Patent Grant
10450451
This patent application is the U.S. national phase of International Application No. PCT/EP2015/060896, filed on May 18, 2015, which claims the benefit of European Patent Application No. 14169074.3, filed May 20, 2014, the disclosures of which are incorporated herein by reference in their entireties for all purposes.
The present invention is directed to a new polypropylene composition based on heterophasic propylene copolymer as well as to articles made there from.
Automotive interior parts like dashboards, door claddings, trims etc. are commonly made from polymers. Especially propylene based resins are widely used for these applications. For such parts it is often tried to maintain the high-quality perception till the end of the car's lifetime. Thus the polymer should provide a high resistance to scratches e.g. from keys, fingernails, rings etc.
In comparison to metals polymers have rather low stiffness and surface hardness and thus are much more prone to scratches. Therefore quite often additives, like fillers, are used to over-come this drawback apart. However additives have the drawback to enhance the emission values of the automotive interior parts, which is undesired.
Combining the requirement of high scratch resistance and low emission with good mechanics is challenging, especially in view of the often high expectations regarding processability respectively flowability.
It is therefore an object of the present invention to provide a polypropylene composition with high scratch resistance and good mechanical properties, like high flexural modulus and high impact.
The finding of the present invention is that a heterophasic polypropylene must be combined with mineral filler. Preferably the heterophasic propylene copolymer is comonomer rich, e.g. ethylene rich.
Thus the present invention is directed in a first aspect to a polypropylene composition comprising
Preferably the heterophasic propylene copolymer (HECO) according to the first aspect has 2,1 regio-defects of at least 0.2% determined by 13C-NMR spectroscopy. Still more preferably the matrix (M) of the heterophasic propylene copolymer (HECO) has melt flow rate MFR2 (230° C.) measured according to ISO 1133 in the range of 20 to 80 g/10 min.
In a second aspect of the present invention the polypropylene composition comprises
Preferably the matrix (M) of the heterophasic propylene copolymer (HECO) of the polypropylene composition according to the second aspect has melt flow rate MFR2 (230° C.) measured according to ISO 1133 in the range of 20 to 80 g/10 min.
In one preferred embodiment of the present invention the polypropylene composition according to the first and second aspect comprises additionally a high density polyethylene (HDPE), preferably the amount of the high density polyethylene (HDPE), based on the total weight of the polypropylene composition, is at least 5.0 wt.-%.
Additionally or alternatively to the previous paragraph, the polypropylene composition comprises additionally a plastomer (P) being chemically different to the elastomeric propylene copolymer (EC) of the heterophasic propylene copolymer (HECO), preferably the amount of the plastomer (P), based on the total weight of the polypropylene composition, is at least 5.0 wt.-%.
Preferably the xylene cold soluble (XCS) fraction of the heterophasic propylene copolymer (HECO) as described herein has a comonomer content in the range of 60 to 95 wt.-%.
In one preferred embodiment the matrix (M) of the heterophasic propylene copolymer (HECO) is a propylene homopolymer (H-PP).
Preferably the intrinsic viscosity of the xylene cold soluble fraction (XCS) of the heterophasic propylene copolymer (HECO) is at least 1.0, preferably in the range of 1.0 to 4.2 dl/g.
It is especially preferred that the comonomer content of the heterophasic propylene copolymer (HECO), based on the total weight of the heterophasic propylene copolymer (HECO) is in the range of 5.5 to 35 wt.-%, preferably in the range of 15 to 35 wt.-%.
In still another preferred embodiment the melt flow rate MFR2 (230° C.) measured according to ISO 1133 of the polypropylene composition is in the range of 1.0 to 25 g/10 min, preferably in the range of 1.0 to 20 g/10 min, and/or of the heterophasic propylene copolymer (HECO) is in the range of 1.0 to 30 g/10 min, preferably in the range of 1.0 to 25 g/10 min.
Preferably the heterophasic propylene copolymer (HECO) has a first glass transition temperature Tg(1) and a second glass transition temperature Tg(2), wherein said first glass transition temperature Tg(1) is above the second glass transition temperature Tg(2), more preferably
Preferably the high density polyethylene (HDPE) has a density of at least 940 kg/m3 and/or a melt flow rate MFR2 (190° C.) of 0.2 to 15 g/10 min.
Preferably the plastomer (P) is a polyethylene, more preferably said polyethylene comprises units derived from ethylene and C3 to C8 α-olefins, and/or has a density of equal or less than 920 kg/m3, and/or has a melt flow rate MFR2 (190° C.) measured according to ISO 1133 in the range of 0.5 to 30.0 g/10 min.
The invention is further directed to an article, preferably the article is an automotive interior article, comprising a polypropylene composition according to the present invention.
In the following the invention is described in more detail.
Composition
Essential components of the polypropylene composition are the heterophasic propylene copolymer (HECO) and the mineral filler (F). In preferred embodiments the polypropylene composition comprises additionally a high density polyethylene (HDPE) and/or a plastomer (P).
Preferably the weight ratio between heterophasic propylene copolymer (HECO) and the mineral filler (F) [(HECO)/(F)] is in the range of 2/1 to below 4/1, more preferably in the range of 2/1 to 7/2, yet more preferably in the range of 5/2 to 7/2.
Preferably the polypropylene composition comprises as polymer components only the heterophasic propylene copolymer (HECO), the high density polyethylene (HDPE) and the plastomer (P). In other words the polypropylene composition comprises not more than 8 wt.-%, more preferably not more than 5 wt.-%, yet more preferably not more than 2.5 wt.-%, based on the total weight of the polypropylene composition, of polymers other than the heterophasic propylene copolymer (HECO), the high density polyethylene (HDPE) and the plastomer (P).
