• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
  • 引用文献
  • 法律状态
  • 优先权
    • 专利摘要:
    COMPOSITION OF POLYOLEFIN WITH LOW CLTE AND REDUCED OCCURRENCE OF FLOW BRANDS The present invention relates to a new polyolefin composition having a low coefficient of thermal expansion (CLTE) and having a reduced occurrence of flow marks. The new polylefin composition comprises a heterophasic polypropylene composition, ethylene / 1-butene elastomer and an inorganic filler.
    公开号:BR112013022136B1
    申请号:R112013022136-4
    申请日:2012-03-02
    公开日:2020-12-08
    发明作者:Cornelia Kock；Michael Tranninger
    申请人:Borealisag；
    IPC主号:
    专利说明:

    [001] The present invention relates to a new polyolefin composition that has a low thermal expansion coefficient (CLTE) and has a reduced occurrence of flow marks. More particularly, the invention relates to a polyolefin composition which comprises a heterophasic polypropylene composition, an ethylene / 1-butene elastomer and an inorganic filler.
    [002] The polyolefin compositions of the present invention are especially useful for automotive applications, in particular for external automotive parts, which require a good balance of impact force and rigidity, for example bumpers, which additionally require surface properties " Class A ”and low thermal expansion. Background of the Invention
    [003] Modern polymer materials for external automotive parts are often composed of mixtures of polypropylene resins. Polypropylene resins are usually crystalline and have low impact resistance especially at low temperatures. To improve the impact strength, polypropylene can be mixed with polyethylene or ethylene copolymers and rubber-like materials, such as polyisobutylene, polybutadiene, or ethylene-a-olefin-based copolymers.
    [004] Normally, resins are then injection molded into the desired articles. If items are relatively large, such as, for example, car bumpers, instrument panels or center consoles, the problem of optical irregularities arises due to the long required flow paths of the resin.
    [005] Such surface defects, which are also known as flow marks, tiger stripes or flow lines, are detrimental to the aesthetics of the surface, as they manifest themselves during injection molding as a series of gloss stripes high and low perpendicular alternations towards the molten flow.
    [006] Many attempts to avoid these surface defects while maintaining a good balance of other physical properties were made, for example, in DE 19754061. However, it has been found that both the occurrence of flow marks cannot be sufficiently avoided or the mechanical properties of the polymer compositions were unsatisfactory.
    [007] An additional requirement for automotive parts is a low coefficient of Thermal Expansion (CLTE), that is, in automotive parts your CLTE should be as close as possible to those adjacent steel parts. Without a low CLTE, parts made of such polymer materials would be easily deformed due to the difference between their CLTE and those of automotive body parts. Conventionally, a low polypropylene CLTE can be achieved with the addition of an inorganic filler such as talc. goal
    [008] It is, therefore, an objective of the present invention to provide a polyolefin composition that has a low CLTE and a reduced tendency to flow marks.
    [009] Surprisingly, the above objective could be achieved with a polyolefin composition comprising: a.35 to 90% by weight, based on the weight of the polyolefin composition, of a heterophasic polypropylene composition comprising: i - 10 to 50 % by weight, based on the weight of the heterophasic polypropylene composition, of a first propylene homopolymer (PPH1) that has an MFR2 measured according to ISO 1133 from 30 to 80 g / 10 min (230 ° C, 2, 16 kg), ii.20 to 65% by weight based on the weight of the heterophasic polypropylene composition, of a second propylene homopolymer (PPH2) which has MFR2 measured according to ISO 1133 from 100 to 250 g / 10 min (230 ° C, 2.16 kg), iii.5 to 30% by weight based on the weight of the heterophasic polypropylene composition of a first cold soluble xylene fraction (XS1) having an intrinsic IVXS1 viscosity of 2.0 to 3.0 dl / g, iv.5 to 25% by weight based on the weight of the heterophasic polypropylene composition of a second fraction of soluble xylene cold el (XS2) having an IVXS2 intrinsic viscosity of 1.5 to 2.8 dl / g, with the proviso that IVXS1 ^ IVXS2, b.5 to 40% by weight based on the polyolefin composition, of an inorganic filler , and c.5 to 25% by weight based on the weight of the polyolefin composition, of an ethylene / 1-butene elastomer.
    [010] As will be shown in the examples section, the polyolefin compositions according to the invention have both a low CLTE -30 / + 80 ° C (<49 pm / mK) and a low CLTE + 23 / + 80 ° C (<57 pm / mK), and a very low tendency to show flow marks on injection molded specimens. The low tendency to show flow marks is especially pronounced at high injection speeds.
    [011] Other important mechanical properties, similar to stiffness, impact strength, shrinkage and heat deflection temperature are also at a high level, comparable to the comparative examples tested.
    [012] According to the invention, the polyolefin composition comprises 35 to 90% by weight of a heterophasic polypropylene composition. Preferably, the amount of the heterophasic polypropylene composition is at least 45% by weight, more preferably 50% by weight, even more preferably 55% by weight and most preferably 60% by weight. Preferably, the amount of the heterophasic polypropylene composition is not more than 85% by weight, more preferably not more than 80% by weight, even more preferably not more than 75% by weight, most preferably not more than 70% by weight .
    [013] If the amount of the heterophasic polypropylene composition is less than 35% by weight, the impact strength of the polyolefin composition would be reduced. If the amount of the heterophasic polypropylene composition is less than 90% by weight, the stiffness would be reduced and the CLTE would become very large.
    [014] The heterophasic polypropylene composition that is used according to the invention comprises a continuous matrix phase and a discontinuous phase.
    [015] The continuous matrix phase of the heterophasic polypropylene composition comprises two propylene homopolymers having MFR2 measured according to ISO 1133.
    [016] According to the invention, the first propylene homopolymer (PPH1) has an MFR2 from 30 to 80 g / 10 min (230 ° C, 2.16 kg) and is present in an amount of 10 to 50 % by weight based on the weight of the heterophasic polypropylene composition.
    [017] According to a more preferred embodiment, the PPH1 MFR2 is from 35 to 75 g / 10 min, even more preferable from 40 to 70 g / 10 min, even more preferably from 45 to 65 g / 10 min, most preferably from 50 to 60 g / 10 min (230 ° C, 2.16 kg).
    [018] The lower limit for the amount of PPH1 is, more preferably, at least 15% by weight, even more preferably at least 20% by weight, even more preferably at least 24 and most preferably at at least 27% by weight based on the weight of the heterophasic polypropylene composition.
    [019] The upper limit for the amount of PPH1 is, more preferably not more than 45% by weight, even more preferably not more than 40% by weight, even more preferably not more than 36 and most preferably not more than 33 % by weight based on the weight of the heterophasic polypropylene composition.
    [020] According to the invention, the second propylene homopolymer (PPH2) has an MFR2 from 100 to 250 g / 10 min (230 ° C, 2.16 kg) and is present in an amount of 20 to 65 % by weight based on the weight of the heterophasic polypropylene composition.
    [021] According to a more preferred embodiment, the PPH2 MFR2 is from 110 to 230 g / 10 min, even more preferable from 120 to 210 g / 10 min, even more preferably from 130 to 190 g g / 10 min, most preferably from 140 to 180 g / 10 min (230 ° C, 2.16 kg).
    [022] The lower limit for the amount of PPH2 is, more preferably, at least 25% by weight, even more preferably at least 30% by weight, even more preferably at least 34% by weight and most preferably at least 38% by weight based on the weight of the heterophasic polypropylene composition.
    [023] The upper limit for the amount of PPH2 is, more preferable not more than 60% by weight, even more preferably not more than 55% by weight, even more preferably not more than 51% by weight and the more preferably not more than 47% by weight based on the weight of the heterophasic polypropylene composition.
    [024] The specific selection of the two propylene homopolymers with different MFR2 ensures that, on the one hand, the general polyolefin composition has the necessary stiffness, to which the homopolymer with low MFR2 contributes and that, simultaneously, this composition presents a high fluidity, which is helped by the homopolymer with the highest MFR2.
    [025] If the amount of PPH1 is below 10% by weight or the amount of PPH2 is above 65% by weight based on the weight of the heterophasic polypropylene composition, the stiffness of the polyolefin composition becomes very small. If the amount of PPH1 is above 50% by weight or the amount of PPH2 is below 20% by weight based on the weight of the heterophasic polypropylene composition, the fluidity of the polyolefin composition becomes insufficient.
    [026] The discontinuous phase of the heterophasic polypropylene composition comprises two ethylene-propylene rubbers with different molecular weights.
