Polypropylene composition for extrusion as a laminated film for automotive interior products

Abstract

The present invention relates to a polypropylene composition comprising an atactic polypropylene copolymer and an elastomeric ethylene atactic copolymer, a film comprising the polypropylene composition, and an injection-molded polypropylene article laminated from the film.

Description

Technical Field

[0001] The present invention relates to a polypropylene composition comprising a random propylene copolymer and an elastomeric ethylene random copolymer, a film comprising the polypropylene composition, and an injection molded polypropylene article laminated from the film. Background Art

[0002] Polypropylene is one of the main polymeric materials used for manufacturing automotive parts due to its good mechanical properties, including the balance of stiffness and impact strength. Due to the high complexity available on a large scale, these automotive parts are typically obtained by injection molding. Although polypropylene is the polymer of choice for both exterior and interior automotive parts, the properties of most polypropylene grades need to be improved for injection molded interior products because the surface properties and appearance of these products are crucial. Due to the rheological properties of polypropylene, unstable flow during the injection molding process can lead to surface appearance defects such as tiger stripes, gloss differences, and gate whitening.

[0003] Although overcoming these drawbacks has long been a goal in the field of polypropylene development, it is difficult to appropriately adjust the rheological properties without adversely affecting the mechanical properties of the product. Summary of the Invention

[0004] The discovery of the present invention is that a polypropylene composition can be used to produce a film for laminating injection molded polypropylene articles, avoiding undesirable aesthetic defects without affecting the critical mechanical properties of the articles.

[0005] Accordingly, the present invention relates to a polypropylene composition (PC) comprising:

[0006] a) 60 to 90% by weight of a random propylene copolymer (R-PP) having propylene monomer units and one or more comonomer units selected from ethylene and / or α-olefins having 4 to 12 carbon atoms, wherein

[0007] i) the melt flow rate MFR 2 (230 °C, 2.16 kg, ISO 1133) is in the range of 0.1 to 15.0 g / 10 min, and

[0008] ii) the Vicat softening temperature, Method A is in the range of 110 to 140 °C (ISO 306),

[0009] b) 5 to 35% by weight of an elastomeric ethylene random copolymer (E) having ethylene monomer units and one or more comonomer units selected from α-olefins having 4 to 12 carbon atoms,

[0010] wherein the melting temperature (ISO 11357) is at least 75 °C,

[0011] c) 0 to 5% by weight of additive (A),

[0012] wherein the % by weight given for each component is relative to the total weight of the polypropylene composition, and the melt flow rate MFR 2 (230 °C, 2.16 kg, ISO 1133) is in the range of 1.0 to 5.0 g / 10 min.

[0013] In a preferred embodiment, the propylene random copolymer (R-PP) has a content of comonomer units determined by quantitative 13 C-NMR spectroscopy in the range of 2 to 5% by weight, and the comonomer units are selected from ethylene and / or α-olefins having 4 to 12 carbon atoms.

[0014] In a preferred embodiment, the elastomeric ethylene random copolymer (E) has a content of comonomer units determined by quantitative 13 C-NMR spectroscopy in the range of 30 to 50% by weight, and the comonomer units are selected from α-olefins having 4 to 12 carbon atoms.

[0015] In a preferred embodiment, the combined content of (R-PP), (E) and (A) in the propylene composition (PC) is at least 90% by weight, preferably at least 95% by weight, and most preferably the propylene composition (PC) consists of (R-PP), (E) and (A).

[0016] In a preferred embodiment, the ratio (R-PP) / (E) of the content of the propylene random copolymer (R-PP) to the content of the elastomeric ethylene random copolymer (E) in the polypropylene composition (PC) is in the range of 2 to 5.

[0017] In another preferred embodiment, the melting temperature (ISO 11357) of the polypropylene composition (PC) is in the range of 110 to 125 °C, more preferably in the range of 112 to 120 °C.

[0018] In another preferred embodiment, the Vicat softening temperature, Method A (ISO 306) of the polypropylene composition (PC) is in the range of 85 to 105 °C.

[0019] In another preferred embodiment, the propylene random copolymer (R-PP) consists of propylene monomer units and ethylene comonomer units.

[0020] In another preferred embodiment, the propylene random copolymer (R-PP) has a flexural modulus (ISO 527) of at least 800 MPa.

[0021] In another preferred embodiment, the elastomeric ethylene random copolymer (E) has a melt flow rate MFR in the range of 0.1 to 2.0 g / 10 min 2 (190 °C, 2.16 kg, ISO 1133).

[0022] In another preferred embodiment, the elastomeric ethylene random copolymer (E) consists of ethylene monomer units and 1-octene comonomer units.

[0023] In another preferred embodiment, the additive (A) is selected from antioxidants, UV stabilizers, scratch resistant agents, mold release agents, acid scavengers, lubricants, antistatic agents, and mixtures thereof.

[0024] In another preferred embodiment, the polypropylene composition (PC) does not contain talc and preferably does not contain any inorganic fillers.

[0025] In another aspect, the present invention relates to an article comprising, preferably consisting of, the polypropylene composition (PC).

[0026] In a preferred embodiment, the article is a film, preferably a cast film.

[0027] In another preferred embodiment, the film is a laminated film for polypropylene articles, preferably polypropylene automotive articles, and most preferably polypropylene automotive interior articles.

[0028] In another aspect, the present invention relates to an automotive interior article comprising injection molded polypropylene laminated with the film of the present invention, the film comprising, preferably consisting of, the polypropylene composition (PC).

[0029] In yet another aspect, the present invention relates to the use of the film of the present invention for laminating polypropylene articles, preferably for laminating polypropylene automotive articles, and most preferably for laminating polypropylene automotive interior articles.

[0030] The present invention will now be described in more detail. Detailed Description

[0031] Random Propylene Copolymer (R-PP)

[0032] The main component of the polypropylene composition (PC) of the present invention is a random propylene copolymer (R-PP).

[0033] In the context of the present invention, the term random propylene copolymer is understood to exclude multiphase propylene copolymers. That is, the random propylene copolymer (R-PP) of the present invention is a single-phase random propylene copolymer.

[0034] The random propylene copolymer (R-PP) of the present invention comprises propylene monomer units and one or more comonomer units selected from ethylene and / or α-olefins having 4 to 12 carbon atoms, and the amount of the one or more comonomer units determined by quantitative 13 C-NMR spectroscopy is preferably in the range of 2 to 5% by weight, more preferably in the range of 2.0 to 5.0% by weight, still more preferably in the range of 3.0 to 4.5% by weight, and most preferably in the range of 3.5 to 4.5% by weight.

[0035] Preferably, the random propylene copolymer (R-PP) of the present invention comprises propylene monomer units and ethylene comonomer units, and the amount of the ethylene comonomer units determined by quantitative 13 C-NMR spectroscopy is in the range of 2 to 5% by weight, preferably in the range of 2.0 to 5.0% by weight, more preferably in the range of 3.0 to 4.5% by weight, and most preferably in the range of 3.5 to 4.5% by weight.

[0036] More preferably, the random propylene copolymer (R-PP) of the present invention consists of propylene monomer units and ethylene comonomer units, and the amount of the ethylene comonomer units determined by quantitative 13 C-NMR spectroscopy is in the range of 2 to 5% by weight, preferably in the range of 2.0 to 5.0% by weight, more preferably in the range of 3.0 to 4.5% by weight, and most preferably in the range of 3.5 to 4.5% by weight.

