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    • 专利摘要:
    POLYMERIC COMPOSITION, ITEM, AND, USE OF POLYMERIC COMPOSITION. The present invention relates to a composition of polypropylene and polyethylene, which contains a specific compatibilizer and a flow enhancer. Furthermore, the present invention is also related to articles comprising said composition and the use of said articles in packaging applications.
    公开号:BR112018005269B1
    申请号:R112018005269-8
    申请日:2016-11-03
    公开日:2022-01-25
    发明作者:Bhawna Kulshreshtha；Markus Gahleitner
    申请人:Borealis Ag；
    IPC主号:
    专利说明:

    [001] The present invention relates to a composition of polypropylene and polyethylene, which contains specific compatibilizer and flow enhancer. Furthermore, the present invention also relates to articles comprising said composition and the use of said articles in packaging use.
    [002] Polyolefins, such as polypropylene and polyethylene, are typical polymeric raw materials with many application areas and a remarkable growth rate. The reason is not just a favorable price/performance ratio, but also the versatility of these materials and a wide range of possible modifications, which allow adaptation of end-use properties over a wide range. Chemical modifications, copolymerization, joining, extraction, heat treatment and combination of these techniques can convert common polyolefins into valuable products with special properties.
    [003] In recent years, the demand for the use of recycled polyolefins, from waste plastic material derived from post-consumer waste (RPC) and/or post-industrial waste (RPI), in a composite with virgin polymer has increased in recent years. years, not least because there are legal requirements in some segments, such as automotive applications.
    [004] One of the main problems in polyolefin recycling, especially when it comes to post-consumer waste (RPC) material streams, is the difficulty of quantitatively separating polypropylene (PP) and polyethylene (PE). Commercial recycles from RPC sources were commonly found containing blends of PP and PE, the minor component reaching up to < 50% by weight.
    [005] Such recycled PP/PE unions typically suffer from deteriorated mechanical and optical properties, have poor odor and taste performance, and generally suffer from poor compatibility between major polymer phases, resulting in limited impact strength and toughness. to thermal deflection. This inferior performance is partly caused by PE with its lower stiffness and melting point forming the continuous phase even at PP concentrations of up to 65% due to the normally higher viscosity of PE components in RPC.
    [006] This normally excludes application to high quality parts, and only allows use in low-cost, non-demanding applications.
    [007] Some research has been done to improve the compatibility between PP and PE. According to Wei Zhu et al.; Journal of Applied Polymer Science, Vol. 58, p. 515-521 (1995), the addition of ethylene-propylene copolymer as a compatibilizer for polypropylene and polyethylene unions can remedy the situation of high incompatibility to some extent and that ethylene-propylene rubber (EPR) or ethylene-propylene rubber Propylene diene (EPDM) can substantially improve the hardness of joints, but at the expense of degraded moduli and tensile strength.
    [008] WO2013075241 A1 also describes a method of using ethylene-propylene-diene rubber (EPDM) or a random ethylene-propylene copolymer (EP-RACO) as a compatibilizer for recycling plastic joints.
    [009] However, until now, most compatibilization efforts require the presence of a high molecular weight component, thus limiting the fluidity of the final composition.
    [0010] Accordingly, it is an object of the present invention to obtain PP/PE joints that show high stiffness as well as high impact strength and thermal deflection temperature, while showing good fluidity and processability. A further objective of the present invention is to improve both the mechanical properties and the processability of recycled PP/PE joints simultaneously, to make them suitable for use in different applications.
    [0011] The finding of the present invention is that with the special combination of a high flux polypropylene and a heterophasic polyolefin composition which is a compatibilizer, a high flux PP/PE composition is obtained with an optimal balance of stiffness and impact, as well as a higher thermal deflection temperature.
    [0012] Accordingly, the present invention is directed to a polymer composition comprising a) 10 to 50% by weight of a polymer joint (A) comprising 30 to 70% by weight of polypropylene (A1) and 70 to 30% by weight of polyethylene (A2), b) 47 to 90% by weight of a polypropylene (B) having an MFR2 melt flow rate (230°C) measured in accordance with ISO 1133 of not less than 50 g /10 min, and c) 3 to 25% by weight of a Compatibilizer (C) which is a heterophasic polyolefin composition comprising 55 to 90% by weight of a matrix (C1) which is a polypropylene and 45 to 10% by weight of an elastomer (C2) which is a copolymer of ethylene and propylene or alpha-olefin C4 to C10 with a glass transition temperature Tg measured in accordance with ISO 6721-7 below -25 °C and an intrinsic viscosity measured in accordance with to DIN ISO 1628/1 at 135 °C of at least 3.0 dl/g, wherein the polymer composition has an MFR2 melt flow rate (230 °C) measured in accordance with with the ISO 1133 standard greater than 25 g/10 min.
    [0013] Additionally, the present invention, in another aspect, is directed to an article comprising the polymeric composition as defined in this application. Preferably, the article is a film or molded article, more preferably, the article is a molded article, such as bottles, caps and automotive parts.
    [0014] However, a further aspect of the present invention is the use of the polymeric composition as defined in this application in packaging applications, for example: in the production of flexible packaging, containers and household items such as bottles and caps.
    [0015] In the following, the invention is defined in more detail. The polymeric composition
    [0016] It is essential that the polymeric composition, according to this invention, comprises a polymer union (A), a polypropylene (B) and a Compatibilizer (C) which is a heterophasic polyolefin composition, as three main components.
    [0017] Accordingly, the polymeric composition comprising 10 to 50% by weight, preferably 15 to 45% by weight, more preferably 20 to 40% by weight of a polymer joint (A) 47 to 90% by weight, preferably 50 to 85% by weight, more preferably 50 to 80% by weight of a polypropylene (B) and 3 to 25% by weight, preferably 4 to 20% by weight, more preferably 5 to 15% by weight of a Compatibility (C).