In a preferred embodiment the polypropylene composition comprises
Preferably the polypropylene composition according to this invention has a melt flow rate MFR2 (230° C.) in the range of 1.0 to 25 g/10 min, preferably in the range of 1.0 to 20 g/10 min, still more preferably in the range of 1.5 to 18 g/10 min.
In a preferred embodiment the polypropylene composition according to this invention has
The polypropylene composition as defined in the instant invention may contain up to 5.0 wt.-%, based on the total weight of the composition, additives, like nucleating agents and antioxidants, as well as slip agents and antiblocking agents. Preferably the additive content is below 2.5 wt.-%, like below 1.0 wt.-%, based on the total weight of the composition.
The polypropylene composition of the present invention can be prepared by any suitable method known in the art, such as by blending the heterophasic propylene copolymer (HECO) with the other components either directly, e.g., in an extruder, such that the same extruder is used to make the finished product, or by pre-melt mixing in a separate mixer or extruder. For mixing, a conventional compounding or blending apparatus, e.g. a Banbury mixer, a 2-roll rubber mill, Buss-co-kneader or a twin screw extruder may be used.
In the following the individual components are described in more detail.
Heterophasic Propylene Copolymer (HECO)
The present invention is directed to a heterophasic propylene copolymer (HECO). More precisely the present invention is directed to a heterophasic propylene copolymer (HECO) comprising a matrix (M) being a propylene homopolymer (H-PP) or a propylene copolymer (R-PP) and dispersed therein an elastomeric propylene copolymer (EC). Thus the matrix (M) contains (finely) dispersed inclusions being not part of the matrix (M) and said inclusions contain the elastomeric propylene copolymer (EC). The term “inclusion” according to this invention shall preferably indicate that the matrix and the inclusion form different phases within the heterophasic propylene copolymer (HECO), said inclusions are for instance visible by high resolution microscopy, like electron microscopy or atomic force microscopy, or by dynamic mechanical thermal analysis (DMTA). Specifically in DMTA the presence of a multiphase structure can be identified by the presence of at least two distinct glass transition temperatures.
Preferably, the heterophasic propylene copolymer (HECO) according to this invention comprises as polymer components only the polymer matrix (M), i.e. the propylene homopolymer (H-PP) or the propylene copolymer (R-PP), and the elastomeric propylene copolymer (EC). In other words, the heterophasic propylene copolymer (HECO) may contain further additives but no other polymer in an amount exceeding 5.0 wt.-%, more preferably exceeding 3.0 wt.-%, like exceeding 1.0 wt.-%, based on the total heterophasic propylene copolymer (HECO). One additional polymer which may be present in such low amounts is a polyethylene which is a by-reaction product obtained by the preparation of the heterophasic propylene copolymer (HECO). Accordingly, it is in particular appreciated that the instant heterophasic propylene copolymer (HECO) contains only the polymer matrix (M), i.e. the propylene homopolymer (H-PP) or the propylene copolymer (R-PP), the elastomeric propylene copolymer (EC) and optionally polyethylene in amounts as mentioned in this paragraph.
The heterophasic propylene copolymer (HECO) according to this invention is featured by a moderate melt flow rate. Accordingly, the heterophasic propylene copolymer (HECO) has a melt flow rate MFR2 (230° C.) in the range of 1.0 to 30.0 g/10 min, preferably in the range of 1.0 to 25.0 g/10 min, more preferably in the range of 2.0 to 21.0 g/10 min.
Preferably, it is desired that the heterophasic propylene copolymer (HECO) is thermo mechanically stable. Accordingly, it is preferred that the heterophasic propylene copolymer (HECO) has a melting temperature of at least 140° C., more preferably in the range of 140 to 155° C., still more preferably in the range of 145 to 152° C.
Preferably the heterophasic propylene copolymer (HECO) has a crystallization temperature Tc (if not α-nucleated) of at most 120° C., more preferably in the range of 105 to 120° C., like in the range of 108 to 118° C.
The heterophasic propylene copolymer (HECO) comprises apart from propylene also comonomers. Preferably the heterophasic propylene copolymer (HECO) comprises apart from propylene ethylene and/or C4 to C8 α-olefins. Accordingly the term “propylene copolymer” according to this invention is understood as a polypropylene comprising, preferably consisting of, units derivable from
Thus, the heterophasic propylene copolymer (HECO) as well as its individual polymer components, i.e. the propylene copolymer (R-PP) (if present), as well as the elastomeric propylene copolymer (EC), comprises monomers copolymerizable with propylene, for example comonomers such as ethylene and/or C4 to C8 α-olefins, in particular ethylene and/or C4 to C8 α-olefins, e.g. 1-butene and/or 1-hexene. Preferably, the heterophasic propylene copolymer (HECO) according to this invention comprises, especially consists of, monomers copolymerizable with propylene from the group consisting of ethylene, 1-butene and 1-hexene. More specifically, the heterophasic propylene copolymer (HECO) of this invention comprises—apart from propylene—units derivable from ethylene and/or 1-butene. In a preferred embodiment, the heterophasic propylene copolymer (HECO) according to this invention comprises units derivable from ethylene and propylene only. Still more preferably the propylene copolymer (R-PP) (if present) as well as the elastomeric propylene copolymer (EC) of the heterophasic propylene copolymer (HECO) contains the same comonomers, like ethylene.
Accordingly, the elastomeric propylene copolymer (EC) is preferably an ethylene propylene rubber (EPR) whereas the propylene copolymer (R-PP) is a propylene ethylene copolymer (R-PP), i.e. consist only units derived from propylene and ethylene. Accordingly in one specific embodiment the comonomer in the heterophasic propylene copolymer (HECO) is ethylene only. In an especially preferred case the matrix (M) of the heterophasic propylene copolymer (HECO) is a propylene homopolymer (H-PP) whereas the elastomeric propylene copolymer (EC) is an ethylene propylene rubber (EPR).