[0037] The melt flow rate MFR of the random propylene copolymer (R-PP) of the present invention 2 (230 °C, 2.16 kg, ISO 1133) is in the range of 0.1 to 15.0 g / 10 min, preferably in the range of 0.5 to 10.0 g / 10 min, more preferably in the range of 0.8 to 5.0 g / 10 min, and most preferably in the range of 1.0 to 3.0 g / 10 min.

[0038] The Vicat softening temperature of the random propylene copolymer (R-PP) of the present invention, Method A (ISO 306) is in the range of 110 to 140 °C, preferably in the range of 112 to 135 °C, more preferably in the range of 114 to 130 °C, and most preferably in the range of 115 to 125 °C.

[0039] Preferably, the random propylene copolymer (R-PP) of the present invention has a flexural modulus (ISO 527) of at least 800 MPa, preferably at least 825 MPa, more preferably at least 850 MPa, and most preferably at least 875 MPa.

[0040] The flexural modulus is generally not greater than 1400 MPa.

[0041] Therefore, it is preferred that the random propylene copolymer (R-PP) of the present invention has a flexural modulus (ISO 527) in the range of 800 to 1400 MPa, preferably in the range of 825 to 1300 MPa, more preferably in the range of 850 to 1200 MPa, and most preferably in the range of 875 to 1100 MPa.

[0042] Preferably, the random polypropylene copolymer (R-PP) has a xylene cold soluble content (XCS) measured according to ISO 16152 (25 °C) in the range of 2 to 15 wt%, preferably in the range of 3 to 10 wt%.

[0043] The random propylene copolymer (R-PP) of the present invention can be synthesized or selected from commercially available random propylene copolymers.

[0044] Elastomeric ethylene random copolymer (E)

[0045] As another basic component, the polypropylene composition (PC) comprises an elastomeric ethylene random copolymer (E).

[0046] The elastomeric ethylene random copolymer (E) of the present invention comprises ethylene monomer units and one or more comonomer units in an amount in the range of 30 to 50 wt%, wherein the one or more comonomer units are selected from α-olefins having 4 to 12 carbon atoms, more preferably selected from 1-hexene and 1-octene, and most preferably 1-octene.

[0047] Preferably, the elastomeric ethylene random copolymer (E) of the present invention consists of ethylene monomer units and 1-octene comonomer units.

[0048] The comonomer units of the elastomeric ethylene random copolymer (E) are preferably present in the range of 30 to 50 wt%, more preferably in the range of 35 to 45 wt%, as determined by 13 C-NMR spectroscopy.

[0049] The elastomeric ethylene random copolymer (E) of the present invention has a melting temperature (ISO 11357) of at least 75 °C, preferably at least 90 °C, more preferably at least 100 °C, and most preferably at least 110 °C.

[0050] The elastomeric ethylene random copolymer (E) of the present invention preferably has a density in the range of 860 to 890 kg / m 3 range, more preferably in the range of 862 to 880 kg / m 3 range, and most preferably in the range of 865 to 875 kg / m 3 range.

[0051] The elastomeric ethylene random copolymer (E) of the present invention preferably has a melt flow rate MFR in the range of 0.1 to 2.0 g / 10 min, more preferably in the range of 0.2 to 1.5 g / 10 min, and most preferably in the range of 0.3 to 1.0 g / 10 min. 2 (190 °C, 2.16 kg, ISO 1133).

[0052] The elastomeric ethylene random copolymer (E) of the present invention can be selected from commercially available elastomeric ethylene random copolymers or synthesized directly. Preferably, the elastomeric ethylene random copolymer (E) is a commercially available elastomeric ethylene random copolymer.

[0053] In a particularly preferred embodiment, the elastomeric ethylene random copolymer (E) is a commercial product Engage XLT 8677 available from Dow Chemical Company (USA). TM XLT 8677.

[0054] Additive (A)

[0055] The polypropylene composition (PC) of the present invention may contain an additive (A) in an amount of 0 to 5.0% by weight. Skilled practitioners can select suitable additives known in the art.

[0056] Additive (A) is preferably selected from antioxidants, UV stabilizers, scratch resistant agents, mold release agents, acid scavengers, lubricants, antistatic agents, and mixtures thereof.

[0057] Skilled practitioners will recognize that talc can be used in similar compositions as a nucleating agent or as an inorganic filler. If talc is present in the polypropylene composition (PC) of the present invention, the talc must be present only in an amount suitable for its use as a nucleating agent, suitably less than 1.0% by weight, more preferably less than 0.5% by weight, and most preferably less than 0.3% by weight.

[0058] Preferably, the polypropylene composition (PC) does not contain talc, and more preferably does not contain any type of inorganic filler.

[0059] It should be understood that the content of additive (A) given relative to the total weight of the polypropylene composition (PC) includes any carrier polymer used to introduce the additive into the polypropylene composition (PC), i.e., the masterbatch carrier polymer. Examples of such carrier polymers can be polypropylene homopolymers in powder form.

[0060] Polypropylene composition (PC)

[0061] It is desirable that the polypropylene composition of the present invention has properties suitable for use as a laminated film for injection-molded polypropylene articles. Important properties are those required for extrusion into a film (melt flow rate and softness) and those required for lamination (melting temperature).

[0062] Thus, the polypropylene composition (PC) of the present invention has a melt flow rate MFR in the range of 1.0 to 5.0 g / 10 min, preferably in the range of 1.1 to 4.0 g / 10 min, more preferably in the range of 1.2 to 3.0 g / 10 min, and most preferably in the range of 1.3 to 2.0 g / 10 min 2 (230 °C, 2.16 kg, ISO 1133).

[0063] The polypropylene composition (PC) of the present invention preferably has a melting temperature (ISO 11357) in the range of 110 to 125 °C, more preferably in the range of 111 to 122 °C, and most preferably in the range of 112 to 120 °C.

[0064] The polypropylene composition (PC) of the present invention preferably has a Vicat softening temperature, Method A (ISO 306) in the range of 85 to 105 °C, more preferably in the range of 88 to 102 °C, and most preferably in the range of 90 to 100 °C.

[0065] The polypropylene composition (PC) of the present invention comprises several basic components, including an atactic polypropylene copolymer (R-PP), an elastomeric ethylene random copolymer (E), and optionally additives (A). Thus, the polypropylene composition (PC) comprises:

[0066] a) 60 to 90 wt% of an atactic polypropylene copolymer (R-PP) having propylene monomer units and one or more comonomer units selected from ethylene and / or α-olefins having 4 to 12 carbon atoms, wherein

[0067] i) the melt flow rate MFR 2 (230 °C, 2.16 kg, ISO 1133) is in the range of 0.1 to 15.0 g / 10 min, and

[0068] ii) the Vicat softening temperature, Method A (ISO 306) is in the range of 110 to 140 °C,

[0069] b) 5 to 35 wt% of an elastomeric ethylene random copolymer (E) having ethylene monomer units and one or more comonomer units selected from α-olefins having 4 to 12 carbon atoms,

[0070] wherein the melting temperature (ISO 11357) is at least 75 °C,

[0071] c) 0 to 5% by weight of additive (A).

[0072] The random propylene copolymer (R-PP) preferably has a comonomer unit content in the range of 2 to 5% by weight, determined by quantitative 13 13C-NMR spectroscopy, and the comonomer unit is selected from ethylene and / or α-olefins having 4 to 12 carbon atoms.

[0073] The elastomeric ethylene random copolymer (E) preferably has a comonomer unit content in the range of 30 to 50% by weight, determined by quantitative 13 13C-NMR spectroscopy, and the comonomer unit is selected from α-olefins having 4 to 12 carbon atoms.