    [0018] The union of polymer (A), polypropylene (B) and Compatibilizer (C) is therefore generally different.
    [0019] It is also essential that the polymeric composition according to this invention has an MFR2 melt flow rate (230°C), measured in accordance with ISO 1133, greater than 25 g/10 min, preferably in the range of 26 to 80 g/10 min, more preferably in the range of 30 to 60 g/10 min.
    [0020] It has surprisingly been found that the polymeric composition described in the present invention shows a significantly increased thermal deflection temperature (HDT) and simultaneously improved impact strength and tensile modulus, compared to bonding polymers (A) without polypropylene (B) and Compatibility (C).
    [0021] According to a preferred embodiment, the polymeric composition according to the present invention has a thermal deflection temperature (HDT), measured in accordance with ISO 75B, of at least 5°C, preferably at least 7°C. °C, more preferably, at least 10 °C higher than the HDT of the polymer bond (A). The difference will normally not exceed 30 °C.
    [0022] Additionally, in another preferred embodiment, the polymeric composition has (i) a Charpy Cut Impact Strength, measured in accordance with ISO 179-1eA at 23°C, of at least 15%, preferably at least 20%, more preferably at least 25% higher than the polymer bond (A), and at the same time (ii) a Tensile Modulus, measured in accordance with ISO527-2, of at least 20%, of preferably at least 25%, more preferably at least 30% higher than the polymer bond (A). The difference in both impact strength and modulus will normally not exceed 200%.
    [0023] According to a specific embodiment, the polymeric composition may additionally comprise inorganic or organic reinforcements such as talc, glass fibers or wood fibers.
    [0024] Thus, optionally, the polymeric composition according to the present invention may additionally comprise inorganic or organic reinforcing agents, usually fillers. The total amount of inorganic or organic strengthening agents is preferably from 1 to 20% by weight, more preferably from 2 to 15% by weight based on the total amount of the polymeric composition.
    [0025] Suitable inorganic or organic fillers are talc, chalk, clay, mica, clay or glass fibers, wood fibers and carbon fibers up to a length of 6 mm.
    [0026] The mean particle size d50 of the filler material can be chosen between 0.5 to 40 µm, preferably between 0.7 to 20 µm and more preferably between 1.0 to 15 µm.
    [0027] The average (or median) particle size is the diameter of the particles where 50% of the particles are larger and 50% are smaller. It is denoted as d50 or d50.
    [0028] In principle, this value can be determined by particle measurement techniques, for example, measurement techniques based on the principle of luminous diffraction.
    [0029] Other techniques for determining particle sizes include, for example, granulometry, in which a uniform suspension of a small amount of the powder to be investigated is prepared in a suitable dispersion medium and is then exposed to sedimentation. The percentage distribution of particle sizes can be estimated from the correlation between size and density of spherical particles and their sedimentation rate, as determined by Stokes' law and sedimentation time. Other methods for determining particle size include microscopy, electron microscopy, sieve analysis, sedimentation analysis, surface density determination and the like.
    [0030] The particle size data appearing in the present specification were obtained in a well known manner with a standard test procedure employing Stokes' Law of Sedimentation by settling the particulate material in a fully dispersed condition in an aqueous medium using a Sedigraph 5100 machine as supplied by Micromeritics Instruments Corporation, Norcross, GA, USA (tel: +1 770 662 3620; website: www.micromeritics.com), referred to in this application as the “Micromeritics Sedigraph 5100 unit”.
    [0031] Preferably, talc, glass fibers or wood fibers, more preferably, talc, are used as a filler.
    [0032] Before adding talc, it can be treated with various surface treatment agents such as organic titanate coupling agents, silane coupling agents, fatty acids, fatty acid metal salts, fatty acid esters and the like , in a manner known in the prior art. Talc can also be added without surface treatment. Preferably, the talc is added without surface treatment.
    [0033] In the following, the individual components of the polymer composition are described in more detail. The joining of polymers (A)
    [0034] The joining of polymers (A) in the polymeric composition comprises 30 to 70% by weight of polypropylene (A1) and 70 to 30% by weight of polyethylene (A2).
    [0035] In a preferred embodiment, Component A) is a recycled material, which is recovered from residual plastic material derived from post-consumer and/or post-industrial waste.
    [0036] The polypropylene (A1) may comprise one or more polymeric materials selected from the following: I) isotactic or primarily isotactic propylene homopolymers; II) isotactic random copolymers of propylene with ethylene and/or C4-C10 alpha-olefins, preferably ethylene and/or C4-C8 alpha-olefins, such as, for example, 1-butene, 1-hexene, 1-octene, 4-methyl-1-pentene, in which the total comonomer content varies from 0.05 to 20% by weight, or mixtures of said copolymers with isotactic or mainly isotactic propylene homopolymers; III) heterophasic copolymers comprising an isotactic propylene homopolymer as (I) or propylene random copolymers as (II) and an elastomeric fraction comprising copolymers of ethylene with propylene and/or a C4-C8 α-olefin, optionally containing minor amounts of a diene, such as butadiene, 1,4-hexadiene, 1,5-hexadiene, ethylidene-1-norbornene.
    [0037] For example, a polypropylene suitable for use as polypropylene (A1) may have a density of from 0.895 to 0.920 g/cm3, preferably from 0.900 to 0.915 g/cm3 and more preferably from 0.905 to 0.915 g/cm3 , as determined in accordance with ISO 1183, and a melt flow rate (MFR) of 0.1 to 30 g/10 min, preferably 0.5 to 25 g/10 min, and alternatively , from 1.0 to 20 g/10 min, as determined in accordance with ISO 1133 (at 230 °C; 2.16 kg load). Typically, the melting temperature of polypropylene (A1) is within the range of 135 to 170°C, preferably in the range of 140 to 168°C, more preferably in the range of 142 to 166°C. In case it is a propylene homopolymer like item (I) above, it will generally have a melting temperature of from 150 to 170°C, preferably from 155 to 168°C, and more preferably from 160 to 165°C , as determined by differential scanning calorimetry (DSC) in accordance with ISO 11357-3. In case it is a propylene random copolymer according to item (II) above, it will generally have a melting temperature of from 130 to 162°C, preferably from 135 to 160°C, and more preferably from 140 to 158° C as determined by DSC in accordance with ISO 11357-3.
