Polypropylene composition with improved mechanical, optical and barrier properties

Abstract

The present invention relates to a cast film comprising a polypropylene composition comprising: a) a base polymer comprising a propylene homopolymer in an amount of 95 to 100 wt%, based on the total weight of the polypropylene composition; and b) optionally, an additive selected from the group consisting of antioxidants, acid scavengers, stabilizers, fillers, colorants, nucleating agents, slipping agents, anti-blocking agents and antistatic agents in an amount of 0 to 5 wt%, based on the total weight of the polypropylene composition; wherein the polypropylene composition has: a melt flow rate MFR2, measured according to ISO 1133 at 230 DEG C, under a load of 2.16 kg, of from 6.0 to 10.0 g / 10 min; -a xylene cold soluble (XCS) content, measured according to ISO 16152, of from 1.0 to 2.0 wt%; -a melting temperature Tm of 155 to 175 DEG C, measured according to ISO 11357 / Part 3 / Method C2; -a crystallization temperature Tc of 105 to 130 DEG C, measured according to ISO 11357 / Part 3 / Method C2; -a quintuple regularity [mmmm], measured by 13C-NMR spectroscopy, of from 90 to 99.9 mol%.

Description

Technical Field

[0001] This invention relates to a cast film comprising a polypropylene composition comprising a propylene homopolymer and optionally additives selected from antioxidants, acid scavengers, stabilizers, fillers, colorants, nucleating agents, slip agents, antiblocking agents, and antistatic agents. The invention also relates to the use of this cast film in pharmaceutical packaging. Background Technology

[0002] Based on current industry needs and trends, the pharmaceutical packaging industry also places great emphasis on providing easily recyclable packaging for products. In particular, pharmaceutical blister packaging has received considerable attention in Europe in recent years because many blister packs use polyvinyl chloride (PVC), polyvinylidene chloride (PVDC), or fluoropolymers on the blister side, while the push-through closure is made of aluminum; this makes them essentially impossible to recycle mechanically. These structures have been on the market for many years, but their design is not ideal; for example, there are problems with the seal between the aluminum layer and the PVC-based layer. To improve the seal, an additional sealing layer must be placed between these two layers; this ultimately makes recycling even more complicated and increases production costs. Furthermore, PVC's high moisture permeability also makes it unattractive as a pharmaceutical blister packaging material, as it makes it difficult to keep the package contents free from any contamination.

[0003] Extensive research has been conducted in this field on various blister packaging solutions focused on improving different performance characteristics. For example, US 2020 / 0399037 A1 discloses a multilayer structure suitable for blister packaging applications. This document aims to address moisture permeability issues associated with blister packaging materials and discloses a multilayer structure comprising, in the following order: a first polymer layer (which may be metallized polyethylene terephthalate (PET)), a first adhesive layer (which may be an adhesive varnish), a second polymer layer (which may be a cycloolefin or trifluorochloroethylene homopolymer), a second adhesive layer (which may be an adhesive varnish), and a third polymer layer (which may contain polypropylene or PVC). However, this structure inevitably presents problems during mechanical recycling and requires a lamination step in production, leading to a significant increase in the cost of the final product.

[0004] On the other hand, document EP 0570188 B2 discloses the use of sheets as blister packs or pressure-push-through (PTP) packages, aiming to address issues related to moisture barrier properties. However, blister packs or PTPs comprise a layer consisting of at least one amorphous polyolefin resin and a crystalline polyolefin resin with a possible crystallinity greater than 10% (measured by X-ray diffraction). While each sheet exhibits high moisture barrier properties, its thermal stability is limited by the low glass transition temperature of the amorphous polyolefin used.

[0005] Therefore, there remains a need for polymer-based films exhibiting improved mechanical, optical, and barrier properties. This invention addresses these problems and achieves the aforementioned improved properties through the polymer compositions disclosed herein. Summary of the Invention

[0006] This invention relates to a cast film comprising a polypropylene composition, said polypropylene composition comprising:

[0007] a) A base polymer, based on the total weight of the polypropylene composition, wherein the base polymer comprises 95 to 100% by weight of a propylene homopolymer; and

[0008] b) Optionally, based on the total weight of the polypropylene composition, at least one additive in an amount of 0 to 5% by weight, said additive being selected from antioxidants, acid scavengers, stabilizers, fillers, colorants, nucleating agents, slip agents, antiblocking agents and antistatic agents;

[0009] The polypropylene composition comprises:

[0010] - Melt flow rate MFR2, measured at 230°C and 2.16 kg load according to ISO 1133, is 6.0 to 10.0 g / 10 min.

[0011] - Content of xylene cold solubles (XCS) of 1.0 to 2.0% by weight, as determined by ISO 16152;

[0012] - The melting temperature Tm, measured according to ISO 11357 / Part 3 / Method C2, is between 155 and 175 °C.

[0013] - Crystallization temperature Tc, measured according to ISO 11357 / Part 3 / Method C2, ranging from 105 to 130 °C;

[0014] - pass 13 The pentatonic regularity [mmmm] was measured by C-NMR spectroscopy, ranging from 90 to 99.9 mol%.