[0074] In addition to the basic components defined above, the polypropylene composition (PC) of the present invention may further contain other components. However, it is preferred that the respective contents of the random propylene copolymer (R-PP), the elastomeric ethylene random copolymer (E), and the additive (A) total at least 90% by weight, more preferably at least 95% by weight, based on the total weight of the polypropylene composition (PC). Most preferably, the polypropylene composition (PC) consists only of (R-PP), (E), and (A).

[0075] As described above, it is preferred that the polypropylene composition (PC) does not contain talc, and more preferably does not contain any type of inorganic filler.

[0076] The polypropylene composition (PC) comprises:

[0077] a) 60 to 90% by weight of a random propylene copolymer (R-PP)

[0078] b) 5 to 35% by weight of an elastomeric ethylene random copolymer (E)

[0079] c) 0 to 5% by weight of additive (A).

[0080] The content of the random propylene copolymer (R-PP) in the polypropylene composition (PC) is 60 to 90% by weight, more preferably 63 to 85% by weight, and most preferably 65 to 80% by weight.

[0081] The content of the elastomeric ethylene random copolymer (E) in the polypropylene composition (PC) is 5 to 35% by weight, more preferably 10 to 33% by weight, and most preferably 15 to 30% by weight.

[0082] Therefore, it is preferred that the polypropylene composition (PC) comprises:

[0083] a) 63 to 85% by weight of a random propylene copolymer (R-PP)

[0084] b) 10 to 33% by weight of an elastomeric ethylene random copolymer (E)

[0085] c) 0 to 5% by weight of an additive (A).

[0086] Further preferably, the polypropylene composition (PC) comprises:

[0087] a) 65 to 80% by weight of a random propylene copolymer (R-PP)

[0088] b) 15 to 30% by weight of an elastomeric ethylene random copolymer (E)

[0089] c) 0 to 5% by weight of an additive (A).

[0090] Preferably, the ratio of the content of the random propylene copolymer (R-PP) to the content of the elastomeric ethylene random copolymer (E), (R-PP) / (E), is in the range of 2 to 5, more preferably in the range of 2.0 to 5.0, and most preferably in the range of 2.0 to 4.0.

[0091] The preparation and further processing of the polypropylene composition (PC) includes, for example, mixing the individual components of the polypropylene composition (PC) by using conventional compounding or blending devices (such as a Banbury mixer, a two-roll rubber mill, a Buss-co-kneader, or a twin-screw extruder), and then pelletizing. The typical extrusion temperature is in the range of 160 to 210 °C, or more preferably in the range of 180 to 200 °C. Films, preferably cast films, multi-layer or single-layer films, can be prepared from the pellets of the polypropylene composition (PC).

[0092] Process for the preparation of the random propylene copolymer (R-PP)

[0093] The polymerization system for the preparation of the random propylene copolymer (R-PP) can include one or more conventionally stirred slurry reactors and / or one or more gas-phase reactors. Preferably, the reactors used are selected from the group of loop and gas-phase reactors, and in particular, at least one loop reactor is used in this process. Multiple reactors of each type can also be used, such as one loop reactor and two or three gas-phase reactors in series, or two loop reactors and one or two gas-phase reactors in series.

[0094] Preferably, the process further includes prepolymerization using the selected catalyst system, which, as described in detail below, comprises a Ziegler-Natta main catalyst, an external donor, and a cocatalyst.

[0095] In a preferred embodiment, the prepolymerization is carried out as a bulk slurry polymerization in liquid propylene, i.e. the liquid phase mainly comprises propylene, in which a small amount of other reactants and optionally inert components are dissolved.

[0096] The prepolymerization reaction is typically carried out at a temperature of from 0 to 50 °C, preferably from 10 to 45 °C, and more preferably from 15 to 40 °C.

[0097] The pressure in the prepolymerization reactor is not critical, but must be high enough to maintain the reaction mixture as a liquid phase. Thus, the pressure can be from 20 to 100 bar, for example from 30 to 70 bar.

[0098] Preferably all the catalyst components are introduced into the prepolymerization step. However, in cases where the solid catalyst component (i) and the cocatalyst (ii) can be fed separately, only a part of the cocatalyst can be introduced into the prepolymerization stage, while the remaining part is introduced into the subsequent polymerization stage. Moreover, in such cases, a large amount of cocatalyst needs to be introduced in the prepolymerization stage to obtain a sufficient polymerization reaction therein.

[0099] Other components can also be added in the prepolymerization stage. Thus, hydrogen can be added in the prepolymerization stage to control the molecular weight of the prepolymer, which is known in the art. In addition, antistatic additives can be used to prevent the particles from adhering to each other or to the reactor walls.

[0100] The precise control of the prepolymerization conditions and reaction parameters belongs to the technical scope of the art.

[0101] A slurry reactor means any reactor operating in bulk or slurry and in which the polymer is formed in particulate form, such as a continuous or simple batch stirred tank reactor or a loop reactor. "Bulk" means polymerization in a reaction medium containing at least 60% by weight of monomer. According to a preferred embodiment, the slurry reactor comprises a bulk loop reactor.

[0102] "Gas-phase reactor" means any mechanically stirred or fluidized bed reactor. Preferably, the gas-phase reactor comprises a mechanically stirred fluidized bed reactor with a gas velocity of at least 0.2 m / s.

[0103] A preferred multistage process is a slurry-gas phase process, such as the process developed by Borealis and known as technology. In this regard, reference is made to EP 0 887 379 A1, WO 92 / 12182, WO 2004 / 000899, WO 2004 / 111095, WO 99 / 24478, WO 99 / 24479 and WO 00 / 68315. They are incorporated herein by reference.

[0104] Another suitable slurry-gas phase process is that of Basell's Process

[0105] Preferably, the random propylene copolymer (R-PP) according to the present invention is preferably produced in or in -PP process by using a specific Ziegler-Natta main catalyst in combination with a specific external donor, as described in detail below.

[0106] Therefore, a preferred multi-stage process may include the following steps:

[0107] - Producing a random propylene copolymer (R-PP) in a first slurry reactor and optionally in a second slurry reactor in the presence of a selected catalyst system, as described in detail below, for example, the catalyst system includes a specific Ziegler-Natta main catalyst (i), an external donor (iii) and a cocatalyst (ii), and the same polymerization conditions are used in both slurry reactors.

[0108] - Optionally transferring the slurry reactor product to at least one first gas-phase reactor, such as a gas-phase reactor or a first gas-phase reactor and a second gas-phase reactor connected in series.

[0109] - Recovering the polymer product for further processing.

[0110] Regarding the above preferred slurry or slurry-gas phase process, the following general information about process conditions can be provided.

[0111] The temperature is preferably 40 to 110 °C, preferably between 50 and 100 °C, especially between 60 and 90 °C, and the pressure is in the range of 20 to 80 bar, preferably in the range of 30 to 60 bar. Hydrogen can be optionally added to control the molecular weight in a manner known per se.

[0112] The reaction product of the slurry polymerization preferably carried out in a loop reactor is optionally transferred to one or more subsequent gas-phase reactors, where the temperature is preferably in the range of 50 to 130 °C, more preferably in the range of 60 °C to 100 °C, and the pressure is in the range of 5 to 50 bar, preferably in the range of 8 to 35 bar. Hydrogen can also be optionally added to control the molecular weight in a manner known per se.

[0113] The average residence time in the above reactor zones may vary. In one embodiment, the average residence time in the slurry reactor (e.g., loop reactor) is in the range of 0.5 to 5 hours, for example, in the range of 0.5 to 2 hours, while the average residence time in the gas-phase reactor is generally 1 to 8 hours.

[0114] If desired, the polymerization can be carried out in a slurry reactor (preferably a loop reactor) under supercritical conditions in a known manner and / or in a gas-phase reactor in a condensation mode.