Additionally, it is preferred that the heterophasic propylene copolymer (HECO) has a comonomer content, like ethylene content, based on the total weight of the heterophasic propylene copolymer (HECO), in the range from 5.5 to 35 wt-%, like 5.9 to 35 wt.-%, more preferably in the range from 15 to 35 wt-%, yet more preferably in the range from 17 to 35 wt-%.
The xylene cold soluble (XCS) fraction of the heterophasic propylene copolymer (HECO) is in the range from 20 to equal or below 35 wt.-%, preferably in the range from 22 to 32 wt.-%, more preferably in the range from 24 to 31 wt.-%.
Further it is appreciated that the xylene cold soluble (XCS) fraction of the heterophasic propylene copolymer (HECO) is specified by its intrinsic viscosity. A low intrinsic viscosity (IV) value reflects a low weight average molecular weight. For the present invention it is preferred that the xylene cold soluble fraction (XCS) of the heterophasic propylene copolymer (HECO) has an intrinsic viscosity (IV) of at least 1.0 dl/g, more preferably in the range of 1.0 to 4.2 dl/g, still more preferably in the range of 1.1 to 4.0 dl/g, yet more preferably in the range of 1.1 to 3.7 dl/g.
Additionally it is preferred that the comonomer content, i.e. ethylene content, of the xylene cold soluble (XCS) fraction of the heterophasic propylene copolymer (HECO) is in the range of 18 to 95 wt-%, more preferably in the range of 40 to 95 wt-%, still more preferably in the range of 60 to 95 wt.-%, yet more preferably in the range of 70 to 90 wt.-%, like in the range of 75 to 85 wt.-%.
Still further, the heterophasic propylene copolymer (HECO) according to the invention preferably fulfills in-equation (I), more preferably in-equation (Ia), still more preferably in-equation (Ib),
wherein
C(XCS) is the comonomer content, like ethylene content, [in wt.-%] of the xylene cold soluble (XCS) fraction of the heterophasic propylene copolymer (HECO);
C(total) is the comonomer content, like ethylene content, [in wt-%] of the total heterophasic propylene copolymer (HECO).
Additionally or alternatively to in-equation (I) it is preferred that the heterophasic propylene copolymer (HECO) according to the invention preferably fulfills in-equation (II), more preferably in-equation (IIa), still more preferably in-equation (IIb),
wherein
C(XCS) is the comonomer content, like ethylene content, [in wt.-%] of the total heterophasic propylene copolymer (HECO);
XCS is the content [in wt.-%] of the xylene cold soluble (XCS) fraction of the heterophasic propylene copolymer (HECO).
As mentioned above multiphase structure of the heterophasic propylene copolymer (HECO) (elastomeric propylene copolymer (EC) dispersed in the matrix (M)) can be identified by the presence of at least two distinct glass transition temperatures. The higher first glass transition temperature (Tg(1)) represents the matrix (M) whereas the lower second glass transition temperature (Tg(2)) reflects the elastomeric propylene copolymer (EC) of the heterophasic propylene copolymer (HECO).
Accordingly, it is preferred that the second glass transition temperature Tg(2) is below −25° C., like equal or below −30° C., more preferably is in the range of −60 to −30° C., yet more preferably in the range of −58 to −32° C., still more preferably in the range of −55 to −33° C.
It is further appreciated that the heterophasic propylene copolymer (HECO) according to this invention has additionally a first glass transition temperature Tg(1) (representing the matrix (M) of the heterophasic propylene copolymer (HECO)) in the range of −8 to +5° C., more preferably in the range of −5 to +4° C., like in the range 0 to +5° C.
Accordingly the first glass transition temperature Tg(1) is preferably above the second glass transition temperature Tg(2). Still more preferably the difference between the first glass transition temperature Tg(1) and second glass transition temperature Tg(2) is at least 30° C., more preferably at least 34° C., yet more preferably in the range of 34 to 55° C., still more preferably in the range of 35 to 52° C.
Preferably the heterophasic propylene copolymer (HECO) according to this invention has been produced in the presence of a metallocene catalyst. The catalyst influences in particular the microstructure of the polymer. In particular, polypropylenes prepared by using a metallocene catalyst provide a different microstructure compared to polypropylenes prepared by using Ziegler-Natta (ZN) catalysts. The most significant difference is the presence of regio-defects in metallocene-made polypropylenes. These regio-defects can be of three different types, namely 2,1-erythro (2,1e), 2,1-threo (2,1t) and 3,1 defects. A detailed description of the structure and mechanism of formation of regio-defects in polypropylene can be found in Chemical Reviews 2000, 100(4), pages 1316-1327. By introducing defects into the polymer chain, such as comonomers, stereo-errors or regio-defects, the physical properties of polypropylene can be modified. In particular, by increasing the amount of chain defects, crystallinity and melting point of polypropylene can be reduced.
The term “2,1 regio defects” as used in the present invention defines the sum of 2,1 erythro regio-defects and 2,1 threo regio-defects.
Accordingly it is preferred that the heterophasic propylene copolymer (HECO) according to this invention has 2,1 regio-defects, like 2,1 erythro regio-defects, of at least 0.1%, more preferably of at least 0.2%, still more preferably in the range of 0.2 to 4.0%, determined by 13C-NMR spectroscopy. For example, the heterophasic propylene copolymer (HECO) of the instant invention has 2,1 regio-defects, like 2,1 erythro regio-defects, of from 0.4 to 2.0%, determined by 13C-NMR spectroscopy.
The heterophasic propylene copolymer (HECO) as defined in the instant invention may contain up to 5.0 wt.-% additives, like nucleating agents and antioxidants, as well as slip agents and antiblocking agents. Preferably the additive content is below 3.0 wt.-%, like below 1.0 wt.-%.