    [0038] Preferably, the polypropylene (A1) does not comprise a heterophasic copolymer according to item (III) above.
    [0039] The polyethylene (A2) is preferably a high density polyethylene (HDPE) or a linear low density polyethylene (LLDPE) or a long chain branched low density polyethylene (LDPE).
    [0040] The content of polyethylene comonomer (A2) is generally below 50% by weight, preferably below 25% by weight, and most preferably below 15% by weight.
    [0041] In this application, a HDPE suitable for use as polyethylene (A2) in this description has a density determined in accordance with ISO 1183 equal to or greater than 0.941 g/cm3, preferably from 0.941 to 0.965 g/cm3, plus preferably from 0.945 to 0.960 g/cm 3 . In one embodiment, the HDPE is an ethylene homopolymer. An HDPE suitable for use as A-2) in this description may generally have an MFR determined by ISO 1133 (at 190 °C, 2.16 kg load), from 0.01 g/10 min to 50 g/10 min, preferably from 0.1 to 30 g/10 min, such as from 0.5 to 20 g/10 min.
    [0042] HDPE can also be a copolymer, for example, a copolymer of ethylene with one or more alpha-olefin monomers such as propylene, butene, hexene, etc.
    [0043] An LLDPE suitable for use as polyethylene (A2) in this description may generally have a density as determined by ISO 1183, from 0.900 to 0.920 g/cm3, or from 0.905 to 0.918 g/cm3, or from 0.910 to 0.918 g/cm3 and an MFR determined by ISO 1133 (at 190 °C, 2.16 kg load), from 0.01 to 50 g/min, or from 0.1 to 30 g/10 min, such as from 0 .5 to 20 g/10 min. LLDPE is a copolymer, for example, a copolymer of ethylene with one or more alpha-olefin monomers such as propylene, butene, hexene, etc.
    [0044] An LDPE suitable for use as A-2) in this description may generally have a density as determined by ISO 1183, from 0.915 to 0.935 g/cm3, and an MFR determined by ISO 1133 (190°C; 2 .16 kg), from 0.01 to 20 g/min. LDPE is an ethylene homopolymer.
    [0045] The melting temperature of component A-2) is preferably within the range of 100 to 135°C, more preferably in the range of 105 to 132°C.
    [0046] In a preferred embodiment, the polymeric bond A) is a recycled material, which is recovered from residual plastic material derived from post-consumer and/or post-industrial waste.
    [0047] These post-consumer and/or post-industrial waste can be derived, among others, from electrical and electronic equipment (WEEE) or end-of-life vehicles (ELV) or differentiated waste collection schemes, such as German DSD system, the Austrian ARA system and the Italian “Raccolta Differenziata” system.
    [0048] The unions can be PP-rich or PE-rich materials or unions with approximately equivalent amounts of PP and PE.
    [0049] The term “residue” is used to designate polymeric materials that derive from at least one processing cycle in manufactured articles, as opposed to virgin polymers. As mentioned above, all types of polyethylene, preferably HDPE, LLDPE or LDPE, or polypropylene may be present.
    [0050] Such recyclates are commercially available, for example, from Corpela (Italian Consortium for the collection, recovery, recycling of plastic waste packaging), Resource Plastics Corp. (Brampton, ON), Kruschitz GmbH, Plastics and Recycling (AT), Vogt Plastik GmbH (DE) etc.
    [0051] The amounts of polypropylene (A1) and polyethylene (A2) can be from 30 to 70% by weight of polypropylene (A1) and from 70 to 30% by weight of polyethylene (A2), preferably 40 to 60 % by weight of polypropylene (A1) and 60 to 40% by weight of polyethylene (A2).
    [0052] The polymer bond (A) in the present polymeric composition preferably has an MFR (230°C, 2.16 kg, ISO 1133) of 0.2 to 50 g/10 min, preferably of 0 .5 to 45 g/10 min, more preferably 1.0 to 40 g/10 min. Polypropylene (B)
    [0053] The polypropylene (B) in the present polymer composition is distinguished especially by a rather high melt flow rate. Consequently, polypropylene (B) has a measured melt flow rate MFR2 (230°C) according to ISO 1133 of not less than 50 g/10 min, preferably in the range of 50 to 1000 g/10 min, more preferably in the range 55 to 500 g/10 min, even more preferably in the range 60 to 200 g/10 min.
    [0054] In a preferred embodiment of this invention, the polypropylene (B) is a heterophasic polyolefin composition comprising (a) a matrix (B1) being a propylene polymer (b) an elastomer (B2) being a copolymer comprising units derived from - propylene and - ethylene and/or C4 to C20 α-olefin.
    [0055] Generally, in the present invention, the expression "heterophasic" indicates that the elastomer is (finely) dispersed in the matrix. In other words, the elastomer forms the inclusion in the matrix. Thus, the matrix contains (finely) dispersed inclusions that are not part of the matrix and said inclusions contain the elastomer. The term "inclusion", according to this invention, should preferably indicate that the matrix and the inclusion form different phases within the heterophasic polypropylene, said inclusions being, for example, visible by high resolution microscopy, such as electron microscopy. or force scanning microscopy.
    [0056] Heterophasic polyolefin compositions are generally presented by a cold xylene soluble fraction (XCS) and a cold xylene insoluble fraction (XCI).