    [027] Since the largest amount of an ethylene-propylene rubber is soluble in xylene (XCS content ... cold soluble xylene content) at room temperature, the XCS content of the heterophasic polypropylene composition concerns the amount of ethylene-propylene rubber, but it is not necessarily the same. For example, ethylene-propylene rubber may also comprise part of a very high concentration of ethylene, which is crystalline and would therefore be insoluble in cold xylene.
    [028] For the purpose of this invention, the molecular weight of an ethylene-propylene rubber is expressed as the intrinsic viscosity of a certain cold-soluble xylene fraction of the heterophasic polypropylene composition.
    [029] Consequently, the heterophasic polypropylene composition that is used according to the invention comprises a first fraction of water-soluble xylene (XS1) that has an intrinsic IV viscosity of 2.0 to 3.0 dl / g in an amount from 5 to 30% by weight based on the weight of the heterophasic polypropylene composition.
    [030] According to a more preferred embodiment the minimum limit of the IV of XS1 is at least 2.1 dl / g, even more preferably at least 2.2 dl / g, even more preferably at least 2.3 dl / geo more preferable at least 2.4 dl / g.
    [031] According to a more preferred embodiment, the upper limit of the IV of XS1 is not more than 2.9 dl / g, even more preferably not more than 2.8 dl / g, even more preferably not more than 2 .7 dl / g, more preferable no more than 2.6 dl / g.
    [032] The minimum limit for the amount of XS1 is, more preferably, at least 8% by weight, even more preferably at least 10% by weight, even more preferably at least 12% by weight and most preferably at at least 14% by weight based on the weight of the heterophasic polypropylene composition.
    [033] The maximum limit for the amount of XS1 is eh, more preferably not more than 25% by weight, still more preferably not more than 22% by weight, even more preferably not more than 20% by weight and more preferably not more than 18% by weight based on the weight of the heterophasic polypropylene composition.
    [034] Consequently, the heterophasic polypropylene composition that is used according to the invention comprises a cold soluble xylene fraction (XS2) that has an intrinsic IV viscosity of 1.5 to 2.8 dl / g in an amount of 5 to 25% by weight based on the weight of the heterophasic polypropylene composition.
    [035] According to a more preferred embodiment, the lower limit of the XS2 IV is at least 1.7 dl / g, even more preferably at least 1.8 dl / g, even more preferably at least 1, 9 dl / g and more preferably at least 2.0 dl / g.
    [036] According to a more preferred embodiment the upper limit of the IV of XS2 is not more than 2.7 dl / g, even more preferably not more than 2.6 dl / g, even more preferably not more than 2.5 dl / geo more preferable no more than 2.4 dl / g.
    [037] The minimum limit for the amount of XS2 is, more preferably, at least 7% by weight, even more preferably at least 8% by weight, even more preferably at least 9% by weight and most preferably at at least 10% by weight based on the weight of the heterophasic polypropylene composition.
    [038] The maximum limit for the amount of XS2 is, more preferably not more than 21% by weight, even more preferably not more than 17% by weight, even more preferably not more than 14% by weight and most preferably not more than 12% by weight based on the weight of the heterophasic polypropylene composition.
    [039] The specific selection of ethylene-propylene rubbers and therefore of the first and second cold soluble xylene fractions that have different molecular weights (ie "bimodal rubber") ensures that the overall polyolefin composition has strength sufficient impact at both ambient and low temperatures. The presence of a bimodal rubber in the polyolefin composition also helps to reduce the occurrence of flow marks.
    [040] If the quantities of XS1 and XS2 are less than those claimed, the impact strength of the polyolefin composition is unsatisfactory. If the quantities of XS1 and XS2 are greater than those claimed, the rigidity of the polyolefin composition is unsatisfactory.
    [041] As already mentioned above, the molecular weights of both ethylene-propylene rubbers are different from each other. Consequently, it is necessary that the IV of XS1 is not equal to the IV of XS2. More preferably, IVXS1> IVXS2, even more preferably IVXS1> IVXS2 + 0.1, most preferably IVxs1> IVxs2 + 0.2.
    [042] According to an embodiment of the present invention, the first and second cold soluble xylene fractions are not present in the same amount. It is therefore preferred that the amount of XS1 is greater than the amount of XS2, more preferably that the amount of XS1 is greater than the amount of XS2 by more than 2% by weight, even more preferably by more than 3 % by weight, most preferably more than 4% by weight in each case based on the weight of the heterophasic polypropylene composition.
    [043] An additional parameter, which is useful for adjusting the properties of the polyolefin composition of the present invention is the ethylene content of the cold soluble xylene fractions XS1 + XS2 of the heterophasic polypropylene composition. It has been found that a very low ethylene content helps to ensure a favorable ratio between the impact strength and CLTE. Consequently, the ethylene content of the cold soluble xylene fractions of the heterophasic polypropylene composition is in the range of 20 to 50% by weight, preferably 25 to 45% by weight, more preferably 30 to 45% by weight and more preferably 32 to 42% by weight.
    [044] According to an additional embodiment of the present invention, the ethylene content of the cold soluble xylene fraction XS1 is comparable to the ethylene content of the cold soluble xylene fraction XS2. Consequently, the ethylene content of XS1 is between 80 to 120% of the ethylene content of XS2, more preferably the ethylene content of XS1 is between 90 to 110% of the ethylene content of XS2, even more preferably, the ethylene content. of XS1 is between 95 to 105% of the ethylene content of XS2 and most preferably the ethylene content of XS1 is equal to the ethylene content of XS2.
    [045] According to a further embodiment of the present invention, the first and second propylene homopolymers are not present in the same amount. Consequently, it is preferred that the amount of PPH2 is greater than the amount of PPH1, more preferably that the amount of PPH2 is greater than the amount of PPH1 by more than 4% by weight, even more preferably by more than 7% by weight, even more preferably by more than 10% by weight in each case based on the weight of the heterophasic polypropylene composition.
    [046] According to an advantageous embodiment of the invention, the heterophasic polypropylene composition is composed of 45 to 90% by weight of propylene homopolymers PPH1 and PPH2 and from 10 to 55% by weight of soluble xylene fractions XS1 and XS2. Preferably, the amount of propylene homopolymers is from 50 to 85% by weight, more preferably from 55 to 80% by weight, even more preferably from 60 to 75% by weight. Consequently, the preferred amount of soluble xylene fraction is 15 to 50% by weight, more preferably 20 to 45% by weight, even more preferably 25 to 40% by weight.
    [047] A carefully selected ratio of propylene homopolymers to soluble xylene fractions contributes to the impact strength of the polyolefin composition and also to the wrinkling behavior.
    [048] In order to achieve the desired level of rigidity and CLTE, the polyolefin composition of the invention comprises an inorganic filler in a selected amount. Consequently, the polyolefin composition according to the present invention comprises an inorganic filler in an amount from 5 to 40% by weight.
    [049] The minimum limit for the amount of inorganic filler is more preferably at least 10% by weight, even more preferably at least 13% by weight, even more preferably at least 16% by weight and most preferably at least minus 18% by weight based on the weight of the polyolefin composition.
    [050] The upper limit for the amount of inorganic filler is more preferably not more than 35% by weight, even more preferably not more than 30% by weight, even more preferably not more than 26% by weight and the more preferably not more than 22% by weight based on the weight of the polyolefin composition.
    [051] If the amount of inorganic filler is over 40% by weight, the polyolefin composition does not have the necessary fluidity or the necessary impact force. In addition, the occurrence of flow marks will be very high. If the amount of inorganic filler is below 5% by weight, its contribution to stiffness will be very low and CLTE will be very high.
    [052] The polyolefin composition according to the invention additionally comprises an ethylene / 1-butene elastomer in an amount from 5 to 25% by weight based on the weight of the polyolefin composition.
    [053] It is common to add ethylene / α-olefin elastomers to heterophasic polypropylene compositions in order to improve their impact strength.
    [054] Currently, it has been surprisingly found that when an ethylene / 1-butene elastomer as a specific ethylene / a-olefin elastomer is added to a heterophasic polypropylene composition that presents a bimodal matrix of propylene homopolymer, a bimodal discontinuous phase of ethylene-propylene rubber that contains an inorganic filler, CLTE as well as the occurrence of flow marks can be further reduced (compared to the addition of just any ethylene / a-olefin elastomer or one of the most used of the ethylene / 1-octane elastomers).