[0115] According to the present invention, an atactic propylene copolymer (R-PP) is obtained by the polymerization process as described above in the presence of a catalyst system comprising a Ziegler-Natta main catalyst as component (i), the Ziegler-Natta main catalyst comprising a transesterification product of a lower alcohol and a phthalate ester.

[0116] The main catalyst used according to the present invention is prepared by the following method

[0117] a) Reacting a spray-crystallized or emulsion-solidified adduct of MgCl 2 and C 1 -C 2 alcohol with TiCl 4

[0118] b) Reacting the product of stage a) with the dialkyl phthalate of formula (I) under conditions for transesterification between the C 1 to C 2 alcohol and the dialkyl phthalate of formula (I) to form an internal donor,

[0119]

[0120] wherein R 1’ and R 2’ are each independently at least C 5 alkyl,

[0121] c) Washing the product of stage b), or

[0122] d) Optionally reacting the product of step c) with additional TiCl 4

[0123] The main catalyst is produced as defined, for example, in patent applications WO 87 / 07620, WO 92 / 19653, WO 92 / 19658 and EP 0 491566. The contents of these documents are incorporated herein by reference.

[0124] First, an adduct of MgCl 2 and C 1 -C 2 alcohol is formed, having the formula MgCl 2 *nROH, where R is methyl or ethyl and n is from 1 to 6. Ethanol is preferably used as the alcohol.

[0125] The adduct, which is first melted and then spray-crystallized or emulsion-solidified, is used as the catalyst support. ​​

[0126] In the next step, a spray crystallization or emulsion solidification adduct of the formula MgCl 2 *nROH (wherein R is methyl or ethyl, preferably ethyl, and n is from 1 to 6) is contacted with TiCl 4 to form a titanated support, followed by the steps of:

[0127] · Adding the following compounds to the titanated support to form a first product,

[0128] (i) A dialkyl phthalate of formula (I), wherein R 1’ and R 2’ are independently at least C 5 -alkyl, such as at least C 8 -alkyl,

[0129] or preferably

[0130] (ii) A dialkyl phthalate of formula (I), wherein R 1’ and R 2’ are the same and are at least C 5 -alkyl, such as at least C 8 -alkyl,

[0131] or more preferably

[0132] (iii) A dialkyl phthalate of formula (I) selected from the group consisting of propyl hexyl phthalate (PrHP), dioctyl phthalate (DOP), diisodecyl phthalate (DIDP), and ditridecyl phthalate (DTDP), still more preferably, the dialkyl phthalate of formula (I) is dioctyl phthalate (DOP), such as diisooctyl phthalate or diethylhexyl phthalate, especially diethylhexyl phthalate,

[0133] · Subjecting the first product to suitable transesterification reaction conditions, i.e., to a temperature above 100 °C, preferably between 100 and 150 °C, more preferably between 130 and 150 °C, such that the methanol or ethanol transesterifies with the ester groups of the dialkyl phthalate of formula (I) to form preferably at least 80 mol%, more preferably 90 mol%, most preferably 95 mol% of the dialkyl phthalate of formula (II)

[0134]

[0135] wherein R 1 and R 2 are methyl or ethyl, preferably ethyl,

[0136] The dialkyl phthalate of formula (II) is an internal donor, and

[0137] · Recover the transesterification reaction product as the main catalyst component (component (i)).

[0138] In a preferred embodiment, an adduct of the formula MgCl 2 *nROH (where R is methyl or ethyl and n is from 1 to 6) is melted and then preferably the melt is injected into a cooled solvent or a cooled gas by a gas, whereby the adduct is crystallized into a morphologically favorable form, as described, for example, in WO 87 / 07620. As described in WO 92 / 19658 and WO 92 / 19653, this crystalline adduct is preferably used as a catalyst support and reacted to form the main catalyst useful in the present invention.

[0139] When the catalyst residue is removed by extraction, an adduct of the titanated support and the internal donor is obtained, in which the group derived from the ester alcohol has changed.

[0140] If sufficient titanium remains on the support, it will act as the active element of the main catalyst.

[0141] Otherwise, titanation is repeated after the above treatment to ensure a sufficient titanium concentration and thus ensure activity.

[0142] Preferably, the main catalyst used according to the present invention contains at most 2.5% by weight, preferably at most 2.2% by weight, and more preferably at most 2.0% by weight of titanium. Its donor content is preferably between 4 and 12% by weight, and more preferably between 6 and 10% by weight.

[0143] More preferably, the main catalyst used according to the present invention has been prepared by using ethanol as the alcohol and dioctyl phthalate (DOP) as the dialkyl phthalate of formula (I), yielding diethyl phthalate (DEP) as the internal donor compound.

[0144] In a preferred embodiment, the main catalyst is obtained by the emulsion technology developed by Borealis. In this regard, reference is made to WO 2009 / 040201. Thus, preferably, the main catalyst is obtained by a method comprising the following steps:

[0145] a) Preparing a solution of a complex of the metal and the electron donor by reacting a compound of a Group 2 metal with an electron donor or a precursor thereof in an organic liquid reaction medium;

[0146] b) Adding the solution of the complex to at least one compound of a transition metal of any one of Groups 4 to 6 to produce an emulsion, the dispersed phase of which contains more than 50 mol% of the Group 2 metal in the complex;

[0147] c) Optionally, stir the emulsion in the presence of an emulsion stabilizer so as to maintain the droplets of the dispersed phase within an average particle size range suitably of 5 to 200 μm, preferably 10 to 100 μm, and even more preferably 20 to 50 μm;

[0148] d) Cure the droplets of the dispersed phase; and

[0149] e) Recover the cured particles of the obtained olefin polymerization catalyst.