    [0057] For the purpose of the present application, the cold xylene soluble fraction (XCS) of heterophasic polyolefin compositions is essentially identical to the elastomer of said heterophasic polyolefin compositions.
    [0058] Consequently, when talking about the intrinsic viscosity and ethylene content of the elastomer of heterophasic polyolefin compositions, it is understood the intrinsic viscosity and ethylene content of the cold xylene soluble fraction (XCS) of said polyolefin compositions heterophasic.
    [0059] Note that the matrix (B1) and elastomer (B2) in polypropylene (B), as well as matrix (C1) and elastomer (C2) in Compatibility (C) described below, apply to the above description .
    [0060] Consequently, the content of the matrix (B1), i.e. the insoluble content of cold xylene (XCI), in the polypropylene (B), which is a heterophasic polyolefin composition, is preferably in the range of 75.0 to 93.0% by weight, more preferably in the range of 77.0 to 91.0% by weight, such as 78.0 to 89.0% by weight.
    [0061] On the other hand, the elastomer (B2), that is, the soluble content in cold xylene (XCS), in the polypropylene (B), which is a heterophasic polyolefin composition, is preferably in the range of 7 .0 to 25.0% by weight, more preferably in the range of 9.0 to 23.0% by weight, such as in the range of 11.0 to 22.0% by weight.
    [0062] The first component of Polypropylene (B) as a heterophasic polyolefin composition is the matrix (B1).
    [0063] Polypropylenes suitable for use as a matrix (B1) may include any type of isotactic or predominantly isotactic polypropylene homopolymer or random copolymer known in the art. Thus, the polypropylene can be a propylene homopolymer or an isotactic random copolymer of propylene with ethylene and/or C4 to C8 alpha-olefins, such as, for example, 1-butene, 1-hexene or 1-octene, where the total comonomer content varies from 0.05 to 10% by weight.
    [0064] In addition, and preferably, the polypropylene matrix (B2) has a very high melt flow rate. Consequently, it is preferred that, in the present invention, the polypropylene matrix (B2), i.e. the cold xylene insoluble fraction (XCI) of the polypropylene (B), has an MFR2 (230°C) measured in accordance with the ISO1133 standard, from 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 140.0 to 600.0 g/10 min, as in the range of 150.0 to 500.0 g/10 min.
    [0065] Additionally, the polypropylene matrix (B1) can be multimodal or bimodal in view of molecular weight.
    [0066] The expression "multimodal" or "bimodal" used throughout the present invention refers to the modality of the polymer, that is, ■ the shape of its molecular weight distribution curve, which is the graph of the molecular weight fraction as a function of its molecular weight, and/or ■ the shape of its comonomer content distribution curve, which is the graph of the comonomer content versus the molecular weight of the polymer fractions.
    [0067] The second component of Polypropylene (B) as a heterophasic polyolefin composition is elastomer (B2).
    [0068] The elastomer (B2) preferably comprises consists of units derived from (i) propylene and (ii) ethylene and/or at least one other C4 to C20 α-olefin, such as C4 to C10 α-olefin, more preferably , units derived from (i) propylene and (ii) ethylene and at least one other α-olefin selected from the group consisting of 1-butene, 1-pentene, 1-hexene, 1-heptene and 1-octene. The elastomeric copolymer (E1) may additionally contain units derived from a conjugated diene, such as butadiene, or an unconjugated diene, however, it is preferred that the elastomeric copolymer consists of units derived from (i) propylene and (ii) ethylene and/or only C4 to C20 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 dihydro-ocimene and single-ring alicyclic dienes such as 1,4-cyclohexadiene, 1, 5-cyclooctadiene, 1,5-cyclododecadiene, 4-vinyl cyclohexene, 1-allyl-4-isopropylidene-cyclohexane, 3-allyl cyclopentene, 4-cyclohexene and 1-isopropenyl-4-(4) -butenyl)cyclohexane. Also suitable are bridged ring or multi-fused alicyclic dienes including tetrahydroindene, methyltetrahydroindene, dicyclopentadiene, bicyclo(2,2,1)hepta-2,5-diene, 2-methyl bicycloheptadiene 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 dicyclopentadiene.
    [0069] Consequently, the elastomer (B2) comprises at least units derivable from propylene and ethylene and may comprise other units derivable from an additional α-olefin as defined in the previous paragraph. However, it is particularly preferred that the elastomer (B2) comprises only units derivable from propylene and ethylene and optionally a conjugated diene, such as a butadiene, or an unconjugated diene as defined in the previous paragraph, such as 1,4-hexadiene. Thus, a polymer of unconjugated ethylene propylene diene monomer (EPDM) and/or an ethylene propylene rubber (EPR) as elastomer (B2) is especially preferred, the latter being more preferred.
    [0070] Like the matrix (B1), the elastomer (B2) can be unimodal or multimodal, such as bimodal. As for the definition of unimodal and multimodal, as bimodal, it is referred to in the definition above.
    [0071] In the present invention, the content of units derivable from propylene in the elastomer (B2) is equivalent to the propylene content detectable in the cold xylene soluble fraction (XCS). Accordingly, the detectable propylene in the cold xylene soluble fraction (XCS) ranges from 45.0 to 75.0% by weight, more preferably from 40.0 to 70.0% by weight. Thus, in a specific embodiment, the elastomer (B2), i.e. the cold xylene soluble fraction (XCS), comprises from 25.0 to 65.0% by weight, more preferably from 30.0 to 60 .0% by weight of units derived from ethylene. Preferably, the elastomer (B2) is a polymer of unconjugated ethylene propylene diene monomer (EPDM) or an ethylene propylene rubber (EPR), the latter being especially preferred, with a propylene and/or ethylene content as defined herein. paragraph.