The heterophasic propylene copolymer (HECO) can be further defined by its individual components, i.e. the polymer matrix (M) and the elastomeric propylene copolymer (EC).
The polymer matrix (M) can be a propylene copolymer (R-PP) or a propylene homopolymer (H-PP), the latter is especially preferred.
The expression “propylene homopolymer” as used throughout the instant invention relates to a polypropylene that consists substantially, i.e. of equal or above than 99.0 wt %, more preferably of equal or above than 99.5 wt %, like equal or above than 99.8 wt %, of propylene units. In a preferred embodiment only propylene units in the propylene homopolymer are detectable.
In the case that the polymer matrix is a propylene copolymer (R-PP), said propylene copolymer (R-PP) comprises monomers copolymerizable with propylene, for example comonomers such as ethylene and/or C4 to C8 α-olefins, in particular ethylene and/or C4 to C6 α-olefins, e.g. 1-butene and/or 1-hexene. Preferably the propylene copolymer (R-PP) according to this invention comprises, especially consists of, monomers copolymerizable with propylene from the group consisting of ethylene, 1-butene and 1-hexene. More specifically the propylene copolymer (R-PP) of this invention comprises—apart from propylene—units derivable from ethylene and/or 1-butene. In a preferred embodiment the propylene copolymer (R-PP) comprises units derivable from ethylene and propylene only.
Preferably the comonomer content of the propylene copolymer (R-PP) is in the range of more than 1.0 to 10.0 wt.-%, yet more preferably in the range of 1.5 to 8.0 wt-%, still more preferably in the range of 1.5 to 5.0 wt-%.
As mentioned above, the polymer matrix (M) is preferably a propylene homopolymer (H-PP).
The polymer matrix (M) may consist of a single polymer, like a propylene homopolymer, but may also comprise a mixture of (two) different propylene polymers, like different propylene homopolymers. Ideally, however a single polymer, like a single propylene homopolymer (H-PP), is present.
Preferably the polymer matrix (M), e.g. the propylene homopolymer (H-PP), has a melt flow rate MFR2 (230° C.) in the range of 20 to 80 g/10 min, preferably in the range of 20 to 60 g/10 min, more preferably in the range of 25 to 50 g/10 min.
Preferably the weight ratio between the matrix (M), i.e. the propylene homopolymer (H-PP) or the propylene copolymer (R-PP), and the elastomeric propylene copolymer (EC) is in the range of 3/2 to 5/1, more preferably in the range of 2/1 to 9/2, still more preferably in the range of 2/1 to 4/1.
Accordingly in one preferred embodiment, the heterophasic propylene copolymer (HECO) preferably comprises 55 to 95 wt.-%, more preferably 60 to 90 wt.-%, still more preferably 65.0 to 85.0 wt.-%, of the polymer matrix (M) based on the total weight of the heterophasic propylene copolymer (HECO).
Additionally, the heterophasic propylene copolymer (RAHECO) preferably comprises 5 to 45 wt.-%, more preferably 10 to 40 wt.-%, still more preferably 15 to 35 wt.-% of the elastomeric propylene copolymer (EC), based on the total weight of the heterophasic propylene copolymer (HECO).
Accordingly, a further component of the heterophasic propylene copolymer (HECO) is the elastomeric propylene copolymer (EC) dispersed in the matrix (M). Concerning the comonomers used in the elastomeric propylene copolymer (EC) it is referred to the information provided for the heterophasic propylene copolymer (HECO). Accordingly the elastomeric propylene copolymer (EC) comprises monomers copolymerizable with propylene, for example comonomers such as ethylene and/or C4 to C8 α-olefins, in particular ethylene and/or C4 to C6 α-olefins, e.g. 1-butene and/or 1-hexene. Preferably, the elastomeric propylene copolymer (EC) comprises, especially consists of, monomers copolymerizable with propylene from the group consisting of ethylene, 1-butene and 1-hexene. More specifically, the elastomeric propylene copolymer (EC) comprises—apart from propylene—units derivable from ethylene and/or 1-butene. Thus, in an especially preferred embodiment the elastomeric propylene copolymer (EC) comprises units derivable from ethylene and propylene only.
As a first approximation the xylene cold soluble (XCS) fraction represents the elastomeric propylene copolymer (EC). Accordingly the comonomer content of the xylene cold soluble (XCS) fraction and of the elastomeric propylene copolymer (EC) are similar. Thus, the comonomer content, the ethylene content, of the elastomeric propylene copolymer (EC) preferably is preferably in the range of 18 to 95 wt-%, more preferably in the range of 40 to 95 wt-%, like 40 to 90 wt.-%, still more preferably in the range of 60 to 95 wt.-%, like 60 to 90 wt.-%, yet more preferably in the range of 70 to 90 wt.-%, like in the range of 75 to 85 wt.-%.
The instant heterophasic propylene copolymer (HECO) is preferably produced in a multistage process comprising at least two reactors, preferably at least three reactors, connected in series.
Accordingly the heterophasic propylene copolymer (HECO) according to this invention is produced by polymerizing:
Preferably the heterophasic propylene copolymer (HECO) is obtained by a sequential polymerization process comprising the steps of
For preferred embodiments of the heterophasic propylene copolymer (HECO), the polymer matrix, e.g. the propylene homopolymer (H-PP), and the elastomeric copolymer (EC) reference is made to the definitions given above.
The term “sequential polymerization process” indicates that the heterophasic propylene copolymer (HECO) is produced in at least two, like three, reactors connected in series. Accordingly the present process comprises at least a first reactor, a second reactor, and optionally a third reactor. The term “polymerization process” shall indicate that the main polymerization takes place. Thus in case the process consists of three polymerization reactors, this definition does not exclude the option that the overall process comprises for instance a pre-polymerization step in a pre-polymerization reactor. The term “consist of” is only a closing formulation in view of the main polymerization process.