[0150] The Group 2 metal used in the preparation of the main catalyst according to the emulsion technique is preferably magnesium, and the liquid organic medium used to react the Group 2 metal compound preferably comprises C 6 -C 10 aromatic hydrocarbons, preferably including toluene. The electron donor compound reacting with the Group 2 metal compound is preferably a monoester or diester of an aromatic carboxylic acid or diacid, the latter being capable of forming a complex of a chelate-like structure. The aromatic carboxylic acid ester or diester can be formed in situ by the reaction of an aromatic carboxylic acid acyl chloride or diacyl chloride with C 2 -C 16 alkanols and / or diols, and is preferably dioctyl phthalate or bis-(2-ethylhexyl) phthalate. The reaction for preparing the Group 2 metal complex is generally carried out at a temperature of 20 to 80 °C, and in the case where the Group 2 metal is magnesium, the preparation of the magnesium complex can advantageously be carried out at a temperature of 50 to 70 °C. The compounds of Group 4 to 6 metals are preferably compounds of Group 4 metals. The Group 4 metal is preferably titanium, and the compound reacting with the complex of the Group 2 metal is preferably a halide. In a further embodiment of the present invention, the compounds of Group 4 to 6 metals can also be selected from Group 5 metals and Group 6 metals, such as Cu, Fe, Co, Ni and / or Pd compounds. In a preferred embodiment of the catalyst production process, a turbulence minimizer (TMA) is added to the reaction mixture before curing the particles of the dispersed phase, the TMA being inert under the reaction conditions and soluble in the reaction mixture. The turbulence minimizer (TMA) or its mixture is preferably a polymer having a linear aliphatic carbon backbone, which can be branched only with short side chains to provide uniform flow conditions during stirring. The TMA is particularly preferably selected from those having a high molecular weight M of about 1 to 40×10 6 w(measured by gel permeation chromatography) of alpha-olefin polymers or mixtures thereof. Particularly preferred are polymers of alpha-olefin monomers with 6 to 20 carbon atoms, and more preferably polyoctenes, polynonenes, polydecenes, polyundecenes or polydodecenes or mixtures thereof, having molecular weights and general backbone structures as defined above, and most preferably TMAs are polydecenes. Typically, the turbulence minimizing agent may be added in any process step before the formation of particles, i.e., at the latest before the emulsion solidifies, and is added to the emulsion in an amount of 1 to 1000ppm, preferably 5 to 100ppm and more preferably 5 to 50ppm based on the gross weight of the reaction mixture. In a preferred embodiment of the invention, the primary catalyst is obtained by the following steps: by incorporating C 6 -C 10 Aromatic hydrocarbons or C 6 -C 10 Aromatic hydrocarbons and C 5 -C 9 C of a mixture of aliphatic hydrocarbons 6 -C 10 A solution of a magnesium complex is prepared by reacting an alkoxymagnesium compound and an electron donor or a precursor thereof in an aromatic liquid reaction medium; the magnesium complex is reacted with a compound of at least one tetravalent Group 4 metal at a temperature above 10° C. and below 60° C. to form a denser, insoluble TiCl2O3 having a Group 4 metal / Mg molar ratio of 0.1 to 10 in an oil dispersed phase having a Group 4 metal / Mg molar ratio of 10 to 100. 4 / toluene; maintaining the droplets of the dispersed phase in the size range of 5 to 200 μm by stirring in the presence of an emulsion stabilizer, while heating the emulsion to solidify the droplets and adding a turbulence minimizer to the reaction mixture prior to solidifying the droplets of the dispersed phase, the turbulence minimizer being inert under the reaction conditions and soluble in the reaction mixture; and solidifying the particles of the dispersed phase by heating and recovering the catalyst particles obtained. Thus, the dispersed phase and the dispersed phase are distinguished from each other in that the denser oil will not dissolve in a toluene solution of titanium tetrachloride if it comes into contact therewith. Suitable TiCl 4 / Toluene solution is TiCl 4A solution with a toluene molar ratio of 0.1 to 0.3. The difference between the dispersed phase and the phase to be dispersed also lies in that a large proportion of Mg (as a complex) provided for reaction with the Group 4 metal compound exists in the dispersed phase, as can be seen by comparing the corresponding Group 4 metal / Mg molar ratios. Thus, in fact, the reaction product of the Mg complex with the Group 4 metal (which is the precursor of the final catalyst) almost entirely becomes the dispersed phase and becomes the final dry particle form through further processing steps. The dispersed phase still containing an effective amount of the Group 4 metal can be reprocessed to recover the metal. By carrying out the reaction of the Mg complex / Group 4 metal compound at a low temperature, especially at a temperature higher than 10 °C but lower than 60 °C, preferably between 20 °C and 50 °C, the formation of the two-phase reaction product rather than the single-phase reaction product is promoted. Since the two phases naturally tend to separate into a lower, denser phase and a supernatant lighter phase, it is necessary to maintain the reaction product as an emulsion by stirring, preferably in the presence of an emulsion stabilizer. The particles obtained from the dispersed phase of the emulsion have a certain size, shape (spherical) and uniformity, which makes the final catalyst very effective in olefin polymerization. This morphology is retained during the heating and curing of the particles and, of course, also in the final washing and drying steps. In contrast, due to the substantially uncontrollable nucleation and growth and the large number of variables affecting these events, it is very difficult or even impossible to achieve this morphology by precipitation. The electron donor is preferably an aromatic carboxylic acid ester, and particularly preferred esters are dioctyl phthalate and bis-(2-ethylhexyl) phthalate. The donor can be conveniently formed in situ by the reaction of an aromatic carboxylic acid acyl chloride precursor with a C 2 -C 16 alkanols and / or diols. The liquid reaction medium preferably includes toluene. In addition, an emulsifier / emulsion stabilizer can be additionally used in a manner known in the art to promote the formation and / or stability of the emulsion. For the above purposes, for example, surfactants such as a class based on acrylic polymers or methacrylic polymers can be used. Preferably, the emulsion stabilizer is an acrylic polymer or a methacrylic polymer, especially those having medium-sized ester side chains with more than 10, preferably more than 12 carbon atoms, and preferably less than 30, and preferably 12 to 20 carbon atoms. Particularly preferred are unbranched C 12 -C 20Acrylates, such as poly(hexadecyl)-methacrylate and poly(octadecyl)-methacrylate. It has been found that the best results are obtained when the Group 4 metal / Mg molar ratio of the denser oil is from 1 to 5, preferably from 2 to 4, and the Group 4 metal / Mg molar ratio of the dispersed-phase oil is from 55 to 65. Generally, the ratio of the Group 4 metal / Mg molar ratio in the dispersed-phase oil to the Group 4 metal / Mg molar ratio of the denser oil is at least 10. The droplets of the dispersed phase are solidified by heating, which is suitably carried out at a temperature in the range of 70 to 150 °C, usually in the range of 90 to 110 °C.

[0151] The resulting main catalyst is desirably in the form of particles having an average particle size in the range of 5 to 200 μm, preferably 10 to 100 μm, more preferably 20 to 50 μm. The reagents can be added to the aromatic reaction medium in any order. However, preferably, in the first step, the alkoxymagnesium compound reacts with the carboxylic acid halide precursor of the electron donor to form an intermediate; and in the second step, the obtained product further reacts with the Group 4 metal. Each alkoxy group of the magnesium compound preferably contains 1 to 20 carbon atoms, and the carboxylic acid should contain at least 8 carbon atoms. The reaction of the magnesium compound, the carboxylic acid halide, and the alcohol proceeds satisfactorily at a temperature in the range of 20 to 80 °C, preferably in the range of 50 to 70 °C. The product of this reaction, the "magnesium complex", reacts with the Group 4 metal compound at a lower temperature to form a two-phase oil-in-oil product. The reaction medium used as a solvent can be aromatic or a mixture of aromatic hydrocarbons and aliphatic hydrocarbons, the latter preferably containing 5 to 9 carbon atoms, more preferably containing 5 to 7 carbon atoms, or a mixture thereof. Preferably, the liquid reaction medium used as a solvent in the reaction is aromatic and more preferably selected from hydrocarbons such as substituted and unsubstituted benzene, preferably selected from alkylated benzenes, even more preferably selected from toluene and xylene, and most preferably toluene. The molar ratio of the aromatic medium to magnesium is preferably less than 10, for example 4 to 10, preferably 5 to 9. The alkoxymagnesium compound group is preferably selected from the group consisting of complexes of dialkoxymagnesium, magnesium dihalide, and alcohol, and complexes of magnesium dihalide and dialkoxymagnesium. It can be the reaction product of an alcohol and a magnesium compound selected from the group consisting of dialkylmagnesium, alkylalkoxymagnesium, alkylmagnesium halide, and magnesium dihalide.

[0152] It can also be selected from the group consisting of dialkoxymagnesium, diaryloxymagnesium, alkoxymagnesium halide, aryloxymagnesium halide, alkylalkoxymagnesium, arylalkoxymagnesium, and alkylaryloxymagnesium. Dialkoxymagnesium can be the reaction product of magnesium dihalide (such as magnesium dichloride) or dialkylmagnesium of the formula R'xR"yMg, where x + y = 2 and x and y are in the range of 0.3 to 1.7 and each of R' and R" is a similar or different C 1 -C 20 alkyl group, preferably a similar or different C 4 -C10 Alkyl. Typical alkylmagnesiums are ethylbutylmagnesium, dibutylmagnesium, dipropylmagnesium, propylbutylmagnesium, dipentylmagnesium, butylpentylmagnesium, butyloctylmagnesium, and dioctylmagnesium. Preferably, R' is butyl and R" is octyl, i.e., the dialkylmagnesium compound is butyloctylmagnesium, and most preferably the dialkylmagnesium compound is Mg[(Bu) 1.5 (Oct) 0.5 .