    [055] The lower limit for the amount of ethylene / 1-butene elastomer is more preferably at least 7% by weight, even more preferably at least 8% by weight, even more preferably at least 9% by weight and most preferably at least 10% by weight based on the weight of the polyolefin composition.
    [056] The upper limit for the amount of ethylene / 1-butene elastomer is more preferably not more than 22% by weight, still more preferably not more than 19% by weight, even more preferably not more than 16 % by weight and most preferably not more than 14% by weight based on the weight of the polyolefin composition.
    [057] According to one embodiment of the present invention, the ethylene / 1-butene elastomer has a density of 850 to 880 kg / m3.
    [058] Generally, in ethylene / a-olefin elastomers the density correlates with the a-olefin content, with the higher densities generally meaning low levels of a-olefin.
    [059] Consequently, the lower limit for the density of the ethylene / 1-butene elastomer is more preferably at least 853 kg / m3, even more preferably at least 856 kg / m3, even more preferably at least 858 kg / m m3 and most preferably at least 860 kg / m3.
    [060] The upper limit for the density of the ethylene / 1-butene elastomer is more preferably not more than 876 kg / m3, even more preferably not more than 872 kg / m3, even more preferably not more than 869 kg / m3 and most preferably not more than 867 kg / m3.
    [061] The MFR of the ethylene / 1-butene elastomer that is used for the present invention is preferably selected - along with additional properties described here - to adjust the impact properties of the polyolefin composition.
    [062] An advantageous MFR range for the ethylene / 1-butene elastomer was found to be from 0.5 to 10 g / 10 min (190 ° C, 2.16 kg).
    [063] The lower limit for the MFR of the ethylene / 1-butene elastomer is more preferably at least 0.8 min, even more preferably at least 1.0 g / 10 min.
    [064] A more preferred upper limit for the MFR of the ethylene / 1-butene elastomer is 8g / 10min, even more preferably 7g / 10min.
    [065] In accordance with a preferred embodiment of the present invention, the inorganic filler is selected from the group consisting of talc and wollastonite.
    [066] According to a preferred embodiment of the present invention, the inorganic filler, which is used for the polyolefin composition, has a median particle size (D50) of 0.5 to 15 pm and an upper cut (D95) of 1 at 50 pm.
    [067] With D50> 15 pm and an upper cut> 50 pm, the reinforcing effect of the inorganic load becomes very small. With D50 <0.5 pm and a cut-off <1 pm, many of the charge particles would be in the nanoscale range, which means that the energy which is needed for a homogeneous distribution of the charge particles in the polyolefin would become unfavorably large.
    [068] The average particle size D50 is clearly defined, however, the fraction that is used to define the upper cut depends on the producer of the inorganic filler. A common method for measuring particle size distribution is a laser diffraction method. Common fractions that define the upper section of an inorganic load are D95, D97 and D98. For the present invention, the D95 fraction is preferred for the upper section definition.
    [069] An alternative way to define the upper cut is to specify the fraction of charge particles that have a diameter above a certain limit, that is, the so-called screen residue.
    [070] Accordingly, it is preferred for the present invention that the amount of charge particles having a particle size> 15 pm is not more than five, more preferably not more than three yet more preferably not more than 2%, even more preferably not more than 1%. According to a particularly preferred embodiment, the amount of charge particles having a particle size> 15 pm should not be more than 0.05%.
    [071] Still according to a preferred additional modality, the inorganic filler is talc.
    [072] According to a particularly preferred embodiment, the inorganic filler, which is used for the polyolefin composition of the present invention, is talc which has a mean D50 particle size of 0.8 to 12 pm and an upper cut (D95 ) from 1.0 to 40 pm, even more preferred a D50 from 2.0 to 10 pm and an upper cut from 2 to 30 pm, and a more preferred D50 from 1 to 5 pm and an upper cut (D95) from 2 at 10 pm.
    [073] The MFR of the polyolefin composition can be selected to provide optimum processability while maintaining all other desired properties. The MFR of the polyolefin composition is additionally selected in such a way that it is suitable for a range of applications, particularly for molding applications, especially for injection molding.
    [074] Consequently, the MFR of the polyolefin composition is from 5 to 50 g / 10 min. Preferably the MFR of the heterophasic propylene copolymer is 8 to 50 g / 10 min, more preferably 10 to 40 g / 10 min, even more preferably 13 to 30/10 min, and most preferably 16 to 25 g / 10 min
    [075] According to an embodiment of the present invention, the polyolefin composition comprises at least one alpha-nucleating agent.
    [076] Generally, nucleating agents remove the crystallization core formation when a molten polypropylene is solidified, and thereby increase the crystallization speed and temperature of the nucleated polypropylene compared to the non-nucleated polypropylene. The alpha-nucleating agent-containing polypropylene has improved mechanical properties, particularly rigidity and CLTE, but also HDT etc.
    [077] The polyolefin composition additionally contains more than 2% by weight of at least one alpha-nucleating agent. A lower limit of 0.001% by weight of alpha-nucleating agent is preferred. Preferably, the polyolefin composition comprises 0.005 to 0.5% by weight, more preferably 0.01 to 0.3% by weight and more preferably 0.04 to 0.15% by weight of at least one alpha-nucleating agent. .
    [078] Amounts of alpha-nucleating agent less than 0.001% by weight do not normally provide the desired effect level, while amounts greater than 2% by weight although providing the desired effect, polyolefin compositions become very expensive for because of the high price of nucleating agents.
    [079] Alpha-nucleating agents that can be used for the polyolefin composition of the invention include organic alpha-nucleating agents selected from the phosphorus group based on the nucleating agents similar to esters of metal salts and represented phosphoric acids by formula I

    [080] where R1 is oxygen, sulfur or a hydrocarbon group of 1 to 10 carbon atoms; each of R2 and R3 is hydrogen or a hydrocarbon or a hydrocarbon group of 1 to 10 carbon atoms; R2 and R3 can be the same or different from each other, two from R2, two from R3, or R2 and R3 can be linked together to form a ring, M is a monovalent to trivalent metal atom; n is an integer from 1 to 3 and m is both zero and 1, since n> m.
    [081] Preferred examples of the alpha-nucleating agents represented by the above formula include sodium phosphate-2,2'-methylene-bis (4,6-di-t-butyl-phenyl), sodium phosphate-2,2 ' -ethylidene-bis (4,6-di-t-butylphenyl), lithium-2,2'-methylene phosphate-bis (4,6-di-t-butylphenyl), lithium-2,2'-ethylidene phosphate -bis (4,6-di-t-butylphenyl), sodium phosphate-2,2'-ethylidene-bis (4-i-propyl-6-t-butylphenyl), lithium-2,2'-methylene phosphate -bis (4-methyl-6-t-butylphenyl), lithium-2,2'-methylene-bis (4-ethyl-6-t-butylphenyl) phosphate, calcium-bis [2,2'-thiobis (4-methyl-6-t-butyl-phenyl)], calcium phosphate-bis [2,2'-thiobis (4-ethyl-6-t-butylphenyl)], calcium phosphate-bis [2,2 ' -thiobis (4,6-di-t-butylphenyl)], magnesium phosphate-bis [2,2'-thiobis (4,6-di-t-butylphenyl)], magnesium phosphate [2,2 ' -tiobis (4-t-octylphenyl)], sodium phosphate-2,2'-butylidene-bis (4,6-dimethylphenyl), sodium phosphate-2,2'-butylidene-bis (4,6-di- t-butyl-phenyl) -, sodium phosphate-2,2'-t-octylmethylene-bi s (4,6-dimethyl-phenyl), sodium phosphate-2,2'-t-octylmethylene-bis (4,6-di-t-butylphenyl), calcium-bis [2,2'- methylene-bis (4,6-di-t-butylphenyl)], magnesium phosphate-bis [2,2'-methylene-bis (4,6-di-t-butylphenyl) -], barium-bis phosphate [ 2,2'-methylene-bis (4,6-di-t-butylphenyl)], sodium phosphate-2,2'-methylene-bis (4-methyl-6-t-butylphenyl), sodium phosphate-2 , 2'-methylene-bis (4-ethyl-6-t-butylphenyl), sodium phosphate (4,4'-dimethyl-5,6'-di-t-butyl-2,2'-biphenyl) , calcium phosphate-bis - [(4,4'-dimethyl-6,6'-di-t-butyl-2,2'-biphenyl)], sodium phosphate-2,2'-ethyl-i-dene -bis (4-m-butyl-6-t-butyl-phenyl), sodium phosphate-2,2'-methylene-bis- (4,6-di-methylphenyl), sodium phosphate-2,2'- methylene-bis (4,6-di-t-ethyl-phenyl), potassium-2,2'-ethylidene-bis (4,6-di-t-butylphenyl) phosphate, calcium-bis phosphate [2,2 '-ethylidene-bis (4,6-di-t-butylphenyl)], magnesium phosphate-bis [2,2'-ethyl-deno-bis (4,6-di-t-butylphenyl)], barium phosphate -bis [2,2'-ethylidene-bis- (4,6-di-t-butyl phenyl)], hydroxy-aluminum-bis [2,2'-methylene-bis (4,6-di-t-butylphenyl) phosphate], aluminum-tris [2,2'-ethylidene-bis (4, 6-di-t-butylphenyl)].