The first reactor is preferably a slurry reactor and can be any continuous or simple stirred batch tank reactor or loop reactor operating in bulk or slurry. Bulk means a polymerization in a reaction medium that comprises of at least 60% (w/w) monomer. According to the present invention the slurry reactor is preferably a (bulk) loop reactor.
The second reactor and the third reactor are preferably gas phase reactors. Such gas phase reactors can be any mechanically mixed or fluid bed reactors. Preferably the gas phase reactors comprise a mechanically agitated fluid bed reactor with gas velocities of at least 0.2 m/sec. Thus it is appreciated that the gas phase reactor is a fluidized bed type reactor preferably with a mechanical stirrer.
Thus in a preferred embodiment the first reactor is a slurry reactor, like loop reactor, whereas the second reactor and the third reactor are gas phase reactors (GPR). Accordingly for the instant process at least three, preferably three polymerization reactors, namely a slurry reactor, like loop reactor, a first gas phase reactor and a second gas phase reactor are connected in series are used. If needed prior to the slurry reactor a pre-polymerization reactor is placed.
A preferred multistage process is a “loop-gas phase”-process, such as developed by Borealis A/S, Denmark (known as BORSTAR® technology) described e.g. in patent literature, such as in EP 0 887 379, WO 92/12182 WO 2004/000899, WO 2004/111095, WO 99/24478, WO 99/24479 or in WO 00/68315.
A further suitable slurry-gas phase process is the Spheripol® process of Basell.
Preferably, in the instant process for producing the heterophasic propylene copolymer (HECO) as defined above the conditions for the first reactor, i.e. the slurry reactor, like a loop reactor, may be as follows:
Subsequently, the reaction mixture of the first reactor is transferred to the second reactor, i.e. gas phase reactor, where the conditions are preferably as follows:
The condition in the third reactor is similar to the second reactor.
The residence time can vary in the three reactors.
In one embodiment of the process for producing the heterophasic propylene copolymer (HECO) the residence time in bulk reactor, e.g. loop is in the range 0.1 to 2.5 hours, e.g. 0.15 to 1.5 hours and the residence time in gas phase reactor will generally be 0.2 to 6.0 hours, like 0.3 to 4.0 hours.
If desired, the polymerization may be effected in a known manner under supercritical conditions in the first reactor, i.e. in the slurry reactor, like in the loop reactor, and/or as a condensed mode in the gas phase reactors.
In the following the catalyst component is defined in more detail. Preferably the catalyst comprises (i) a complex of formula (I):
(i) a transition metal compound of formula (I)
Rn(Cp′)2MX2 (I)
Preferred catalysts and their prepartion are for instance described in WO 2010/052263 A1, EP 2 487 203 as well as in WO2013/007650.
In one preferred embodiment the transition metal compound is selected from the group consisting of: rac-methyl(cyclohexyl)silanediylbis(2-methyl-4-(4-tert-butylphenyl)indenyl)zirconium dichloride, rac-dimethylsilanediyl bis(2-methyl-4-(4-tert-butylphenyl)-1,5,6,7-tetrahydro-s-indacen-1-yl)zirconium dichloride and rac-dimethylsilanediyl bis(2-methyl-4-phenyl-5-methoxy-6-tert-butylindenyl)zirconium dichloride.
In another preferred embodiment the transition metal compound is selected from the tables given below:
Mineral Filler (F)
Any mineral filler can be used in the present invention. However it is preferred that the mineral filler (F) is a phyllosilicate, mica or wollastonite. Even more preferred the mineral filler (F) is selected from the group consisting of mica, wollastonite, kaolinite, smectite, montmorillonite and talc. The most preferred the inorganic filler is talc.
The mineral filler (F) preferably has a median particle size d50 [mass percent] of equal or below 10 μm, more preferably below 5.0 μm, like below 3.0 μm.
The mineral filler (F) preferably has a cutoff particle size d95 [mass percent] of equal or below 20 μm, more preferably below 10.0 μm, like below 8.0 μm.
Typically the mineral filler (F) has a surface area of less than 50 m2/g, more preferably of less than 30 m2/g, yet more preferably of less than 25 m2/g. Mineral fillers (F) fulfilling these requirements are preferably anisotropic mineral fillers, like talc, mica and wollastonite.
High Density Polyethylene (HDPE)
The polypropylene composition according to the present invention may further comprise a high density polyethylene (HDPE). A high density polyethylene (HDPE) in the sense of the present invention has preferably a density of at least 940 kg/m3, more preferably of at least 950 kg/m3, yet more preferably in the range of 940 to 975 kg/m3, still yet more preferably in the range of 950 to 970 kg/m3.
Preferably the high density polyethylene (HDPE) has a melt flow rate MFR2 (190° C.) of 0.2 to 15 g/10 min, more preferably of 0.3 to 10.0 g/10 min.
The Plastomer (P)
In a preferred embodiment, the composition of the present invention further comprises a plastomer (P). That is to say, a plastomer (P) can be present in the inventive polypropylene composition. The plastomer (P) is (chemically) different to the elastomeric propylene copolymer (EC) of the heterophasic propylene copolymer (HECO). More precisely the plastomer (P) is preferably selected from the group consisting of a linear low density polyethylene (LLDPE), a styrenic block copolymer (SBC), and mixtures thereof. In one embodiment the inventive composition comprises as plastomer (P) a linear low density polyethylene (LLDPE), especially a linear low density polyethylene (LLDPE) as defined below.
The linear low density polyethylene (LLDPE) has preferably a density in the range 820 to 920 kg/m3, more preferably in the range of 850 to 900 kg/m3, yet more preferably in the range of 840 to 880 kg/m3, like in the range of 860 to 885 kg/m3.