[0153] The dialkylmagnesium, alkylalkoxymagnesium, or magnesium dihalide can react with a polyhydric alcohol R(OH) m (where m ranges from 2 to 4) or a monohydric alcohol ROH or a mixture thereof. Typical C 2 to C 6 polyhydric alcohols can be straight-chain or branched-chain and include ethylene glycol, propylene glycol, propylene glycol (also known as 1,3-propanediol), 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,8-octanediol, pinacol, diethylene glycol, triethylene glycol, and triols such as glycerol, trimethylolpropane, and pentaerythritol. The aromatic reaction medium can also contain a monohydric alcohol, which can be straight-chain or branched-chain. Typical C 1 -C 5 monohydric alcohols are methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, sec-butanol, tert-butanol, n-pentanol, isopentanol, sec-pentanol, tert-pentanol, diethylmethanol, 2-methyl-1-butanol, sec-isopentanol, tert-butylmethanol. Typical C 6 -C 10 monohydric alcohols are hexanol, 2-ethyl-1-butanol, 4-methyl-2-pentanol, 1-heptanol, 2-heptanol, 4-heptanol, 2,4-dimethyl-3-pentanol, 1-octanol, 2-octanol, 2-ethyl-1-hexanol, 1-nonanol, 5-nonanol, diisobutylmethanol, 1-decanol, and 2,7-dimethyl-2-octanol. Typical >C 10 monohydric alcohols are n-1-undecanol, n-1-dodecanol, n-1-tridecanol, n-1-tetradecanol, n-1-pentadecanol, 1-hexadecanol, n-1-heptadecanol, and n-1-octadecanol. The monohydric alcohols can be unsaturated provided they do not act as catalyst poisons. Preferred monohydric alcohols are those of the formula ROH where R is C 2 -C 16 alkyl, most preferably C 4 -C 12 alkyl, especially 2-ethyl-1-hexanol or 1-octanol.

[0154] Preferably, substantially all aromatic carboxylic acid esters are carboxylic acid halides, preferably dicarboxylic acid dihalides, more preferably unsaturated dicarboxylic acid dihalides, and most preferably the reaction product of phthaloyl chloride with a monohydric alcohol.

[0155] Compounds of Group 4 metals in the tetravalent state containing halogens are preferably titanium tetrahalides. Equivalent to titanium tetrahalides is a combination of titanium alkoxyhalides and a halogenating agent, which are capable of forming titanium tetrahalide in situ. The most preferred halide is chloride.

[0156] It is well known that adding at least one halogenated hydrocarbon during the main catalyst preparation process can further improve the catalytic activity. The reactive halogenated hydrocarbons preferably have the formula R'"X'", n wherein R'" is a C 1 -C 20 hydrocarbyl group, especially a C 1 -C 10 aliphatic hydrocarbyl group, X'" is a halogen, preferably chlorine, and n is an integer from 1 to 4.

[0157] Such chlorinated hydrocarbons include methyl chloride, methylene chloride, chloroform, carbon tetrachloride, chloroethane, (1,1)-dichloroethane, (1,2)-dichloroethane, (1,1,1)-trichloroethane, (1,1,2)-trichloroethane, (1,1,1,2)-tetrachloroethane, (1,1,2,2)-tetrachloroethane, pentachloroethane, hexachloroethane, 1-chloropropane, 2-chloropropane, (1,2)-dichloropropane, (1,3)-dichloropropane, (1,2,3) trichloropropane, 1-chlorobutane, 2-chlorobutane, isobutyl chloride, tert-butyl chloride, (1,4)-dichlorobutane, 1-chloropentane, and (1,5)-dichloropentane. The chlorinated hydrocarbons can also be unsaturated, provided that the unsaturation is not a catalyst poison in the final catalyst.

[0158] In the above formula, R'" is preferably a C 1 -C 10 alkyl group, X'" is preferably chlorine, and n is preferably 1 or 2. Preferred compounds include butyl chloride (BuCl), dichloroalkanes such as (1,4)-dichlorobutane, and tert-butyl chloride.

[0159] The catalyst preparation as described herein can be carried out batchwise, semi-continuously or continuously. In such a semi-continuous or continuous process, a solution of a complex of a Group 2 metal and the electron donor (prepared by reacting a compound of the metal with the electron donor in an organic liquid reaction medium) is mixed with at least one transition metal compound, which may be dissolved in the same or a different organic liquid reaction medium. Then, the solution thus obtained can be stirred in the presence of an emulsion stabilizer, and then the stirred emulsion is fed into a temperature gradient reactor, in which the emulsion is subjected to a temperature gradient, resulting in the solidification of the droplets of the dispersed phase of the emulsion. TMA is preferably included in the solution of the complex or added to the solution before feeding the stirred solution into the temperature gradient reactor.

[0160] When feeding the stirred emulsion to a temperature gradient reactor, an inert solvent in which the droplets are insoluble can additionally be fed into the gradient reactor to improve the formation of the droplets, thereby resulting in a uniform particle size of the catalyst particles formed in the temperature gradient reactor when passing through the pipeline. This additional solvent can be the same as the organic liquid reaction medium for preparing the solution of the complex of Group 2 metals as explained in more detail above.

[0161] Subsequently, the solidified particles of the catalyst can be recovered by an in-stream filtration unit and preferably washed to remove unreacted starting components.

[0162] The recovered particulate product is washed with a hydrocarbon at least once, preferably at least twice, and most preferably at least three times. The hydrocarbon is preferably selected from aromatic hydrocarbons and aliphatic hydrocarbons, preferably washed with toluene, especially with hot (e.g., 90 °C) toluene, which may include a small amount (preferably about 0.01 to 10 vol%) of TiCl 4 or an alkyl aluminum chloride such as diethyl aluminum chloride (DEAC). Advantageously, a further washing step is carried out with heptane, most preferably with hot (e.g., 90 °C) heptane, and a still further washing step is carried out with pentane. The washing steps generally include several sub-steps. For example, a preferred washing sequence is one washing step with toluene at 90 °C, two washing steps with heptane at 90 °C, and one or two washing steps with pentane at room temperature.

[0163] Finally, the washed catalyst is dried, for example, by evaporation or flushing with nitrogen.

[0164] The catalyst system used according to the present invention also includes a cocatalyst, preferably an alkyl aluminum compound, as defined in detail below. In the case of producing the main catalyst by the emulsion technique, the cocatalyst is added in pure form or in solution shortly before the formation of the emulsion begins until it is added to the washing liquid (e.g., toluene) in an amount such that the final Al content of the particles is 0.05 to 1 wt%, preferably 0.1 to 0.8 wt%, and most preferably 0.2 to 0.7 wt% of the final catalyst particles. The most preferred Al content may vary depending on the type of Al compound and the addition step. For example, in some cases, the most preferred amount may be 0.1 to 0.4 wt%.

[0165] In a further embodiment, the Ziegler-Natta main catalyst can be modified by polymerizing a vinyl compound in the presence of a catalyst system comprising a specific Ziegler-Natta main catalyst, an external donor, and a cocatalyst, and the vinyl compound has the following formula:

[0166] CH2 =CH-CHR 3 R 4

[0167] wherein R 3 and R 4 together form a 5- or 6-membered saturated, unsaturated or aromatic ring or independently represent an alkyl group having 1 to 4 carbon atoms, and the modified catalyst is used for preparing the atactic polypropylene copolymer (R-PP) according to the present invention. The polymerized vinyl compound can be used as an α-nucleating agent.