    [082] A second group of matches based on the nucleating agents includes, for example, hydroxy-bis [2,4, 8,10-tetrakis (1,1-dimethylethyl) -6-hydroxy-12H-dibenzo- [d, g] -dioxa-phosphocin-6] aluminum and mixtures of these with Li-myristate or Li-stearate.
    [083] Of matches based on nucleating agents, sodium phosphate-2,2'-methylene-bis (4,6-di-t-butylphenyl) or aluminum-hydroxy-bis [2,2'-methylene phosphate -bis (4,6-di-t-butyl-phenyl)] or aluminum-hydroxy-bis- [2,4,8,10-tetrakis (1,1-dimethylethyl) - 6-hydroxy -12H-dibenzo - [d, g] -dioxa-phosphocin-6] or mixtures thereof with Li-myristate or Li-stearate are especially preferred.
    [084] Nucleation agents also based on sorbitol, similar to the optionally substituted dibenzylidine sorbitol (eg 1.3: 2.4 dibenzylidene sorbitol, 1.3: 2.4 di (methylbenzylidene) sorbitol, 1.3: 2.4 of Di sorbitol (ethyl benzylidene), 1.3: 2.4 of Bis sorbitol (3,4-dimethylbenzylidene), etc.) or pine pitch can be used as nucleating agents.
    [085] Additional suitable alpha-nucleating agents are polymeric nucleating agents selected from the group consisting of vinylcycloalkane polymers and vinylalkane polymers. Nucleation with these polymeric nucleating agents is carried out either through a special reactor technique, where the catalyst is polymerized with similar monomers, for example, vinylcyclohexane (VCH), or by mixing the propylene polymer with the polymer vinyl (cyclo) alkane. These methods are described in more detail in, for example, EP 0316187A2 and WO 99/24479, the description of which is incorporated herein by reference.
    [086] Alpha-nucleating agents suitable for the polyolefin composition of the invention are additionally nucleating agents, as described, for example, in Macromolecules 2005, 38, 36883695, the description of which is incorporated herein by reference.
    [087] Nucleating agents such as ADK NA-11 sodium phosphate salt of (Methylene-bis (4,6-di-t-butylphenyl)) and ADK NA-21 (comprising hydroxy-bis oxidate [2,4 , 8,10- tetrakis (1,1-dimethylethyl) -6-hydroxy-12H-dibenzo- [d, g] - dioxa-phosphocin-6]) are commercially available from Asahi Denka Kokai and are among those who are preferably added to the polyolefin composition of the invention. Millad 3988 (3,4-Dimethylbenzylidene sorbitol), Millad 3905 and Millad 3940 available from Milliken & Company are other examples of nucleating agents that can be used in the invention.
    [088] Additional commercially available alpha-nucleating agents that can be used for the composition of the invention are, for example, Irgaclear XT 386 (N- [3,5-bis- (2,2-dimethyl-propionylamino) -phenyl ] -2,2-dimethylpropionamide) from Ciba Specialty Chemicals, Hyperform HPN-68L and Hyperform HPN-20E from Milliken & Company.
    [089] Among all the alpha-nucleating agents mentioned above, the nucleating agents based on hydroxy-bis [2,4,8,10-tetrakis (1,1-dimethylethyl) -6-hydroxy-12H -dibenzo- [d, g] -dioxa-phosphocin-6] similar to ADK NA-21, NA-21 E, NA-21 F, etc., sodium phosphate-2,2'-methylene-bis (4, 6-di-t-butylphenyl) (ADK NA-11), aluminum-hydroxy-bis [2,2'-methylene-bis (4,6-di-t-butyl-phenyl) phosphate.], Nucleating agents based on sorbitol similar to Millad 3988, Millad 3905 and Millad 3940 and polymeric nucleating agents selected from the group consisting of vinylcycloalkane polymers and vinylalkane polymers are particularly preferred.
    [090] According to an embodiment of the present invention, the at least one alpha-nucleating agent is composed of a polymeric nucleating agent selected from the group consisting of vinylcycloalkane polymers and vinylalkane polymers, preferably polyvinylcyclohexane ( pVCH).
    [091] According to an additional embodiment, at least one alpha-nucleating agent is selected from the group consisting of hydroxy-bis [2,4,8,10-tetrakis (1,1-dimethylethyl) aluminum oxide] - 6-hydroxy -5 12H- dibenzo- [d, g] -dioxa-phosphocin-6] based on the nucleating agents (eg ADK NA-21, NA-21 E, NA-21 F), sodium phosphate -2,2'-methylene-bis (4,6-di-t-butylphenyl) (ADK NA-11), aluminum-hydroxy-bis [2,2'-methylene-bis (4,6-di- t-butyl-phenyl)] and sorbitol-based nucleating agents (for example, Millad 3988, Millad 3905 and Millad 3940).
    [092] For the modality where at least one alpha-nucleating agent is selected from the group consisting of vinylcycloalkane polymers and vinylalkane polymers, preferably polyvinylcyclohexane (pVCH), the typical concentration of the vinyl polymer (cycle ) alkane in the polyolefin composition is from 0.0001 to 1.0% by weight, preferably 0.0001 to 0.1% by weight, more preferably 0.001 to 0.05% by weight and most preferably 0.001 to 0 , 01% by weight.
    [093] For the embodiment where the at least one alpha-nucleating agent is not a polymeric nucleating agent, the nucleating agent is typically present in the polyolefin composition in an amount from 0.001 to 1.0% by weight, preferably 0.001 to 0.5% by weight, more preferably 0.01 to 0.5% by weight and most preferably 0.01 to 0.3% by weight.
    [094] The polyolefin compositions that are used for the invention can contain various additives, which are generally used in polypropylene compositions, such as stabilizers, antioxidants, acid neutralizing agents, lubricants, ultraviolet absorbents and pigments provided so that they do not adversely affect the desired properties of the composition.
    [095] Therefore it is preferred that the additives are not more than 10.0% by weight, preferably not more than 8.0% by weight, more preferably not more than 5.0% by weight, even more preferably not more than 4.0% by weight, even more preferably not more than 3.0% by weight in the total polyolefin composition.
    [096] In addition, the polyolefin composition present may comprise additional polymer components other than the heterophasic composition of polypropylene and ethylene / 1-butene elastomer. However, the present invention is directed in particular to a polyolefin composition where the heterophasic polypropylene composition and the ethylene / 1-butene elastomer together add up to at least 90.0% by weight of all polymeric components of the polyolefin composition, preferably at least 93.0% by weight, more preferably at least 95.0% by weight, still preferably at least 97.0% by weight, even more preferably at least 98.0% by weight of all polymeric components of the composition polyolefin.
    [097] The polyolefin compositions of the present invention are suitable for a wide range of applications.
    [098] They are particularly suitable for the production of molded articles, in particular for the production of injection molded articles. Preferred examples of such injection molded articles are the applications of large parts for exterior applications in the automotive industry, in particular body panels.
    [099] Accordingly, a further aspect of the invention is a molded article comprising a polyolefin composition as described herein.
    [100] Yet a further aspect of the invention is an injection molded article comprising a polyolefin composition as described herein.
    [101] Compared to other polyolefin compositions, which are used today for similar or identical applications, the inventive polyolefin compositions have a unique balance of properties. They show a unique combination of low CLTE (<55 pm / m.K) and little or no occurrence of flow marks. Furthermore, rigidity (Flexural Module> 1700 MPa) and HDT (> 55 ° C) are at a high level.
    [102] Consequently, an additional aspect of the invention is directed to the use of a polyolefin composition as described here for the production of injection molded articles which have the following properties: a.CLTE -30 / + 80 ° C <49 pm / mK and b.CLTE + 23 / + 80 ° C <57 pm / mK Description of the heterophasic polypropylene composition
    [103] A heterophasic polypropylene composition being used according to the invention preferably has a multifaceted structure with a continuous matrix of propylene homopolymer and inclusions comprising at least two amorphous ethylene-propylene rubbers, which is in an elastomeric phase.