Preferably the linear low density polyethylene (LLDPE), is featured by a specific melt flow rate, namely by a melt flow rate MFR2 (190° C.) measured according to ISO 1133 in the range of 0.5 to 100.0 g/10 min, preferably in the range of 1.0 to 25.0 g/10 min, like in the range of 1.5 to 12.0 g/10 min.
In a preferred embodiment the linear low density polyethylene (LLDPE), is a copolymer containing as a major part units derivable from ethylene. Accordingly it is appreciated that the linear low density polyethylene (LLDPE) comprises at least 50.0 wt.-% units derivable from ethylene, more preferably at least 55.0 wt.-% of units derived from ethylene. Thus it is appreciated that the linear low density polyethylene (LLDPE) comprises 50.0 to 70.0 wt.-%, more preferably 55.0 to 65 wt.-%, units derivable from ethylene. The comonomers present in the linear low density polyethylene (LLDPE), are C4 to C20 α-olefins, like 1-butene, 1-hexene and 1-octene, the latter especially preferred. Accordingly in one specific embodiment the linear low density polyethylene (LLDPE) is an ethylene-1-octene copolymer with the amounts given in this paragraph.
Article
The polypropylene composition of the present invention is preferably used for the production of articles, preferably automotive articles, like molded automotive articles, e.g. automotive injection molded articles. Even more preferred is the use of the inventive polypropylene composition for the production of automotive interiors and exteriors, like bumpers, side trims, step assists, body panels, spoilers, dashboards, interior trims and the like.
According to a preferred embodiment of the present invention, the composition of the present invention is used for the production of automotive articles, preferably interior automotive articles, more preferably dash boards, instrument panels, door claddings, arm rests, gear sticks, shift lever knobs, mats, interior skins, trunk claddings, or interior trims.
The present invention also provides (automotive) articles, like injection molded articles, comprising at least to 60 wt.-%, preferably at least 80 wt.-%, more preferably at least 95 wt.-%, and most preferably consisting of the inventive composition. Accordingly the present invention is especially directed to automotive articles, especially to car interiors and exteriors, like bumpers, side trims, step assists, body panels, spoilers, dashboards, interior trims and the like, comprising at least to 60 wt.-%, preferably at least 80 wt.-%, more preferably at least 95 wt.-%, and most preferably consisting of the inventive polypropylene composition.
According to a preferred embodiment of the present invention, the automotive article is an interior automotive article, more preferably a dash board, instrument panel, door cladding, arm rest, map pocket, column trim, shift lever knob, interior skin, trunk cladding, or interior trim in general.
In the following the present invention is further illustrated by means of examples.
1. Measuring Methods
The following definitions of terms and determination methods apply for the above general description of the invention as well as to the below examples unless otherwise defined.
Calculation of comonomer content of the elastomeric propylene copolymer (EC), respectively:
wherein
Quantitative nuclear-magnetic resonance (NMR) spectroscopy was used to quantify the comonomer content of the polymers.
Quantitative 13C {1H} NMR spectra were recorded in the solution-state using a Bruker Advance III 400 NMR spectrometer operating at 400.15 and 100.62 MHz for 1H and 13C respectively. All spectra were recorded using a 13C optimised 10 mm extended temperature probehead at 125° C. using nitrogen gas for all pneumatics. Approximately 200 mg of material was dissolved in 3 ml of 1,2-tetrachloroethane-d2 (TCE-d2) along with chromium-(III)-acetylacetonate (Cr(acac)3) resulting in a 65 mM solution of relaxation agent in solvent as described in G. Singh, A. Kothari, V. Gupta, Polymer Testing 2009, 28(5), 475. To ensure a homogenous solution, after initial sample preparation in a heat block, the NMR tube was further heated in a rotatory oven for at least 1 hour. Upon insertion into the magnet the tube was spun at 10 Hz. This setup was chosen primarily for the high resolution and quantitatively needed for accurate ethylene content quantification. Standard single-pulse excitation was employed without NOE, using an optimised tip angle, 1 s recycle delay and a bi-level WALTZ16 decoupling scheme as described in Z. Zhou, R. Kuemmerle, X. Qiu, D. Redwine, R. Cong, A. Taha, D. Baugh, B. Winniford, J. Mag. Reson. 187 (2007) 225 and V. Busico, P. Carbonniere, R. Cipullo, C. Pellecchia, J. Severn, G. Talarico, Macromol. Rapid Commun. 2007, 28, 1128. A total of 6144 (6k) transients were acquired per spectra. Quantitative 13C {1H} NMR spectra were processed, integrated and relevant quantitative properties determined from the integrals. All chemical shifts were indirectly referenced to the central methylene group of the ethylene block (EEE) at 30.00 ppm using the chemical shift of the solvent. This approach allowed comparable referencing even when this structural unit was not present.
With characteristic signals corresponding to 2,1 erythro regio defects observed (as described in L. Resconi, L. Cavallo, A. Fait, F. Piemontesi, Chem. Rev. 2000, 100 (4), 1253, in Cheng, H. N., Macromolecules 1984, 17, 1950, and in W-J. Wang and S. Zhu, Macromolecules 2000, 33 1157) the correction for the influence of the regio defects on determined properties was required. Characteristic signals corresponding to other types of regio defects were not observed.
Characteristic signals corresponding to the incorporation of ethylene were observed (as described in Cheng, H. N., Macromolecules 1984, 17, 1950) and the comonomer fraction calculated as the fraction of ethylene in the polymer with respect to all monomer in the polymer.
The comonomer fraction was quantified using the method of W-J. Wang and S. Zhu, Macromolecules 2000, 33 1157, through integration of multiple signals across the whole spectral region in the 13C {1H} spectra. This method was chosen for its robust nature and ability to account for the presence of regio-defects when needed. Integral regions were slightly adjusted to increase applicability across the whole range of encountered comonomer contents.