[0168] Regarding the modification of the catalyst, reference is made to International Applications WO 99 / 24478, WO 99 / 24479, especially WO 00 / 68315, regarding the reaction conditions related to the catalyst modification and regarding the polymerization reaction, which are incorporated herein by reference.

[0169] As described above, for the production of the atactic polypropylene copolymer (R-PP) according to the present invention, the catalyst system used preferably further includes an organometallic cocatalyst as component (ii) in addition to a specific Ziegler-Natta main catalyst.

[0170] Therefore, the cocatalyst is preferably selected from the group consisting of trialkylaluminums (such as triethylaluminum (TEA)), dialkylaluminum chlorides and alkyl sesquichlorides.

[0171] Component (iii) of the catalyst system used is an external donor represented by formula (III)

[0172] Si(OCH 3 ) 2 R 2 5 (III)

[0173] wherein R 5 represents a branched alkyl group having 3 to 12 carbon atoms, preferably a branched alkyl group having 3 to 6 carbon atoms, or a cycloalkyl group having 4 to 12 carbon atoms, preferably a cycloalkyl group having 5 to 8 carbon atoms.

[0174] Particularly preferably, R 5 is selected from the group consisting of isopropyl, isobutyl, isopentyl, tert-butyl, tert-pentyl, neopentyl, cyclopentyl, cyclohexyl, methylcyclopentyl and cycloheptyl.

[0175] More specific examples of the alkoxysilane compounds that can be used as the external electron donor in the present invention are diphenyldimethoxysilane, dicyclopentyldimethoxysilane (D-donor), dicyclopentyldiethoxysilane, cyclopentylmethyldimethoxysilane, cyclopentylmethyldiethoxysilane, dicyclohexyldimethoxysilane, dicyclohexyldiethoxysilane, cyclohexylmethyldimethoxysilane (C-donor), cyclohexylmethyldiethoxysilane, methylphenyldimethoxysilane, diphenyldiethoxysilane, cyclopentyltrimethoxysilane, phenyltrimethoxysilane, cyclopentyltriethoxysilane, phenyltriethoxysilane. Most preferably, the organosilane compound is diethylamino-triethoxy-silane (U-donor), cyclohexylmethyldimethoxysilane (C-donor) or dicyclopentyldimethoxysilane (D-donor), with the latter being particularly preferred.

[0176] The properties of the propylene random copolymer (R-PP) containing ethylene and / or C 4 to C 12 α-olefins produced by the method outlined above can be adjusted and controlled using process conditions known to those skilled in the art, for example, by adjusting and controlling one or more of the following process parameters: temperature, hydrogen feed, comonomer feed, propylene feed, catalyst, type and amount of external donor, split ratio between two or more components of the multimodal polymer.

[0177] Preparation of polypropylene composition (PC)

[0178] To mix the various components of the polypropylene composition of the present invention, conventional compounding or blending equipment can be used, such as a Banbury mixer, a two-roll rubber mill, a Brutus co-kneader or a twin-screw extruder. Preferably, the mixing is completed in a co-rotating twin-screw extruder. The polymer material recovered from the extruder is usually in the form of pellets. Then, preferably, these pellets are further processed, for example, by compression molding to produce articles and products of the polypropylene composition (PC) of the present invention.

[0179] Film

[0180] The present invention also relates to a film comprising the polypropylene composition (PC) of the present invention.

[0181] Preferably, relative to the total weight of the film, the film of the present invention comprises at least 90% by weight, more preferably at least 95% by weight, still more preferably at least 97% by weight, and even more preferably at least 99% by weight of the polypropylene composition (PC) of the present invention.

[0182] Particularly preferably, the film of the present invention is composed of the propylene composition (PC) of the present invention.

[0183] Preferably, the film of the present invention is a cast film.

[0184] Particularly preferably, the film of the present invention is a laminated film for polypropylene articles, preferably polypropylene automotive articles, and most preferably polypropylene automotive interior articles.

[0185] The term interior means that the article is not part of the exterior of the vehicle, but part of the interior of the vehicle. Preferred automotive interior articles include door modules, seat structures, armrests, pedals, instrument panels, and interior trim.

[0186] Accordingly, the present invention also relates to an automotive interior article comprising injection-molded polypropylene laminated with a film according to the present invention, the film comprising a polypropylene composition (PC), preferably consisting of a polypropylene composition (PC).

[0187] The laminated automotive interior article according to the present invention will not have typical aesthetic defects usually associated with the injection molding process, such as tiger stripes, gloss differences, etc.

[0188] Another aspect of the present invention is the use of the film according to the present invention for laminating polypropylene articles, preferably for laminating polypropylene automotive articles, and most preferably for laminating polypropylene automotive interior articles.

[0189] Preferably, the film of the present invention is used for laminating injection-molded polypropylene articles, more preferably injection-molded polypropylene automotive articles, and most preferably injection-molded polypropylene automotive interior articles.

[0190] Using the film of the present invention in the lamination of injection-molded articles helps to avoid adverse aesthetic defects usually associated with the injection molding process, such as tiger stripes, gloss differences, etc.

[0191] The present invention will now be described in more detail by way of the examples provided below. It will be clear to those skilled in the art that the following examples are illustrative only and do not impose any further limitation on the present invention described above.

[0192] Examples

[0193] 1. Definitions / Measurement Methods

[0194] Unless otherwise defined, the following definitions of terms and measurement methods apply to the above general description of the present invention and the following examples.

[0195] Density is measured according to ISO 1183-187. Sample preparation is carried out by compression molding according to ISO 1872-2:2007.

[0196] Melting temperature T m is measured according to ISO 11357-3.

[0197] MFR 2It was measured according to ISO 1133 (230 °C, 2.16 kg load).

[0198] The comonomer content was quantified by FTIR spectroscopy

[0199] The comonomer content was determined by quantitative 13 Fourier transform infrared spectroscopy (FTIR) after basic distribution calibration via quantitative C nuclear magnetic resonance (NMR) spectroscopy in a manner known in the art. The film was pressed to a thickness between 100 and 500 μm and the spectrum was recorded in transmission mode.

[0200] Specifically, the baseline-corrected peak areas of the quantitative bands found at 720 to 722 and 730 to 733 cm -1 were used to determine the ethylene content of the polypropylene-co-ethylene copolymer. The quantitative results were obtained on the basis of the reference film thickness.

[0201] Xylene solubles (XCS, wt%): The content of xylene cold solubles (XCS) was determined according to ISO 16152; First Edition; 2005-07-01 at 25 °C.

[0202] Vicat softening temperature: The Vicat softening temperature was determined according to Method A of ISO 306.

[0203] 2. Examples

[0204] 2.1 Synthesis of propylene random copolymer (R-PP)

[0205] The catalyst used for the preparation of R-PP was the self-supported Ziegler-Natta catalyst described in WO 2004 / 029112; triethylaluminum (TEAL) was used as the cocatalyst, and dicyclopentyldimethoxysilane was used as the donor. R-PP was polymerized in a sequential reactor process as described in Table 1:

[0206] Table 1: Preparation of propylene random copolymer (R-PP) by sequential polymerization:

[0207]

[0208] 2.2 Compounding of examples

[0209] The propylene compositions of inventive examples IE1 to IE3 and comparative example CE1 were prepared by compounding based on the formulations shown in Table 2 under the conditions described in Table 3 in a co-rotating twin-screw extruder.

[0210] Table 2: Formulations and their properties for inventive and comparative examples.

