melt index (HMF-PP) is a heterophasic propylene copolymer (H-PP2), comprising: ( i) a polypropylene matrix (M2) and (ii) an elastomeric copolymer (E2) comprising units derived from - propylene, e - ethylene and / or α-olefin C4 to C12.
[7]
7. Composition according to claim 6, characterized by the fact that the cold soluble xylene content (XCS) of the heterophasic propylene copolymer (H-PP2), measured according to ISO 6427, is: (a) more low compared to the cold soluble xylene content (XCS) of the heterophasic propylene copolymer (H-PP1), measured according to ISO 6427, and / or (b) in the range of 7.0 to 20.0% in Weight.
[8]
8. Composition according to claim 6 or 7, characterized by the fact that the fluidity index MFR2 (230 ° C), measured according to ISO 1133, of the fraction of cold insoluble xylene (XCI), of the copolymer of heterophasic propylene (H-PP2), is in the range of 100.0 to 1500.0 g / 10 min.
[9]
9. Composition according to any one of claims 6 to 8, characterized by the fact that the heterophasic propylene copolymer (H-PP2) has: (a) a total propylene content of 85.0 to 96.0% in weight, and / or (b) a higher total propylene content compared to the heterophasic propylene copolymer (H-PP1), and / or (c) a propylene content in the cold soluble xylene fraction (XCS) of 50.0 to 75.0% by weight.
[10]
10. Composition according to any one of claims 6 to 9, characterized in that the intrinsic viscosity (IV) measured according to ISO 1268-1 (decalin) of the cold insoluble xylene fraction (XCS) of the copolymer of heterophasic propylene (H-PP2) is below 3.0 dL / g.
[11]
11. Composition according to any one of claims 1 to 10, characterized in that the styrenic block copolymer (SBC) has: (i) a styrene content equal to or less than 20% by weight, and / or ( ii) an MFR fluidity index (230 ° C / 5.0 kg) of at least 8.0 g / 10 min, and / or (iii) a density equal to or below 0.910 g / m3.
[12]
Composition according to any one of claims 1 to 11, characterized in that the mineral filler (F) is talc.
[13]
13. Composition according to any one of claims 1 to 12, characterized in that it further comprises high density polyethylene (HDPE).
[14]
14. Composition according to claim 1, characterized by the fact that it is for use in the manufacture of an automotive article.
[15]
15. Composition according to claim 1, characterized by the fact that the mineral filler (F) is a talc comprising a d95 particle size distribution in the range of 1 to 20 pm.

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引用文献:

---

公开号 | 申请日 | 公开日 | 申请人 | 专利标题

---

---

FI80055C|1986-06-09|1990-04-10|Neste Oy|Process for preparing catalytic components for polymerization of olefins|

---

FI86866C|1990-12-19|1992-10-26|Neste Oy|FOERFARANDE FOER MODIFIERING AV CATALYSTATOR AVSEDDA FOER POLYMERISATION AV OLEFINER|

---

FI86867C|1990-12-28|1992-10-26|Neste Oy|FLERSTEGSPROCESS FOR FRAMSTAELLNING AV POLYETEN|

---

FI88048C|1991-05-09|1993-03-25|Neste Oy|Coarse-grained polyolefin, its method of preparation and a catalyst used in the method|

---

FI88047C|1991-05-09|1993-03-25|Neste Oy|Catalyst-based catalyst for polymerization of olivines|

---

US6214934B1|1997-05-28|2001-04-10|Mitsui Chemicals Inc|Polypropylene resin composition for use in automotive inner and outer trims|

---

FI111848B|1997-06-24|2003-09-30|Borealis Tech Oy|Process and equipment for the preparation of homopolymers and copolymers of propylene|

---

FI980342A0|1997-11-07|1998-02-13|Borealis As|Polymerroer och -roerkopplingar|

---

FI974175A|1997-11-07|1999-05-08|Borealis As|Process for producing polypropylene|

---

FI991057A0|1999-05-07|1999-05-07|Borealis As|High stiffness propylene polymers and process for their preparation|

---

US20040159972A1|2000-08-04|2004-08-19|Koschmieder Stefan U.|Propylene polymers having agreeable odor characteristics and shaped articles thereof|

---

BR0215768A|2002-06-25|2005-03-15|Borealis Tech Oy|Process for the preparation of a biomodal rubber polypropylene polymer composition, polymer product, use of polymer, and molded article|

---

US8003725B2|2002-08-12|2011-08-23|Exxonmobil Chemical Patents Inc.|Plasticized hetero-phase polyolefin blends|

---

EP1484343A1|2003-06-06|2004-12-08|Universiteit Twente|Process for the catalytic polymerization of olefins, a reactor system and its use in the same process|

---

EP1670854A1|2003-09-30|2006-06-21|Sunoco, Inc. |Paintable, in-reactor blended, thermoplastic polyolefin|

---

US8071681B2|2004-08-13|2011-12-06|Exxonmobil Chemical Patents Inc.|Polymeric compositions including their uses and methods of production|