    [104] The homopolymer matrix comprises the propylene homopolymers PPH1 and PPH2.Optionally, the rubber also comprises some crystalline polyethylene.
    [105] Preferably each of the polypropylene homopolymer (s) is isostatic. The isotacticity of polypropylene is determined using 13C-NMR as a triad percentage (mm%). Consequently, it can be appreciated that the polypropylene homopolymer has a higher triad percentage, that is, greater than 90%, more preferably greater than 92%, even more preferably greater than 93%, even more preferably greater than 95% and most preferably greater than 98%.
    [106] Additionally, it can be appreciated that the polypropylene homopolymer (s) (PPH1, PPH2) as well as the total polypropylene heterophasic composition are not chemically modified as it is known, for example, from high melt polymers (HMS-polymer). Therefore, the heterophasic polypropylene composition and / or the polypropylene homopolymer (s) (PPH1, PPH2) are not cross-linked. The impact behavior can normally also be improved through the use of branched polypropylenes as described, for example, in EP 0787750, that is, unique types of branched polypropylene (Y-polypropylenes which have a structure with a single long side chain and an architecture mounting a "Y"). Such polypropylenes are characterized by a very high melting force. A parameter of the degree of branching is the branching index g '. The branching index g 'corresponds to the number of branches of a polymer. The branching index g 'is defined as g' = [IV] br / [IV] lin where g 'is the branching index, [IVbr] is the intrinsic viscosity of the branched polypropylene and [IV] lin is the intrinsic viscosity of linear polypropylene which has the same molecular weight measurement (within a range of ± 10%) as branched polypropylene. Hereby, a low value of g 'is an indicator for a highly branched polymer. In other words, if the value of g' decreases, the branching of polypropylene increases. Reference is made in this context to BH Zimm and WH Stockmeyer, J Chem. Phys. 17, 1301 (1949). This document is included here by reference. Therefore, it is preferred that the branching index g 'of the polypropylene homopolymer (s) (PPH1, PPH2) is at least 0.85, more preferably at least 0.90, even more preferably at least 0.95, similar to 1.00.
    [107] The term propylene homopolymer used in the imminent invention refers to a polypropylene that consists substantially, that is, at least 97% by weight, preferably at least 98% by weight, more preferably at least 99% by weight. weight, even more preferably at least 99.8% by weight of propylene units. 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.
    [108] Each propylene homopolymer can be unimodal or multimodal, similar to bimodal in view of the molecular weight distribution.
    [109] The term "multimodal" or "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 weight .
    [110] As will be explained below, a propylene homopolymer can be produced in a single step or in a sequential step process, using series reactors or parallel configuration and which can be operated under different reaction conditions. As a consequence, each fraction prepared in a specific reactor may have its own molecular weight distribution.
    [111] When the distribution curves from these fractions are superimposed to obtain the molecular weight distribution curve of the final polymer, these curves can have two or more maximums or at least be distinctly enlarged when compared to curves for the individual fractions. A given polymer, produced in two or more series or parallel steps, is called bimodal or multimodal, depending on the number of steps.
    [112] Consequently, the propylene homopolymer can be multimodal or bimodal in view of its weight.
    [113] As a further necessity of the present invention, the propylene heterophasic copolymer must comprise an ethylene-propylene rubber.
    [114] Similar to polypropylene homopolymer, ethylene-propylene elastomeric rubber can be unimodal or multimodal, similar to bimodal. However, it is preferred that ethylene / propylene rubber be unimodal. With respect to the definition of unimodal and multimodal, similar for bimodal, the above definition is preferred.
    [115] According to the present invention, a process is also provided for the manufacture of the polyolefin composition discussed above. The ethylene-propylene rubber (s) can be mixed with the homopolymer (s) of polypropylene after their respective polymerizations and are subsequently mixed with the ethylene / 1-butene elastomer and the inorganic filler and the optional alpha-nucleating agent. In an alternative method, a heterophasic polypropylene composition is produced in a multi-step process , comprising at least four consecutive reactors and subsequently mixed with the ethylene / 1-butene elastomer and the inorganic filler and the optional alpha-nucleating agent.
    [116] However, more desirably, two heterophasic propylene copolymers are produced in separate multistage processes and subsequently mixed with the ethylene / 1-butene elastomer and the inorganic filler and the optional alpha-nucleating agent.
    [117] In a particularly preferred embodiment, a PPH1 polypropylene homopolymer is produced in at least one slurry reactor or a gas and slurry reactor and subsequently an ethylene-propylene rubber is produced in at least one slurry reactor. gas phase to obtain a first heterophasic propylene copolymer. In addition, a PPH2 polypropylene homopolymer is produced in at least one slurry reactor or a gas and slurry phase reactor and subsequently an ethylene-propylene rubber is produced in at least one gas phase reactor to obtain a second propylene heterophasic copolymer.
    [118] Consequently, each propylene heterophasic copolymer of the impending invention can typically be produced in a cascade of more than four reactors, where the first reactor is a liquid volume reactor preferably of closed circuit design, the second reactor or is a reactor of liquid volume preferably of closed loop design or a gas phase reactor and all subsequent reactors are gas phase reactors preferably of fluidized bed design. The component (s) produced in the first two reactors are (are) crystallisable propylene homopolymers while the component produced in the third and / or fourth reactor is a largely amorphous copolymer with high amounts of co-monomer. According to a specific modality, only three reactors are used both with the two reactors that produce homopolymer and with the third reactor that produces ethylene / propylene rubber or with a reactor that produces homopolymer and two subsequent reactors that produce ethylene / propylene rubber According to another specific modality, only two reactors are used, one producing homopolymer and the second producing ethylene-propylene rubber.
    [119] In the following, a preferred process is described in more detail: such a process for manufacturing the present invention comprises the following steps: (i) polymerization of propylene in a first reactor system, preferably comprising a closed volume reactor and an optional gas phase reactor, to obtain a PPH1 polypropylene homopolymer; (ii) transferring the propylene homopolymer PPH1 obtained within a second reactor system preferably comprising at least one gas phase reactor; (iii) polymerization of propylene and ethylene in said second reactor system in the presence of the polypropylene homopolymer to produce an ethylene-propylene rubber and obtain a first propylene heterophasic copolymer containing PPH1 and XS1, and - regardless of the process steps ( i) to (iii); (iv) polymerization of propylene in a third reactor system, preferably comprising a closed loop volume reactor and an optional gas phase reactor, to obtain a PPH2 polypropylene homopolymer; (v) transferring the PPH2 propylene homopolymer obtained into a fourth reactor system preferably comprising at least one gas phase reactor; (vi) polymerization of propylene and ethylene in said fourth reactor system in the presence of the polypropylene homopolymer PPH2 to produce an ethylene-propylene rubber and to obtain a second heterophasic propylene copolymer containing PPH2 and XS2 and; (vii) mixing, in particular foundry mixture, the first and second heterophasic propylene copolymers obtained with ethylene / 1-butene elastomer and inorganic filler.
    [120] Co-monomer feeds within various reactors can be adapted to produce the heterophasic propylene copolymer with the desired properties and the amounts of co-monomer will be readily determined by a person skilled in the art.
    [121] Additional details regarding the manufacture of heterophasic propylene copolymers (HECO) can be derived from WO 9740080.
    [122] In such a procedure, the catalyst system used can be varied between stages, but is preferably the same for all stages. In particular, a prepolymerized heterogeneous catalyst is preferably used.
    [123] A Ziegler-Natta catalyst system is preferably used as a catalyst for the preparation of the heterophasic propylene copolymer. Such Ziegler-Natta catalyst systems are known in the art and comprise a catalyst component, a co-catalyst component and an external donor. The catalyst component of the catalyst system primarily contains magnesium, titanium, halogen and an internal donor. Electron donors control stereospecific properties and / or improve the activity of the catalyst system. Various electron donors including ethers, esters, polysilanes, polysiloxanes and alkoxysilanes are known in the art.
    [124] The catalyst preferably contains a transition metal compound as a pro-catalyst component. The transition metal compound is selected from the group consisting of titanium compounds that have a degree of oxidation of 3 or 4, vanadium compounds, zirconium compounds, cobalt compounds, nickel compounds, tungsten compounds composed of rare earth metal, titanium trichloride and titanium tetrachloride are particularly preferred.