    [0072] A further preferred requirement of the present invention is that the intrinsic viscosity (IV) of the cold xylene soluble fraction (XCS) of polypropylene (B), which is a heterophasic polyolefin composition, is quite low. Accordingly, it is recognized that the intrinsic viscosity of the cold xylene soluble fraction (XCS) of polypropylene (B), which is a heterophasic polyolefin composition, is less than 3.5 dl/g, more preferably not greater than 3, 4 dl/g. Even more preferably, the intrinsic viscosity of the cold xylene soluble fraction (XCS) of polypropylene (B), which is a heterophasic polyolefin composition, is in the range of 1.8 to 3.5 dl/g, more preferably, in the range of 1.8 to 3.5 dl/g. range from 1.9 to 3.4 dl/g, such as 2.0 to 3.4 dl/g. Intrinsic viscosity is measured according to ISO 1628 in decalin at 135°C.
    [0073] Preferably, the propylene content of polypropylene (B) is from 85.0 to 96.0% by weight, more preferably from 88.0 to 94.0% by weight, based on the total weight of polypropylene (B), more preferably, based on the amount of matrix (B1) and elastomeric copolymer (B2) together, in case the polypropylene (B) is a heterophasic polyolefin composition as defined above. The compatibilizer (C)
    [0074] A compatibilizer is acting as an interface in the composition of polypropylene and polyethylene to improve the compatibility of different components.
    [0075] Accordingly, the Compatibilizer (C) of the polymeric composition according to the invention is a heterophasic polyolefin composition comprising (i) 55 to 90% by weight of a matrix (C1) being a polypropylene and (ii) 45 at 10% by weight of an elastomer (C2) being a copolymer of ethylene and propylene or a C4 to C10 alpha olefin with a Tg measured with DMTA according to ISO 6721-7 below 25°C and an intrinsic viscosity ( measured in decalin according to DIN ISO 1628/1 at 135 °C) of at least 3.0 dl/g.
    [0076] Polypropylenes suitable for use as a matrix (C1) may include any type of isotactic or predominantly isotactic polypropylene homopolymer or random copolymer known in the art. Thus, the polypropylene can be a propylene homopolymer or an isotactic random copolymer of propylene with ethylene and/or C4 to C8 alpha-olefins, such as, for example, 1-butene, 1-hexene or 1-octene, where the total comonomer content varies from 0.05 to 10.0% by weight.
    [0077] A polypropylene suitable for use as a matrix (C1) may have a density of from 0.895 to 0.920 g/cm3, preferably from 0.900 to 0.915 g/cm3 and more preferably from 0.905 to 0.915 g/cm3, as determined according to the ISO 1183 standard.
    [0078] Normally, the matrix (C1) has a melting temperature of from 130 to 170°C, preferably from 135 to 168°C and more preferably from 140 to 165°C.
    [0079] In case it is a propylene homopolymer, it will have a melting temperature of 150 to 170 °C, preferably 155 to 168 °C, such as 160 to 165 °C, as determined by differential scanning calorimetry ( DSC), according to ISO 11357-3. If it is a random copolymer of propylene with ethylene and/or C4 to C8 alpha-olefins, it will have a melting temperature of 130 to 162 °C, preferably 135 to 160 °C, such as 140 to 158 °C , as determined by DSC, in accordance with ISO 11357-3.
    [0080] The melt flow rate of the matrix melt (C1) ranges from 1.0 to 300.0 g/10 min, preferably from 2.0 to 200.0 g/10 min, and most preferably from 2.0 to 200.0 g/10 min. from 4.0 to 150.0 g/10 min, for example 4.5 to 150.0 g/10 min as determined in accordance with ISO 1133 (230°C, 2.16 kg). In one embodiment, the die melt flow rate (C1) ranges from 4.0 to 75.0 g/10 min as determined in accordance with ISO 1133 (230°C, 2.16 kg).
    [0081] As the (C2) elastomer, a copolymer of ethylene and propylene or a C4 to C10 alpha-olefin is used. The alpha-olefin is preferably butene, hexene or octene, more preferably butene or octene, and most preferably octene.
    [0082] Elastomer (C2) copolymers have a glass transition temperature Tg (measured with DMTA according to ISO 6721-7) below -25°C, preferably below -28°C, plus preferably below -30°C, more preferably below -45°C and an intrinsic viscosity (measured in decalin according to DIN ISO 1628/1 at 135°C) of at least 3.0 dl/ g, preferably at least 3.1 dl/g, more preferably at least 3.2 dl/g and even more preferably at least 3.3 dl/g.
    [0083] The glass transition temperature Tg (measured with DMTA, according to ISO 6721-7) of the elastomer (C2) is usually -65°C or above, preferably -60°C or above and, more preferably -58°C or above.
    [0084] The intrinsic viscosity (measured in decalin according to DIN ISO 1628/1 at 135 °C) of elastomer (C2) is generally 10.0 or less, preferably 9.0 or less, and more preferably 8.5 or less.
    [0085] In case the elastomer (C2) is a copolymer of ethylene and propylene, it has an ethylene content of from 10 to 55% by weight, preferably from 15 to 50% by weight, and more preferably from 18 to 48% by weight and more preferably from 20 to 46% by weight.
    [0086] In case the elastomer (C2) is a copolymer of ethylene and a C4 to C10 alpha-olefin, it has an ethylene content of 60 to 95% by weight, preferably 65 to 90% by weight and , more preferably, from 70 to 85% by weight.
    [0087] Note that elastomer (C2) is different from polyethylene (A2). Typically, elastomer (C2) differs from polyethylene (A2) in terms of its comonomer contents determined as a percentage by weight. Preferably, the comonomer content of polyethylene (A2) is lower compared to the comonomer content of the elastomer (C2), more preferably, the comonomer content of polyethylene (A2) is at least 2 percentage points lower compared to the content of (C2) elastomer comonomer and, more preferably, the polyethylene (A2) comonomer content is at least 5 percentage points lower compared to the (C2) elastomer comonomer content.