---

DE602007009102D1|2007-09-14|2010-10-21|Borealis Tech Oy|Polyolefin compounds with improved properties|EP2809718B1|2012-02-03|2018-07-25|Borealis AG|Improved scratch resistance polypropylene at high flow|

---

EP2746326B1|2012-12-19|2017-11-29|Borealis AG|Automotive compound with reduced tigerskin|

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EP2746335A1|2012-12-19|2014-06-25|Borealis AG|Automotive compounds featuring low surface tack|

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EP2746325A1|2012-12-19|2014-06-25|Borealis AG|Automotive compounds with improved odor|

---

EP3033389B1|2013-08-14|2017-10-11|Borealis AG|Propylene composition with improved impact resistance at low temperature|

---

WO2015024887A1|2013-08-21|2015-02-26|Borealis Ag|High flow polyolefin composition with high stiffness and toughness|

---

KR101805396B1|2013-08-21|2017-12-06|보레알리스 아게|High flow polyolefin composition with high stiffness and toughness|

---

PL2853563T3|2013-09-27|2016-12-30|Films suitable for BOPP processing from polymers with high XS and high Tm|

---

ES2568615T3|2013-10-11|2016-05-03|Borealis Ag|Label film oriented in the machine direction|

---

RU2612103C1|2013-10-18|2017-03-02|Лисец Аустриа Гмбх|Method for objects surface processing|

---

ES2574428T3|2013-10-24|2016-06-17|Borealis Ag|Blow molded article based on bimodal random copolymer|

---

WO2015059229A1|2013-10-24|2015-04-30|Borealis Ag|Low melting pp homopolymer with high content of regioerrors and high molecular weight|

---

US9670293B2|2013-10-29|2017-06-06|Borealis Ag|Solid single site catalysts with high polymerisation activity|

---

CN105722872B|2013-11-22|2017-10-13|博里利斯股份公司|Low emission Noblen with high melt flows|

---

US9828698B2|2013-12-04|2017-11-28|Borealis Ag|Phthalate-free PP homopolymers for meltblown fibers|

---

MX2016007438A|2013-12-18|2016-10-03|Borealis Ag|Bopp film with improved stiffness/toughness balance.|

---

CN105829364B|2014-01-17|2017-11-10|博里利斯股份公司|Method for preparing the butylene copolymer of propylene/1|

---

JP2017508032A|2014-02-06|2017-03-23|ボレアリス エージー|Soft copolymer with high impact strength|

---

JP6474417B2|2014-02-06|2019-02-27|ボレアリス エージー|Soft and transparent impact copolymers|

---

EP2907841A1|2014-02-14|2015-08-19|Borealis AG|Polypropylene composite|

---

US10287431B2|2014-04-30|2019-05-14|Exxonmobil Chemical Patents Inc.|Polypropylene compositions and methods to produce the same|

---

EP2947118B1|2014-05-20|2017-11-29|Borealis AG|Polypropylene composition for automotive interior applications|

---

US10081212B2|2014-07-03|2018-09-25|Bostik, Inc.|Cohesively failing, non-staining hot melt adhesives|

---

CN108137885B|2015-07-02|2020-06-30|Sabic环球技术有限责任公司|Composition comprising a heterophasic propylene copolymer|

---

US20180201771A1|2015-07-16|2018-07-19|Total Research & Technology Feluy|Polypropylene Composition and Thermoformed Sheet Thereof|

---

EP3124537B1|2015-07-31|2020-01-08|Borealis AG|Low volatile polypropylene composition|

---

WO2017041296A1|2015-09-11|2017-03-16|Borouge Compounding Shanghai Co., Ltd.|Polypropylene composition|

---

US10472507B2|2015-11-17|2019-11-12|Sabic Global Technologies B.V.|Polymer composition having improved impact strength|

---

WO2018031564A1|2016-08-08|2018-02-15|Ticona Llc|Thermally conductive polymer composition for a heat sink|

---

WO2018114977A1|2016-12-23|2018-06-28|Sabic Global Technologies B.V.|Automotive part|

---

EP3559109A1|2016-12-23|2019-10-30|SABIC Global Technologies B.V.|Interior automotive part|

---

US20190322851A1|2016-12-23|2019-10-24|Sabic Global Technologies B.V.|Exterior or semi-exterior automotive part|

---

EP3395377A1|2017-04-28|2018-10-31|Borealis AG|Soft polypropylene composition with improved properties|

法律状态:
2018-04-10| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|

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2019-09-10| B06U| Preliminary requirement: requests with searches performed by other patent offices: procedure suspended [chapter 6.21 patent gazette]|

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2020-01-14| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|

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2020-03-10| 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 15/04/2011, OBSERVADAS AS CONDICOES LEGAIS. |

优先权:

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申请号 | 申请日 | 专利标题

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EP10160393A|EP2386602B1|2010-04-20|2010-04-20|Automotive interior compound|

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EP10160393.4|2010-04-20|

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PCT/EP2011/056002|WO2011131579A1|2010-04-20|2011-04-15|Automotive interior compound|

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