    [125] It is preferred to use catalysts that can withstand the high temperatures that predominate in the closed loop reactor. Conventional Ziegler-Natta catalysts for isostatic propylene polymerization generally have an operating temperature limit of around 80 ° C, above which they either become deactivated or lose their stereoselectivity. This low polymerization temperature can put a practical limit on the heat removal efficiency of the closed loop reactor.
    [126] A preferred catalyst for use according to the invention is described in EP 591224 which describes a method for the preparation of a pro-catalyst composition from magnesium dichloride, a titanium compound, a lower alcohol and a phthalic acid ester containing at least five carbon atoms. According to EP 591224, a transesterification reaction is carried out at an elevated temperature between the lower alcohol and the phthalic acid ester, by means of which the groups of esters from the lower alcohol change places.
    [127] Magnesium dichloride can be used as such or it can be combined with silica, for example, by absorbing silica with a solution or slurry containing magnesium dichloride. The lower alcohol used can preferably be methanol or ethanol, particularly ethanol.
    [128] The titanium compound used in the preparation of the pro-catalyst is preferably an organic or inorganic titanium compound, which is in the oxidation stage of 3 or 4. Other transition metal compounds as well, such as vanadium, zirconium compounds , chromium, molybdenum and tungsten can be mixed with the titanium compound. The titanium compound is usually an oxyhalide halide, an organic metal halide, or a purely metal organic compound in which only organic binders have been attached to the transition metal. Titanium halides are particularly preferred, especially titanium tetrachloride.
    [129] The alkoxy group of the phthalic acid ester used comprises at least five carbon atoms, preferably at least eight carbon atoms. Therefore, since the ester can be used, for example, propylhexyl phthalate, dioctyl phthalate, diisodecyl phthalate and di-tridecyl phthalate, the molar ratio of the magnesium halide phthalic acid ester is preferably about 0, 2: 1.
    [130] Transesterification can be performed, for example, by selecting a phthalic acid ester - a pair of lower alcohols that spontaneously transesterifies the catalyst at an elevated temperature or through the help of a catalyst, which does not damage the composition of pro-catalyst. It is preferred that the transesterification is carried out at a temperature which is 110 to 115 ° C, preferably 120 to 140 ° C.
    [131] The catalyst is used in conjunction with an organometallic cocatalyst and an external donor. Generally, the external donor has the formula RnR'm Si (R "O) 4-nm where R and R 'can be the same or different and represent a linear, branched or cyclic aliphatic or aromatic group; R" is methyl or ethyl; n is an integer from 0 to 3; m is an integer from 0 to 3; and n + m is 1 to 3.
    [132] In particular, the external donor is selected from the group consisting of cyclohexyl methylmethoxy silane (CHMMS), dicyclopentyl dimethoxy silane (DCPDMS), diisopropyl dimethoxy silane, diisobutyl dimethoxy silane, and di-t -butyl dimethoxy silane. An organoaluminium compound is used as a cocatalyst. The organoaluminium compound is preferably selected from the group consisting of trialkyl aluminum, aluminum dialkyl chloride and alkyl aluminum sesquichloride.
    [133] According to the invention, such catalysts are typically introduced only within the first reactor. The catalyst components can be fed into the reactor separately or simultaneously or the components of the catalyst system can be pre-contacted before the reactor.
    [134] Such pre-contact may also include a catalyst prepolymerization before feeding into the polymerization reactor itself. In prepolymerization, the catalyst components are contacted for a short period with a monomer before being fed to the reactor.
    [135] If the polyolefin composition comprises a polymeric nucleating agent which is carried out by prepolymerizing the catalyst with vinyl (cyclo) hexane, this is also preferably done in the aforementioned catalyst prepolymerization.
    [136] As described above, after the manufacture of the heterophasic propylene copolymer the mixture with the ethylene / alpha-olefin and the inorganic filler and the alpha-nucleating agent (s) follow. Production of ethylene elastomer / a-olefin
    [137] The production of the ethylene / a-olefin elastomer is described in detail in: Chum SP, Kao CI and Knight GW: Structure, properties and preparation of polyolefins produced by single-site technology. In: Metallocene-based Polyolefins - Volume 1, Scheirs J and Kaminsky W Eds, John Wiley and Sons Ltd, Chichester (West Sussex, England), 2000 pages 262 to 264.
    [138] Alternatively, the ethylene-1-butene elastomers, which are commercially available and fulfill the indicated requirements, can be used. Composition
    [139] Heterophasic copolymers, ethylene / 1-butene elastomer, inorganic filler and optional nucleating agent can be mixed, in particular mixed by casting, according to any conventional procedure known in the art.
    [140] The polyolefin compositions of the present invention are preferably produced by combining heterophasic propylene copolymers, the ethylene / 1-butene elastomer, the inorganic filler, the optional alpha-nucleating agent and any additional pigment-like additives , stabilizers, processing aids, etc. in a melt mixing device.
    [141] Foundry mixing devices suitable for this process are batch and continuous kneaders, twin screw extruders and single screw extruder with special mixing sections and co-kneaders. The residence time must be chosen so that a sufficiently high degree of homogenization is achieved. XCS measurement methods
    [142] Cold soluble xylenes are determined at 23 ° C according to ISO 6427. Soluble xylenes are defined as the percentage by weight left in the solution after the polymer sample is dissolved in hot xylene and the solution is allowed to cool to 23 ° C. MFR
    [143] The casting flow rates were measured with a loading of 2.16 kg at 230 ° C for the polypropylene and the inventive polyolefin compositions of the examples. The melt flow rate is measured with a 2.16 kg load at 190 ° C for the ethylene / alpha-olefin elastomers. The melt flow rate is that amount of polymers in grams that the ISO 1133 standardized tester expels within 10 minutes at a temperature of 230 ° C or 190 ° C under a load of 2.16 kg. Flexural test
    [144] Flexural tests are carried out in accordance with ISO 178: 2001 at + 23 ° C on injection molded samples of 80x10x4 mm3 prepared through injection molding in line with ISO 1873-2. The flexural module (E-module) was calculated from the linear part of the results of said flexural test. Charpy notch impact test
    [145] Charpy impact force was determined according to ISO 179-1eA: 2000 on samples with V-notches of 80x10x4 mm3 at + 23 ° C, -20 ° C and -30 ° C. The test specimens were prepared by in-line injection molding with ISO 1873-2. Intrinsic viscosity
    [146] Intrinsic viscosity was measured according to DIN ISO 1628-1 (October 1999) in decal at 135 ° C. Density
    [147] The density has been determined according to ISO 1183. NMR spectrometry measurements:
    [148] The co-monomer content was determined using quantitative nuclear magnetic resonance spectrometry (13C-NMR) after basic assignment (eg, "NMR Spectra of Polymers and Polymer Additives", AJ Brandolini and DD Hills, 2000, Marcel Dekker, Inc. New York). The experimental parameters were adjusted to ensure measurement of quantitative spectra for this specific task (for example, "200 and More NMR Experiments: A Practical Course", S. Berger and S. Braun, 2004, Wiley-VCH, Weinheim). Quantities were calculated using simple correct ratios of the sign integrals of representative locations in a manner known in the art. CLTE
    [149] The Termolinear Expansion coefficient was determined according to ISO 11359-2: 1999 on 10 mm long pieces cut from injection molded test specimens with dimensions of 80 x 10 x 4 mm3 prepared according to ISO 1873-2. The measurement was carried out between +23 and + 80 ° C as well as between -30 and + 80 ° C with a heating rate of 1 ° C / min. Heat Deflection Temperature (HDT):
    [150] HDT was determined on 80x10x4 mm3 injection molded test specimens prepared according to ISO 1873-2 and stored at + 23 ° C for at least 96 hours before measurement. The test was carried out on specimens supported flat in accordance with ISO 75, condition A, with a nominal surface tension of 1.80 MPa and according to ISO 75, condition B, with a nominal surface tension of 0.45 MPa. Particle size
    [151] The average particle size D50 and the upper section (D95) are determined by laser diffraction in accordance with ISO 13320-1: 1999. Wrinkling
    [152] The wrinkle is determined on the blocked center, injection-molded circular discs (diameter 180mm, thickness 3mm, having a flow angle of 355 ° and a cutout of 5 °). Both specimens are molded by applying two different pressure retention times (10s and 20s respectively). The casting temperature at the gate is 260 ° C, and the average frontal flow rate in the mold is 100mm / s.
    [153] Tool temperature: 40 ° C, back pressure: 60000 kPa.