    [0088] In the heterophasic polyolefin composition suitable as the Compatibilizer (C), the matrix (C1) is present in an amount of 55 to 90% by weight, preferably in an amount of 60 to 88% by weight, and more preferably in an amount of 65 to 85% by weight and more preferably in an amount of 65 to 80% by weight and the elastomer (C2) is present in an amount of 10 to 45% by weight, preferably in in an amount of 12 to 40% by weight, even more preferably in an amount of 15 to 35% by weight, and more preferably in an amount of 20 to 35% by weight.
    [0089] Compatibilizer (C) preferably has an ethylene homopolymer content of not more than 10% by weight, more preferably not more than 5% by weight, and most preferably Compatibilizer (C) is free from ethylene homopolymers.
    [0090] The heterophasic polyolefin composition suitable as the Compatibilizer (C) can be prepared by mechanically joining the matrix (C1) and the elastomer (C2).
    [0091] Polypropylene homopolymers or copolymers suitable as a matrix (C1) for mechanical bonding are commercially available, INTER ALIA, from Borealis AG or can be prepared by known processes, such as in a one-stage or two-stage polymerization process. stages comprising a loop reactor or a loop reactor with a subsequent gas phase reactor, in the presence of highly stereospecific Ziegler-Natta catalysts or single-site catalysts such as metallocene catalysts known to those skilled in the art.
    [0092] Suitable copolymers such as (C2) elastomer for mechanical bonding may be any copolymer of ethylene and propylene or ethylene and alpha olefin C4 to C10 with the properties defined above, which may be commercially available from INTER ALIA from Borealis AG (AT) under the trademark Queo®, from DOW Chemical Corp (USA) under the trade name Engage®, or from ENI SpA (IT).
    [0093] Alternatively, these copolymers can be prepared by known processes, in a one-stage or two-stage polymerization process, comprising solution polymerization, slurry polymerization, gas phase polymerization or combinations thereof, in the presence of Ziegler catalysts - Highly stereospecific natta, suitable vanadium oxide catalysts or single site catalysts such as metallocene or restricted geometry catalysts known to those skilled in the art.
    [0094] In another embodiment, the heterophasic polyolefin composition suitable as the Compatibilizer (C) can be prepared by sequential polymerization, comprising at least two reactors in which first the matrix (C1) is produced and secondly the elastomer (C2) ) is produced in the presence of the matrix (C1).
    [0095] A preferred sequential polymerization process comprises at least one closed loop reactor and at least one subsequent gas phase reactor. This process can have up to 3 gas phase reactors.
    [0096] The matrix (C1), which is polyethylene, is produced first, that is, in the loop reactor and subsequently transferred to at least one gas-phase reactor, where the polymerization of ethylene, propylene or a C4 to C10 alpha olefin or mixtures thereof occurs in the presence of the matrix (C1). It is possible that the polymer produced in this way is transferred to a second reactor in the gas phase.
    [0097] An additional possibility is that the matrix (C1) is produced in the closed loop reactor and the first reactor in the subsequent gas phase. The matrix (C1) is then transferred to at least the second gas-phase reactor where the polymerization of ethylene and propylene or a C4 to C10 alpha-olefin or mixtures thereof takes place in the presence of the matrix (C1). It is possible that the polymer produced in this way will be transferred to a third reactor in the gas phase.
    [0098] In a specific embodiment, the heterophasic polyolefin composition suitable as the Compatibilizer (C) is prepared by sequential polymerization comprising at least four reactors in which first the matrix polypropylene (C1) is produced in the closed loop reactor and the first reactor in subsequent gas phase. The matrix (C1) is then transferred to the second gas phase reactor where the polymerization of ethylene and propylene or a C4 to C10 alpha-olefin or mixtures thereof takes place in the presence of the matrix (C1). The polymer produced in this way is then transferred to the third gas-phase reactor where the polymerization of ethylene and propylene or a C4 to C10 alpha-olefin or mixtures thereof takes place in the presence of the product obtained in the second gas-phase reactor.
    [0099] The polymerization takes place in the presence of highly stereospecific Ziegler-Natta catalysts or single-site catalysts such as metallocene catalysts, known to those skilled in the art.
    [00100] A suitable sequential polymerization process is, INTER ALIA, the Borstar® process from Borealis AG.
    [00101] Preferably, the heterophasic polyolefin composition such as Compatibilizer (C) is produced by sequential polymerization if the elastomer (C2) is an ethylene-propylene copolymer.
    [00102] If the (C2) elastomer is a C4 to C10 ethylene alpha-olefin, the heterophasic polyolefin composition such as the Compatibilizer (C) is preferably produced by mechanical joining. EXAMPLES measurement methods
    [00103] MFR was measured according to ISO 1133 with a load of 2.16 kg at 230 °C for pure PP components and all compositions.
    [00104] Charpy Cut Impact Strength was determined in accordance with ISO 179 1eA at 23 °C using injection molded 80x10x4 mm3 test bars in accordance with EN ISO 1873-2.
    [00105] The Traction Module was determined according to ISO 527-2 (crosshead speed = 50 mm/min; 23 °C) using injection molded samples as described in EN ISO 1873-2 (shape of dog bone, 4 mm thick).
    [00106] The Thermal Deflection Temperature (HDT) was determined in accordance with ISO 75 B with a load of 0.45 MPa using 80x10x4 mm3 injection molded test bars in accordance with EN ISO 1873-2.
    [00107] The content of cold xylene solubles (XCS) was determined at 25 °C according to ISO 16152; first edition; 2005-07-01.