[0211] Component Unit CE1 IE1 IE2 IE3 HomoPP wt% 98 R-PP wt% 78 73 68 <![CDATA[Engage TM XLT 8677]]> wt% 20 25 30 PP-H,GD,225 wt% 1.0 1.0 1.0 1.0 Irgafos 168 wt% 0.2 0.2 0.2 0.2 Irganox 1076 wt% 0.2 0.2 0.2 0.2 CaSt wt% 0.3 0.3 0.3 0.3 Rikemal AS-105 wt% 0.3 0.3 0.3 0.3 Total wt% 100 100 100 100 Physical properties of the obtained PP composition compound of the present invention <![CDATA[MFR 2 (230℃)]]> g / 10min 25 1.5 1.4 1.3 Melting temperature ℃ 168 118 116 114 Vicat softening temperature, Method A ℃ 145 100 95 90

[0212] HomoPP polypropylene homopolymer, trade name "HG385MO", commercially available from Borouge Pte Co. (Singapore)

[0213] Engage TM XLT 8677 ethylene / 1-octene elastomer, density 870 kg / m 3 , melt flow rate MFR 2 (at 190 °C, 2.16 kg) is 0.50 g / 10 min, and the melting temperature is 118 °C. Engage TM XLT 8677 is commercially available from Dow Chemical Company (US)

[0214] PP-H, GD 225 polypropylene homopolymer carrier in powder form, melting temperature 160 °C;

[0215] Irgafos 168 tris(2,4-di-tert-butylphenyl) phosphite from BASF SE (CAS No. 31570-04-4), having a melting temperature of 182 °C

[0216] Irganox 1076 octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate from BASF SE (CAS No. 2082-79-3), having a melting temperature of 50 °C;

[0217] CaSt calcium stearate, CAS No. 1592-23-0, commercially available from Faci

[0218] Rikemal AS-105 glycerol monostearate, CAS No. 31566-31-1, commercially available from Riken Vitamin

[0219] Table 3: Conditions for compounding the propylene composition of the present invention

[0220]

[0221] As can be seen from the examples, the polypropylene composition of the present invention according to the present invention has very excellent properties for forming laminated films, wherein the Vicat A temperature and the melt flow rate are much lower, and within the range required for film extrusion, the melting temperature is much higher than room temperature, suitable for laminating automotive interiors. Using such a film for laminating injection-molded automotive interior products can be expected to reduce the appearance of aesthetic defects usually associated with injection-molded products.

Claims

1. A polypropylene composition (PC) comprising a) 60 to 90% by weight of a random propylene copolymer (R-PP) having propylene monomer units and one or more comonomer units selected from ethylene and / or α-olefins having 4 to 12 carbon atoms, wherein i) Melt flow rate MFR measured according to ISO 1133 at 230 °C and a load of 2.16 kg 2 in the range from 0.1 to 15.0 g / 10 min and ii) the Vicat softening temperature measured according to ISO 306, Method A is in the range of 110 to 140 °C, b) 5 to 35% by weight of an elastomeric ethylene random copolymer (E) having ethylene monomer units and 1-hexene or 1-octene, wherein the melting temperature measured according to ISO 11357 is at least 75 °C, c) 0 to 5% by weight of an additive (A), The weight percentages given for each component are relative to the total weight of the polypropylene composition, and the melt flow rate MFR of the polypropylene composition is determined according to ISO 1133 at 230 °C and a load of 2.16 kg. 2 is in the range of 1.0 to 5.0 g / 10 min.

2. The polypropylene composition (PC) according to claim 1, wherein the propylene random copolymer (R-PP) has a content of comonomer units in the range of 2 to 5% by weight, determined by quantitative 13 13C-NMR spectroscopy, and the comonomer units are selected from ethylene and / or α-olefins having 4 to 12 carbon atoms.

3. The polypropylene composition (PC) according to claim 1 or 2, wherein the elastomeric ethylene random copolymer (E) has a content of comonomer units determined by quantitative 13 C-NMR spectroscopy in the range of 30 to 50% by weight, and the comonomer units are selected from α-olefins having 4 to 12 carbon atoms.

4. The polypropylene composition (PC) according to claim 1 or 2, wherein the combined content of the random propylene copolymer (R-PP), the elastomeric ethylene random copolymer (E) and the additive (A) is at least 90% by weight.

5. The polypropylene composition (PC) according to claim 1 or 2, wherein the combined content of the random propylene copolymer (R-PP), the elastomeric ethylene random copolymer (E) and the additive (A) is at least 95% by weight.

6. The polypropylene composition (PC) according to claim 1 or 2, wherein the polypropylene composition (PC) consists of the random propylene copolymer (R-PP), the elastomeric ethylene random copolymer (E) and the additive (A).

7. The polypropylene composition (PC) according to claim 1 or 2, wherein the ratio of the content of the random propylene copolymer (R-PP) to the content of the elastomeric ethylene random copolymer (E) (R-PP) / (E) is in the range of 2 to 5.

8. The polypropylene composition (PC) according to claim 1 or 2, having a melting temperature measured according to ISO 11357 in the range of 110 to 125 °C.

9. The polypropylene composition (PC) according to claim 1 or 2, having a melting temperature measured according to ISO 11357 in the range of 112 to 120 °C.

10. The polypropylene composition (PC) according to claim 1 or 2, having a Vicat softening temperature measured according to ISO 306, Method A in the range of 85 to 105 °C.

11. The polypropylene composition (PC) according to claim 1 or 2, wherein the random propylene copolymer (R-PP) consists of propylene monomer units and ethylene comonomer units.

12. The polypropylene composition (PC) according to claim 1 or 2, wherein the random propylene copolymer (R-PP) has a flexural modulus of at least 800 MPa measured according to ISO 527.

13. The polypropylene composition (PC) according to claim 1 or 2, wherein the elastomeric ethylene random copolymer (E) has a melt flow rate MFR in the range of 0.1 to 2.0 g / 10 min measured according to ISO 1133 at 190 °C and a load of 2.16 kg 2 .

14. The polypropylene composition (PC) according to claim 1 or 2, wherein the elastomeric ethylene random copolymer (E) consists of ethylene monomer units and 1-octene comonomer units.

15. The polypropylene composition (PC) according to claim 1 or 2, wherein the additive (A) is selected from antioxidants, UV stabilizers, scratch resistant agents, mold release agents, lubricants, antistatic agents, acid scavengers, and mixtures thereof.

16. The polypropylene composition (PC) according to claim 1 or 2, which does not contain talc.

17. The polypropylene composition (PC) according to claim 1 or 2, which does not contain any inorganic fillers.

18. A film comprising the polypropylene composition (PC) according to any one of claims 1 to 17.

19. The film according to claim 18, which consists of the polypropylene composition (PC) according to any one of claims 1 to 17.

20. The film according to claim 18 or 19, wherein the film is a cast film.

21. The film according to claim 18 or 19, wherein the film is a laminated film for polypropylene articles.

22. The film according to claim 18 or 19, wherein the film is a laminated film for polypropylene automotive articles.

23. The film according to claim 18 or 19, wherein the film is a laminated film for polypropylene automotive interior articles.

24. An automotive interior article comprising an injection molded polypropylene article laminated with the film according to any one of claims 18 to 23, the film comprising the polypropylene composition (PC) according to any one of claims 1 to 17.

25. The automotive interior article according to claim 24, wherein the film consists of the polypropylene composition (PC) according to any one of claims 1 to 17.

26. Use of the film according to any one of claims 18 to 23 for laminating polypropylene articles.

27. Use of the film according to any one of claims 18 to 23 for laminating polypropylene automotive articles.

28. Use of the film according to any one of claims 18 to 23 for laminating polypropylene automotive interior articles.

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