The mole percent comonomer incorporation was calculated from the mole fraction.
The weight percent comonomer incorporation was calculated from the mole fraction.
Comonomer content in polyethylene [HDPE, Plastomer (P)] was measured in a known manner based on Fourier transform infrared spectroscopy (FTIR) calibrated with 13C-NMR, using Nicolet Magna 550 IR spectrometer together with Nicolet Omnic FTIR software. Films having a thickness of about 250 μm were compression molded from the samples. Similar films were made from calibration samples having a known content of the comonomer. The comonomer content was determined from the spectrum from the wave number range of from 1430 to 1100 cm−1. The absorbance is measured as the height of the peak by selecting the so-called short or long base line or both. The short base line is drawn in about 1410-1320 cm−1 through the minimum points and the long base line about between 1410 and 1220 cm−1. Calibrations need to be done specifically for each base line type. Also, the comonomer content of the unknown sample needs to be within the range of the comonomer contents of the calibration samples.
MFR2 (230° C.) is measured according to ISO 1133 (230° C., 2.16 kg load).
MFR2 (190° C.) was measured according to ISO 1133 (190° C., 2.16 kg load).
The Density was measured according to ISO 1183-1—method A (2004). Sample preparation is done by compression moulding in accordance with ISO 1872-2:2007.
Intrinsic viscosity is measured according to DIN ISO 1628/1, October 1999 (in Decalin at 135° C.).
The xylene solubles (XCS, wt.-%): Content of xylene cold solubles (XCS) is determined at 25° C. according ISO 16152; first edition; 2005-07-01.
Melting temperature (Tm) and heat of fusion (Hf), crystallization temperature (Tc) and heat of crystallization (Hc): measured with Mettler TA820 differential scanning calorimetry (DSC) on 5 to 10 mg samples. DSC is run according to ISO 11357-3:1999 in a heat/cool/heat cycle with a scan rate of 10° C./min in the temperature range of +23 to +210° C. Crystallization temperature and heat of crystallization (Hc) are determined from the cooling step, while melting temperature and heat of fusion (Hf) are determined from the second heating step.
The glass transition temperature Tg is determined by dynamic mechanical analysis according to ISO 6721-7. The measurements are done in torsion mode on compression moulded samples (40×10×1 mm3) between −100° C. and +150° C. with a heating rate of 2° C./min and a frequency of 1 Hz.
Flexural Modulus: The flexural modulus was determined in 3-point-bending according to ISO 178 on 80×10×4 mm3 test bars injection molded at 23° C. in line with EN ISO 1873-2.
Charpy notched impact strength is determined according to ISO 179 leA at 23°, and at −20° C. by using an 80×10×4 mm3 test bars injection molded in line with EN ISO 1873-2.
Cutoff particle size d50 and 95 (Sedimentation) is calculated from the particle size distribution [mass percent] as determined by gravitational liquid sedimentation according to ISO 13317-3 (Sedigraph).
Surface area: BET with N2 gas according to DIN 66131/2, apparatus Micromeritics Tristar 3000: sample preparation at a temperature of 50° C., 6 hours in vacuum.
Scratch Visibility
To determine the scratch visibility a Cross Hatch Cutter Model 420P, manufactured by Erichsen, was used. For the tests, plaques of 70×70×4 mm size were cut from a moulded grained (grain parameters: average grain size=1 mm, grain depth=0.12 mm, conicity=6°) plaque of size 140×200×4 mm. The period between injection moulding of specimens and scratch-testing was 7 days.
For testing the specimens must be clamped in a suitable apparatus as described above. Scratches were applied at a force of 10 N using a cylindrical metal pen with a ball shaped end (radius=0.5 mm±0.01). A cutting speed of 1000 mm/min was used.
A minimum of 20 scratches parallel to each other were brought up at a load of 10 N with a distance of 2 mm. The application of the scratches was repeated perpendicular to each other, so that the result was a scratching screen. The scratching direction should be unidirectional. The scratch visibility is reported as the difference of the luminance ΔL of the unscratched from the scratched areas. ΔL values were measured using a spectrophotometer that fulfils the requirements to DIN 5033. Light source for quantification of ΔL D65/10°.
A detailed test description of the test method (Erichsen cross hatch cutter method) can be found in the article “Evaluation of scratch resistance in multiphase PP blends” by Thomas Koch and Doris Machl, published in POLYMER TESTING 26 (2007), p. 927-936.
2. Examples
The catalyst Cat1 used in the polymerization processes for the heterophasic propylene copolymer (HECO 1 and HECO 3) was prepared as follows:
The catalyst used has been prepared following the general procedures described in WO2013/007650 to prepare catalyst E2P, using the same metallocene complex (E2 in WO2013/007650) rac-anti-dimethylsilanediyl(2-methyl-4-(4′-tert-butylphenyl)inden-1-yl)(2-methyl-4-phenyl-5-methoxy-6-tert-butylinden-1-yl) zirconium dichloride. Its composition is indicated in table 1 below:
Catalyst Synthesis:
Inside the glovebox, 80.0 μl of dry and degassed surfactant was mixed with 2 mL of MAO in a septum bottle and left to react overnight. The following day, 58.7 mg of the metallocene (0.076 mmol, 1 equivalent) was dissolved with 4 mL of the MAO solution in another septum bottle and left to stir inside the glovebox.