    [00108] The intrinsic viscosity (IV) was measured according to DIN ISO 1628/1, October 1999 (in decalin at 135 °C).
    [00109] The glass transition temperature Tg and the storage modulus G' were determined by dynamic mechanical analysis (DMTA) according to ISO 6721-7. Measurements were made in torsion mode on compression molded samples (40x10x1 mm3) between -100 °C and + 150 °C with a heating rate of 2 °C/min and a frequency of 1 Hz. While the Tg was determined from the loss angle curve (tan(δ)), the storage modulus curve (G') was used to determine the temperature for a G' of 40 MPa representing a measure for the resistance to thermal deflection.
    [00110] Melting temperature (Tm) and crystallization temperature (Tc) were measured with Mettler TA820 Differential Scanning Calorimetry (DSC) on 5 to 10 mg samples. DSC is performed according to ISO 11357-3:1999 in a heat/cold/heat cycle with a scan rate of 10 °C/min in the temperature range of +23 to + 210 °C. The crystallization temperature and the crystallization heat (Hc) are determined from the cooling step, while the melting temperature and the fusion heat (Hf) are determined from the second heating step.
    [00111] The comonomer content, especially the ethylene content, is measured with Fourier Transform Infrared Spectroscopy (FTIR) calibrated with 13C-NMR. By measuring the ethylene content in the polypropylene, a thin film of the sample (thickness about 250 μm) was prepared by hot pressing. The area of the absorption peaks 720 and 733 cm-1 for propylene and ethylene copolymers was measured with a Perkin Elmer FTIR 1600 spectrometer.
    [00112] The polyethylene content of the recycle was determined using the DSC technique described above to determine the melting temperature (Tm) and the crystallization temperature (Tc).
    [00113] For the recycled, the polyethylene content was calculated from the enthalpy of melting of PE in DSC (Hm(PE)) associated with the lower melting point for the composition (Tm(PE)) in the range of 110 to 130 °C For the determination of the present invention for fully crystalline PE, an enthalpy of melting of 298 J/g and an average degree of crystallinity of 50% was assumed. Examples Materials used Polymer Union (A)
    [00114] Dipolen S is a blend of recycled polymers comprising polyethylene and polypropylene obtained from mtm plastics GmbH, Niedergebra, Germany and has a polyethylene content of 40% by weight determined by DSC analysis. Melting points determined by DSC were 162°C (PP) and 128°C (PE). Polypropylene (B)
    [00115] PP1: Polypropylene (PP1) is a BJ998MO heterophasic polypropylene copolymer that is commercially available from Borealis AG.
    [00116] PP2: Polypropylene (PP2) is a BJ400HP heterophasic polypropylene copolymer that is commercially available from Borealis AG.
    [00117] PP3: Polypropylene (PP3) is a BJ368MO heterophasic polypropylene copolymer that is commercially available from Borealis AG.
    [00118] The characterization of PP1 to PP3 is summarized in Table 1 Table 1: characterization of PP1 to PP3
    Compatibility (C) HECO-1 heterophasic copolymer:
    [00119] HECO-1 was produced in a Borstar PP pilot plant with a prepolymerization reactor, a circulating slurry slurry reactor and a gas phase reactor.
    [00120] The catalyst used for the preparation of HECO-1 was produced as follows: First, 0.1 mol of MgCl2 x 3 EtOH was suspended under inert conditions in 250 ml of decane in a reactor at atmospheric pressure. The solution was cooled to -15 °C and 300 ml of cold TiCl4 were added while the temperature was maintained at said level. Then, the temperature of the suspension was slowly increased to 20 °C. At this temperature, 0.02 mol of dioctylphthalate (DOP) was added to the aqueous slurry. After the addition of the phthalate, the temperature was raised to 135°C for 90 minutes and the suspension was allowed to stand for 60 minutes. Then, another 300 ml of TiCl4 was added and the temperature was maintained at 135 °C for 120 minutes. After that, the catalyst was filtered from the liquid and washed six times with 300 ml of heptane at 80°C. Then, the solid catalyst component was filtered and dried. (Ti content: 1.9% by weight and Mg content: 22.0% by weight). The Catalyst and its preparation concept are described in general, for example, in patent publications EP491566, EP591224 and EP586390.
    [00121] The catalyst was used in combination with dicyclopentyldimethoxysilane [Si(OCH3)2(cyclopentyl)2] as external donor (DE) and triethylaluminum (TEAL) as activator and scavenger in the ratios indicated in Table 2. The catalyst was modified by polymerization of a vinyl compound in the presence of the catalytic system. The respective process is described in EP 1 028 984 and EP 1 183 307. The specific reaction parameters can be seen in Table 2. Table 2: Preparation of HECO-1 heterophasic copolymer

    [00122] The polymeric bonding compositions of polymer (A), polypropylene (B) and Compatibility (C) were prepared in a Coperion ZSK 25 twin rotary screw extruder equipped with a mixing screw configuration with an L/D ratio of 25. A melt temperature of 200 to 220°C was used during mixing, solidifying the melt strands in a water bath followed by pelletizing the strand.
    [00123] For reasons of good comparison, CE5 is shown in this application to be BH345MO commercially available from Borealis AG with a recognized good combination of high rigidity, good flow properties and good impact resistance. It has an MFR of 45 g/10 min and a density of 0.905 g/cm3.