    [154] After conditioning the specimen at room temperature for 96 hours, the radial and tangential dimensional changes to the flow direction are measured for both discs. The average of respective values from both disks are reported as final results. Flow Marks
    [155] The tendency to show flow marks was examined with a method as described below. This method is described in detail in WO 2010/149529, which is incorporated here in its entirety.
    [156] An optical measurement system, as described by Sybille Frank et al. in PPS 25 Intern. Conf. Polym. Proc. Soc 2009 or Proceedings of the SPIE, Volume 6831, pp 68130T- 68130T-8 (2008) was used to characterize the surface quality. This method consists of two aspects: 1. Image recording: the basic principle of the measurement system is to illuminate the dishes with a defined light source (LED) in an indoor environment and to record an image with a CCD camera system.
    [157] A schematic configuration is given in Figure 1.2. Image analysis: The specimen is illuminated on one side and the portion reflected upstream of the light is deflected through two mirrors to a CCD sensor. The thus created image of gray value is analyzed in lines. From the recorded deviations of gray values, the mean square error (MSE) is calculated allowing a quantification of the surface quality, that is, the higher the MSE value, the more pronounced the surface defect.
    [158] Generally, for one and the same material, the tendency to flow marks increases when the injection speed is increased.
    [159] For this evaluation, 210x148x3mm3 plates with VW K50 grain and a 1.4 mm film port were used and were produced at five different injection speeds using screw speeds of 57, 50, 35, 17 and 8 mm /s.
    [160] Additional Conditions: Melting temperature: 240 ° C Mold temperature 30 ° C Dynamic pressure: 1000 kPa hydraulic
    [161] The lower the MSE value is at a certain injection speed, the lower the tendency for flow marks. Examples
    [162] The following materials were used:
    [163] Polymer 1: Hypophasic propylene copolymer having an MFR of 11 g / 10 min, with 65% by weight of a propylene homopolymer matrix (MFR = 55 g / 10 min) and 35% by weight of a rubber ethylene-propylene. The XCS content is 35% by weight. XCS IV is 2.5 dl / g. The ethylene content of XCS is 38% by weight. Polymer 1 still contains 0.1% by weight of pentaerythrityl-tetrakis (3- (3 ', 5'-di-terc.butyl-4-hydroxyphenyl) -propionate and 0.1% by weight of Tris (2.4 -di-t-butylphenyl) phosphite and 0.05% by weight of calcium stearate.
    [164] Polymer 2: Hypophasic propylene copolymer having an MFR of 70 g / 10 min, with 80% by weight of a propylene homopolymer matrix (MFR = 160 g / 10 min) and 20% by weight of a rubber ethylene-propylene. The XCS content is 20% by weight. XCS IV is 2.2 dl / g. The ethylene content of XCS is 36% by weight. The heterophasic copolymer contains 35 ppm pVCH as a polymeric nucleating agent. Polymer 2 still contains 0.05% by weight of pentaerythrityl-tetrakis (3- (3 ', 5'-di-tert. Butyl-4-hydroxyphenyl) - propionate and 0.05% by weight of Tris (2.4 di-tert-butylphenyl) phosphite and 0.25% by weight of glycerol monostearate.
    [165] Talc: Jetfine 3CA, commercially available from Luzenac. Jetfine 3CA has a D50 of 3.9 pm, an upper cut (D95) of 7.8 pm, both calculated from the particle size distribution measured by laser diffraction according to ISO 13320-1: 1999 and a residue of screen (determined by Alpine Airjet) of max. 0.05% of particles> 15 pm.
    [166] EB 1: ethylene-1-butene copolymer having an MFR (190 ° C, 2.16 kg) of 5.0 g / 10 min and a density of 865 kg / m3. EB 1 is available as Engage 7447 from The Dow Chemical Company.
    [167] EB 2: ethylene-1-butene copolymer having an MFR (190 ° C, 2.16 kg) of 1.2 g / 10 min and a density of 862 kg / m3. EB 2 is available as Engage 7467 from The Dow Chemical Company.
    [168] EO 1: ethylene-1-octene copolymer, having an MFR (190 ° C, 2.16 kg) of 0.5 g / 10 min and a density of 863 kg / m3. EB 3 is available as Engage 8180 from The Dow Chemical Company. EO 2: ethylene-1-octene copolymer, having an MFR (190 ° C, 2.16 kg) of 13.0 g / 10 min and a density of 864 kg / m3. EB 4 is available as Engage 8130 from The Dow Chemical Company. EO 3: ethylene-1-octene copolymer, having an MFR (190 ° C, 2.16 kg) of 1.0 g / 10 min and a density of 870 kg / m3. EB 5 is available as Engage 8100 from The Dow Chemical Company. EO 4: ethylene-1-octene copolymer, having an MFR (190 ° C, 2.16 kg) of 5.0 g / 10 min and a density of 870 kg / m3. EB 6 is available as Engage 8200 from The Dow Chemical Company.
    [169] EO 5: ethylene-1-octene copolymer, having an MFR (190 ° C, 2.16 kg) of 30.0 g / 10 min and a density of 870 kg / m3. EB 7 is available as Engage 8400 from The Dow Chemical Company.
    [170] CB: master batch of carbon black: 40% by weight of carbon black + 60% by weight of LDPE.
    [171] AP: additive package: 0.1 pbw of Pentaerythrityl-tetrakis (3- (3 ', 5'-di-terc.butil-4-hydroxyphenyl) -propionate + 0.1 pbw of Tris (2.4 -di-t-butylphenyl) phosphate + 0.2 pbw% calcium stearate + 1.1 pbw propylene homopolymer (MFR (230 ° C, 2.16 kg) = 3 g / 10 min). Exemplary Compositions)
    Table 2 (Exemplary Compositions Properties)


    [172] It can be seen that for the examples of the invention the CLTE is significantly lower. In addition, the compositions of the invention also show a significantly lower tendency to exhibit flow marks at high injection speeds.
    权利要求:
    Claims (11)
    [0001]
    1. Polyolefin composition characterized by comprising: a) 35-90% by weight, based on the weight of the polyolefin composition, of a heterophasic polypropylene composition having a continuous matrix phase and a discontinuous phase, wherein the continuous matrix phase comprises two propylene homopolymers of different MFR2 and in which the discontinuous phase comprises two ethylene-propylene rubbers with different molecular weight, and in which the heterophasic polypropylene composition comprises: i) 10-50% by weight, based on the weight of the composition of heterophasic polypropylene, of a first propylene homopolymer (PPH1) having an MFR2 measured according to ISO 1133 of 30-80 g / 10 min (230 ° C, 2.16 kg), ii) 20-65% by weight, based on the weight of the heterophasic polypropylene composition, of a second propylene homopolymer (PPH2) having an MFR2 measured according to ISO 1133 of 100-250g / 10 min (230 ° C, 2.16 kg), iii) 5- 30% by weight, based on the weight of the heterophasic polypropylene composition of a first cold soluble xylene fraction (XS1) having an IVxsi intrinsic viscosity of 2.0 - 3.0 dl / g, iv) 5-25% by weight, based on the weight of the heterophasic polypropylene composition of a second xylene fraction cold soluble (xS2) having an intrinsic viscosity IVXS2 of 1.5 —2.8 dl / g, with the condition that IVXS1 ^ IVXS2, b) 5 - 40% by weight, based on the weight of the polyolefin composition, of an inorganic filler , and c) 5 - 25% by weight, based on the weight of the polyolefin composition, of an ethylene / 1-butene elastomer, where the polyolefin composition has a CLTE -30 / + 80 ° C <49 pm / mK , a CLTE + 23 / + 80 ° C <57 pm / m ^ K and a flexural modulus> 1700 MPa.
    [0002]
    2. Polyolefin composition according to claim 1, characterized by the fact that the ethylene / 1-butene elastomer has a density of 850 - 880 kg / m3.
    [0003]
    3. Polyolefin composition according to claim 1 or 2, characterized in that the ethylene / 1-butene elastomer has an MFR2 measured according to ISO 1133 of 0.5 - 10 g / 10 min (190 ° C, 2.16 kg).
    [0004]
    4. Polyolefin composition according to any one of claims 1 to 3, characterized by the fact that the inorganic filler is selected from the group consisting of talc and wollastonite.
    [0005]
    5. Polyolefin composition according to any one of claims 1 to 4, characterized in that the MFR2 measured according to ISO 1133 of the polyolefin composition is 5.0 - 50 g / 10 min (230 ° C, 2.16 kg).
    [0006]
    6. Polyolefin composition according to any one of claims 1 to 5, characterized in that it contains at least one alpha-nucleating agent.