After 60 minutes, 1 mL of the surfactant solution and the 4 mL of the MAO-metallocene solution were successively added into a 50 mL emulsification glass reactor containing 40 mL of perfluoro-1.3-dimethylcyclohexane (PFC) at −10° C. and equipped with an overhead stirrer (stirring speed=600 rpm). Total amount of MAO is 5 mL (300 equivalents). A red emulsion formed immediately and stirred during 15 minutes at −10° C./600 rpm. Then the emulsion was transferred via a 2/4 teflon tube to 100 mL of hot PFC at 90° C., and stirred at 600 rpm until the transfer is completed, then the speed was reduced to 300 rpm. After 15 minutes stirring, the oil bath was removed and the stirrer turned off. The catalyst was left to settle up on top of the PFC and after 35 minutes the solvent was siphoned off. The remaining catalyst was dried during 2 hours at 50° C. under an argon flow. 0.81 g of a red solid catalyst was obtained.
Catalyst off-line prepolymerization (Prepping): The above catalyst was pre-polymerised according to the following procedure: Off-line pre-polymerisation experiment was done in a 125 mL pressure reactor equipped with gas-feeding lines and an overhead stirrer. Dry and degassed PFC (15 cm3) and 801.7 mg of the catalyst to be pre-polymerised were loaded into the reactor inside a glove box and the reactor was sealed. The reactor was then taken out from the glove box and placed inside a water cooled bath kept at 25° C. The overhead stirrer and the feeding lines were connected and stirring speed set to 450 rpm. The experiment was started by opening the propylene feed into the reactor. The propylene feed was left open and the monomer consumption was compensated by keeping the total pressure in the reactor constant (about 5 barg). The experiment was continued until a polymerisation time (17 min.) sufficient to provide the desired degree of polymerisation (DP=3.5). The reaction was stopped by flashing the volatile components. Inside the glove box, the reactor was opened and the content poured into a glass vessel. The PFC was evaporated until a constant weight was obtained to yield 3.59 g of the pre-polymerised catalyst.
The catalyst Cat2 used in the polymerization processes for the heterophasic propylene copolymer (HECO2) is described in example 10 of WO 2010/052263 A1 and its composition is also reported in Table 1.
Polymerization Procedure:
Step 1: Bulk Homopolymerization.
A stirred autoclave, equipped with a double helix stirrer, with a volume of 21.2 dm3 containing 0.2 bar-g propylene was filled with additional 3.97 kg propylene. After adding 0.73 mmol triethylaluminium (Aldrich, 1 molar solution in n-hexane) using a stream of 250 g propylene, the solution was stirred at 20° C. and 250 rpm for 20 min, then the reactor was brought up to the set prepolymerization temperature and the catalyst was injected as described in the following. The solid, pre-polymerized catalyst (type, amount and degree of polymerisation as listed in table 2) was loaded into a 5-mL stainless steel vial inside the glovebox, the vial was attached to the autoclave, then a second 5-mL vial containing 4 ml n-hexane and pressurized with 10 bars of N2 was added on top, the valve between the two vials was opened and the solid catalyst was contacted with hexane under N2 pressure for 2 s, then flushed into the reactor with 250 g propylene. Stirring speed was increased to 250 rpm and pre-polymerisation was run for the set time. At the end of the prepolymerization step the stirring speed was increased to 350 rpm and the temperature raised to 80° C. When the internal reactor temperature reached 71° C., the desired H2 amount was added with a defined flow rate via thermal mass flow controller. The reactor temperature was held constant throughout the polymerization. The polymerization time was measured starting when the inner reactor temperature reached 2° C. below the set polymerization temperature.
Step 2: First Gas Phase Homopolymerisation (GP1)
After the bulk step was completed, the stirrer speed was reduced to 50 rpm and the reactor pressure was reduced to 1 bar below the target gas phase pressure by venting the monomer. Afterwards the stirrer speed was set to 250 rpm, the reactor temperature to 80° C., and additional H2 was added via flow controller. When the reactor pressure reached the target pressure and T=79° C., both P and T have been held constant via mass flow controller and thermostat at a set pressure and at 80° C. for a defined time (max 2 hours) or until the propylene amount required to reach the desired split had been fed.
Step 3: Second Gas Phase Step, C2/C3 Copolymerization (GP2)
After the first gas phase step (GP1) was completed, the stirrer speed was reduced to 50 rpm, the reactor pressure was lowered to 0.3 bar by venting propylene and the temperature control device was set to 70° C. The reactor was then filled with 200 g propylene at a flow of 70 g/min, and then the reactor was vented again down to 0.3 barg, with the purpose of minimizing the amount of hydrogen left in the reactor.
Then the stirrer speed was set to 250 rpm and the thermostat at the target value and the reactor was filled with a mixture of propylene and ethylene in a defined C3/C2 ratio (transition between GP1 and GP2). This ratio depends on the measured relative reactivity ratio (R) of ethylene and propylene for the given catalyst. The speed of the reactor filling during the transition was limited by the max. flow of the gas flow controllers. When the reactor temperature had reached 1° C. below the target temperature (70° C.) and the pressure was at the desired value, the composition of the fed C3/C2 mixture was changed to the desired polymer composition, and the temperature and pressure parameters was held constant until a defined amount of C3 and C2 was consumed to reach the target split of rubber to homopolymer. The reaction was stopped by lowering the stirrer speed to 20 rpm, cooling the reactor to 30° C. and flashing the volatile components.
After purging the reactor twice with N2 and one vacuum/N2 cycle, the product was taken out and dried overnight in a hood and additionally 2 hours in a vacuum drying oven at 60° C. After weighing, the polymer was additivated with 0.2 wt.-% Ionol and 0.1 wt.-% PEPQ.
The results are listed in table 2.
1ratio during transition
2ratio during polymerization at constant T, P
The polypropylene compositions were prepared by melt blending the components on a co-rotating twin screw extruder type Coperion ZSK 40 (screw diameter 40 mm, L/D ratio 38) at temperatures in the range of 170−190° C., using a high intensity mixing screw configuration with two sets of kneading blocks.
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| PCT/EP2015/060896 | 5/18/2015 | WO | 00 |
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