    [00124] The quantities of the different components and the mechanical properties of the inventive examples and comparative examples can be seen in Table 3. Table 3: Composition and mechanical properties of IE 1 to IE5 and CE1 to CE5
    权利要求:
    Claims (14)
    [0001]
    1. Polymeric composition, characterized in that it comprises a) 10 to 50% by weight of a polymer joint (A) comprising 30 to 70% by weight of polypropylene (A1) and 70 to 30% by weight of polyethylene (A2) , b) 47 to 85% by weight of a polypropylene (B) having an MFR2 melt flow rate (230°C) measured in accordance with ISO 1133 not less than 50 g/10 min, and c) 3 to 25% by weight of a Compatibilizer (C) being a heterophasic polyolefin composition comprising 55 to 90% by weight of a matrix (C1) being a polypropylene and 45 to 10% by weight of an elastomer (C2) being a copolymer of ethylene and propylene or alpha-olefin C4 to C10 with a glass transition temperature Tg measured in accordance with ISO 6721-7 below -25 °C and an intrinsic viscosity measured in accordance with DIN ISO 1628/1 to 135 °C of at least 3.0 dl/g, wherein the polymer composition has an MFR2 melt flow rate (230 °C) measured in accordance with ISO 1133 greater than 2 5 g/10 min.
    [0002]
    2. Polymer composition according to claim 1, characterized in that the thermal deflection temperature (HDT), measured in accordance with ISO 75B, of said polymeric composition is at least 5 °C higher than the HDT of the union of polymers (A).
    [0003]
    3. Polymer composition according to claim 1 or 2, characterized in that said polymeric composition has (i) a Charpy Cut Impact Strength measured in accordance with ISO 179-1eA at 23 °C at least 15% higher than the polymer bond (A) and at the same time (ii) a Tensile Modulus measured in accordance with ISO527-2 of at least 20% greater than the polymer bond (A).
    [0004]
    4. Polymer composition according to any of the previous claims 1 to 3, characterized in that the polymer union (A) is a recycled material, which is recovered from residual plastic material derived from post-consumer and/or post-consumer waste. industrial.
    [0005]
    5. Polymer composition according to any of the previous claims 1 to 4, characterized in that the polypropylene (A1) has an MFR2 melt flow rate (230 °C) measured in accordance with ISO 1133 of 0 .1 to 30.0 g/10 min.
    [0006]
    6. Polymer composition according to any one of the previous claims 1 to 5, characterized in that the polypropylene (B) is a heterophasic polyolefin composition that has a cold xylene soluble content (XCS), measured according to the ISO 6427 standard in the range of 7.0 to 25.0% by weight.
    [0007]
    7. Polymer composition according to any of the previous claims 1 to 6, characterized in that the intrinsic viscosity (VI), measured in accordance with ISO 1628-1 (decalin), of the cold xylene soluble fraction (XCS ) of polypropylene (B) which is a heterophasic polyolefin composition is below 3.5 dl/g.
    [0008]
    8. Polymer composition according to any one of the previous claims 1 to 7, characterized in that the MFR2 melt flow rate (230 °C), measured in accordance with ISO 1133, of the polypropylene fraction ( B) soluble in cold xylene (XCI), being a heterophasic polyolefin composition, is in the range of 100.0 to 1500.0 g/10 min.
    [0009]
    9. Polymer composition according to any one of the preceding claims 1 to 8, characterized in that the polypropylene (B) has (i) a total propylene content of 85.0 to 96.0% by weight and/or ( ii) a propylene content in the cold xylene soluble fraction (XCS) of 45.0 to 75.0% by weight.
    [0010]
    10. Polymer composition according to any one of the previous claims 1 to 9, characterized in that the Compatibilizer (C) is selected from (i) a union in a reactor obtained by a sequential polymerization process in at least two reactors , wherein first the matrix (C1) is produced and then an elastomer (C2) being a copolymer of ethylene and propylene is produced in the presence of the matrix (C1) or (ii) a mechanical union of a matrix (C1) and a (C2) elastomer being a copolymer of ethylene and C4 to C10 alpha-olefin.
    [0011]
    11. Polymer composition according to any one of the preceding claims 1 to 10, characterized in that the matrix (C1) is selected from isotactic or predominantly isotactic polypropylene homopolymer or random copolymers of propylene with ethylene and/or alpha-olefins of C4 to C8, where the total comonomer content ranges from 0.05 to 10.0% by weight, whereby polypropylenes have a density of 0.895 to 0.920 g/cm3, measured in accordance with ISO 1183.
    [0012]
    12. Polymeric composition according to any one of the preceding claims 1 to 11, characterized in that the polymeric composition may additionally comprise inorganic or organic reinforcements.
    [0013]
    13. Article, characterized in that it comprises a polymeric composition as defined in any one of the preceding claims 1 to 12.
    [0014]
    14. Use of the polymeric composition as defined in any of the previous claims 1 to 12, characterized in that it is used for packaging articles.
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    同族专利:
    公开号 | 公开日
    EP3165473B1|2018-01-10|
    US20180215846A1|2018-08-02|
    TWI610978B|2018-01-11|
    BR112018005269A2|2018-10-09|
    CN108025826B|2019-02-19|
    JP6472576B2|2019-02-20|
    CN108025826A|2018-05-11|
    ES2663149T3|2018-04-11|
    JP2018532859A|2018-11-08|
    TW201723060A|2017-07-01|
    US10059785B2|2018-08-28|
    WO2017076933A1|2017-05-11|
    KR20180066257A|2018-06-18|
    KR101946771B1|2019-02-11|
    EP3165473A1|2017-05-10|
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    法律状态:
    2020-05-12| B06U| Preliminary requirement: requests with searches performed by other patent offices: procedure suspended [chapter 6.21 patent gazette]|
    2021-11-30| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|
    2022-01-25| 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 03/11/2016, OBSERVADAS AS CONDICOES LEGAIS. |
    优先权:
    申请号 | 申请日 | 专利标题
    EP15192861.1|2015-11-04|
    EP15192861.1A|EP3165473B1|2015-11-04|2015-11-04|Polypropylene-polyethylene composition with improved flowability|
    PCT/EP2016/076474|WO2017076933A1|2015-11-04|2016-11-03|Polypropylene-polyethylene composition with improved flowability|
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