    [0007]
    7. Polyolefin composition according to any one of claims 1 to 6, characterized in that the at least one alpha-nucleating agent is selected from the list consisting of hydroxy-bis [2,4,8,10-tetrakis (1,1-dimethylethyl) -6-hydroxy-12H-dibenzo- [d, g] -doxa-phosphocin-6-oxate] aluminum containing nucleating agents, 2,2'-methylene-bis (4,6- sodium di-t-butylphenyl) phosphate, aluminum m-hydroxy-bis [2,2'-methylene-bis (4,6-di-t-butyl-phenyl) -phosphate, nucleating agents based on sorbitol and polymeric nucleating agents selected from the group consisting of vinylcycloalkane polymers and vinylalkane polymers.
    [0008]
    8. Polyolefin composition according to claim 7, characterized in that the at least one alpha-nucleating agent is a polymeric nucleating agent selected from the group consisting of vinylcycloalkane polymers and vinylalkane polymers.
    [0009]
    Molded article characterized by the fact that it comprises a polyolefin composition, as defined in any one of claims 1 to 8.
    [0010]
    10. Molded article according to claim 9, characterized by the fact that it is an injection molded article.
    [0011]
    11. Use of a polyolefin composition, as defined in any one of claims 1 to 8, characterized in that it is for the production of injection molded articles having the following properties: a) CLTE -30 / + 80 ° C <49 pm / mK e; b) CLTE + 23 / + 80 ° C <57 pm / m.K.
    类似技术:
    公开号 | 公开日 | 专利标题
    BR112013022136B1|2020-12-08|polyolefin composition, molded article and use of a polyolefin composition
    RU2464288C2|2012-10-20|Polyolefin compound with low coefficient of linear thermal expansion
    KR101591215B1|2016-02-02|Polyolefin composition with reduced occurrence of flow marks
    US8207272B2|2012-06-26|Tough composition for food applications
    EP2731988B1|2015-09-09|High flow polyolefin composition with low shrinkage and clte
    US20090131586A1|2009-05-21|High melt flow polymer of improved durability for pipe applications
    EP2084223B1|2010-07-28|Polyolefin compositions
    EP2154194B1|2011-10-19|Polypropylene composition having low shrinkage
    US11111369B2|2021-09-07|Foamed polypropylene composition
    US20200207960A1|2020-07-02|Polypropylene composition with excellent surface appearance
    US8759452B2|2014-06-24|Propylene composition with high stiffness and impact strength
    US11186708B2|2021-11-30|Polypropylene composition with outstanding impact performance
    EP2239298A1|2010-10-13|Polypropylene composition with high stiffness and impact strength
    同族专利:
    公开号 | 公开日
    EP2681277A1|2014-01-08|
    BR112013022136B8|2021-05-25|
    CN103443194A|2013-12-11|
    CN103443194B|2016-06-01|
    US9611382B2|2017-04-04|
    WO2012117086A1|2012-09-07|
    BR112013022136A2|2016-12-06|
    US20150166776A1|2015-06-18|
    EP2681277B1|2015-06-10|
    EP2495280A1|2012-09-05|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    CA1331416C|1987-11-10|1994-08-09|Kizuku Wakatsuki|High-strength polypropylene fiber|
    FI88047C|1991-05-09|1993-03-25|Neste Oy|Catalyst-based catalyst for polymerization of olivines|
    JPH093299A|1995-06-15|1997-01-07|Tonen Chem Corp|Polypropylene composition|
    AT240354T|1996-02-01|2003-05-15|Borealis Gmbh|STRUCTURISOMERE POLY |
    FI104828B|1996-04-19|2000-04-14|Borealis As|New tubular polypropylene composition|
    FI980342A0|1997-11-07|1998-02-13|Borealis As|Polymerroer och -roerkopplingar|
    DE19754061A1|1997-12-05|1999-06-10|Borealis Polymere Holding Gmbh|Propylene copolymer-based resin composition for forming molded articles of improved surface condition|
    JP3993011B2|2002-04-10|2007-10-17|サンアロマー株式会社|Polypropylene composition|
    RU2464288C2|2008-07-14|2012-10-20|Бореалис Аг|Polyolefin compound with low coefficient of linear thermal expansion|
    EP2275476A1|2009-06-09|2011-01-19|Borealis AG|Automotive material with excellent flow, high stiffness, excellent ductility and low CLTE|
    EP2275485B1|2009-06-22|2011-06-08|Borealis AG|Heterophasic polypropylene copolymer composition|ES2552779T3|2011-07-15|2015-12-02|Borealis Ag|Composition of high fluid polyolefin with low shrinkage and CLTE|
    CN104837904B|2012-11-30|2017-07-04|博禄塑料（上海）有限公司|Polypropene composition that is that tiger fur line is reduced or eliminated and retaining excellent mechanical performance|
    EP2746326B1|2012-12-19|2017-11-29|Borealis AG|Automotive compound with reduced tigerskin|
    ES2640797T3|2013-05-31|2017-11-06|Borealis Ag|Rigid polypropylene composition suitable for unprimed paint|
    CN105283503A|2013-06-19|2016-01-27|博里利斯股份公司|Polypropylene with broad molecular weight distribution|
    EP2824142B1|2013-07-12|2016-04-13|Borealis AG|Heterophasic copolymer|
    US9708471B2|2013-08-09|2017-07-18|Equistar Chemicals, Lp|Filled polypropylene compositions and related automotive components|
    US9290646B2|2013-10-04|2016-03-22|Equistar Chemicals, Lp|Molded articlesand related filled thermoplastic polyolefin compositions|
    CN103724807A|2013-12-17|2014-04-16|浙江普利特新材料有限公司|Polypropylene composite material with low after shrinkage, high modulus and high impact resistance and preparation method thereof|
    CN105849178B|2013-12-20|2018-05-15|沙特基础工业公司|Polyolefin composition|
    EP3083822B1|2013-12-20|2021-09-08|Saudi Basic Industries Corporation|Heterophasic propylene copolymer|
    WO2017041296A1|2015-09-11|2017-03-16|Borouge Compounding Shanghai Co., Ltd.|Polypropylene composition|
    CN107805340B|2016-09-09|2021-07-02|中国石油化工股份有限公司|Polyolefin composition and polyolefin material|
    EP3532540A1|2016-10-25|2019-09-04|Borealis AG|High flow heterophasic polypropylene copolymers with improved mechanical and optical properties|
    ES2873505T3|2016-10-25|2021-11-03|Borealis Ag|Heterophasic polypropylene composition with improved optical and mechanical properties|
    EP3559111A1|2016-12-23|2019-10-30|SABIC Global Technologies B.V.|Thermoplastic composition|
    CN112313278A|2018-06-18|2021-02-02|伊奎斯塔化学有限公司|Low density polyolefin resins with stiffness, impact balance and high dimensional stability|
    CN109749248A|2018-12-29|2019-05-14|正雄箱包（河源）有限公司|A kind of polypropylene modified material and preparation method thereof and luggage|
    WO2021078857A1|2019-10-23|2021-04-29|Borealis Ag|Heterophasic polypropylene composition with improved stiffness and impact behaviour|
    EP3812405A1|2019-10-23|2021-04-28|Borealis AG|Polypropylene composition with improved processability and impact strength|
    WO2022034127A1|2020-08-13|2022-02-17|Borealis Ag|Filled automotive polypropylene composition containing recyclates|
    法律状态:
    2018-04-03| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|
    2019-08-27| B06U| Preliminary requirement: requests with searches performed by other patent offices: procedure suspended [chapter 6.21 patent gazette]|
    2020-03-24| B07A| Application suspended after technical examination (opinion) [chapter 7.1 patent gazette]|
    2020-08-11| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|
    2020-12-08| 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 02/03/2012, OBSERVADAS AS CONDICOES LEGAIS. |
    2021-05-25| B16C| Correction of notification of the grant [chapter 16.3 patent gazette]|Free format text: REFERENTE AO DESPACHO 16.1 PUBLICADO NA RPI 2605, QUANTO AO NOME DO TITULAR |
    优先权:
    申请号 | 申请日 | 专利标题
    EP11156746A|EP2495280A1|2011-03-03|2011-03-03|Polyolefin composition with low CLTE and reduced occurrence of flow marks|
    EP11156746.7|2011-03-03|
    PCT/EP2012/053602|WO2012117086A1|2011-03-03|2012-03-02|Polyolefin composition with low clte and reduced occurrence of flow marks|
    [返回顶部]