[0015] This invention also relates to a cast film, wherein the polypropylene composition described herein is obtained through a multi-stage polymerization process, comprising the following steps:

[0016] (a0) Optionally, the zigler-Natta catalyst is modified, preferably with a polymer nucleating agent, more preferably with a vinyl polymer, and propylene is prepolymerized in a prepolymerization reactor;

[0017] a) Propylene is polymerized in the first polymerization reactor (R1) in the presence of a Ziegler-Natta catalyst to obtain the first polymerization product;

[0018] b) The first polymerization product is transferred to the second polymerization reactor (R2) to obtain the final polymerization product;

[0019] c) Optionally, the final polymerization product obtained in step b) is blended with the additive.

[0020] This invention also relates to the use of the articles described herein in pharmaceutical packaging. Detailed Implementation

[0021] All terms used herein should be understood to have the general meaning known to those skilled in the art.

[0022] Polypropylene composition

[0023] Based on the total weight of the polypropylene composition, the polypropylene composition comprises: 95 to 100% by weight, preferably 97 to 100% by weight, more preferably 98.5 to 100% by weight, of a polypropylene homopolymer; and optionally 0 to 5% by weight, preferably 0 to 3% by weight, more preferably 0 to 1.5% by weight, of at least one additive selected from antioxidants, acid scavengers, stabilizers, fillers, colorants, nucleating agents, slip agents, antiblocking agents, and antistatic agents.

[0024] The melt flow rate (MFR2) of the polypropylene composition in the cast film according to the invention (measured according to ISO 1133 at 230°C and 2.16 kg load) is 3.0 to 15.0 g / 10 min. The melt flow rate (MFR2) is preferably 4.5 to 12.0 g / 10 min, more preferably 6.0 to 10.0 g / 10 min.

[0025] Furthermore, the xylene cold solubles (XCS) content (measured according to ISO 16152) of the polypropylene composition in the cast film according to the invention is 0.1 to 3.0 wt%, preferably 0.5 to 2.5 wt%, more preferably 1.0 to 2.0 wt%. Particularly preferably, the melt flow rate MFR2 of the polypropylene composition (measured according to ISO 1133 at 230°C and 2.16 kg load) is 4.5 to 12.0 g / 10 min, more preferably 6.0 to 10.0 g / 10 min, and the xylene cold solubles (XCS) content (measured according to ISO 16152) is 0.5 to 2.5 wt%, more preferably 1.0 to 2.0 wt%.

[0026] Furthermore, the ethylene content of the polypropylene composition in the cast film according to the present invention (by...) 13The concentration (measured by C-NMR spectroscopy) is 0 to 0.5% by weight, preferably 0 to 0.3% by weight, and more preferably 0 to 0.1% by weight.

[0027] The melting temperature Tm of the polypropylene composition in the cast film of the present invention (measured according to ISO 11357 / Part 3 / Method C2) is 155 to 175°C, preferably 160 to 170°C. Furthermore, the crystallization temperature Tc of the polypropylene composition (measured according to ISO 11357 / Part 3 / Method C2) is 105 to 130°C, preferably 110 to 122°C.

[0028] The polypropylene composition in the cast film according to the present invention has a highly isotactic character, and its pentatonic regularity [mmmm] (by...) 13 The concentration (measured by C-NMR spectroscopy) was 90 to 99.9 mol%, preferably 95 to 99.9 mol%.

[0029] Preferably, the polypropylene composition in the cast film of the present invention has the following characteristics:

[0030] - A longitudinal tensile modulus of 500 to 1200 MPa, more preferably 650 to 1000 MPa, and most preferably 700 to 850 MPa, as measured on a 300 µm cast film according to ISO 527-3; and / or

[0031] - Transverse tensile modulus of 500 to 1300 MPa, more preferably 650 to 1100 MPa, and most preferably 700 to 1000 MPa, as measured on a 300 µm cast film according to ISO 527-3.

[0032] Furthermore, the dart impact (DDI) of the polypropylene composition, measured at 23°C on a 300 µm cast film according to ISO 7765-1:1988 / Method A, is preferably 350 to 1500 g, more preferably 400 to 1300 g, and most preferably 700 to 1200 g.

[0033] Furthermore, the haze value (measured on a 300 µm cast film according to ASTM D1003) of the polypropylene composition is preferably 0% to 60%, more preferably 0% to 50%, and most preferably 0% to 40%; and / or the clarity value (measured on a 300 µm cast film according to ASTM D1003) is 20% to 100%, more preferably 40% to 85%, and most preferably 55% to 80%. These haze and clarity values ​​are particularly preferred because a more transparent film makes the contents of the blister pack more visible, and therefore, it is advantageous to use such polypropylene compositions for blister packs.

[0034] More preferably, the optomechanical ability (OMA) of the polypropylene composition in the cast film according to the present invention is 5000 to 40000 MPa·g / %, more preferably 10000 to 35000 MPa·g / %, and most preferably 20000 to 30000 MPa·g / %. The optomechanical ability (OMA) is the ratio of the mechanical properties to the optical properties of the polymer, wherein the mechanical properties are targeted to be as high as possible, while the optical properties (e.g., haze) are targeted to be as low as possible. The optomechanical ability (OMA) is calculated according to the following formula:

[0035]

[0036] In the formula,

[0037] TM is the longitudinal tensile modulus measured in MPa on a 300 µm cast film according to ISO 527-3;

[0038] DDI is the dart impact measured in g on a 300 µm cast film at 23°C according to ISO 7765-1:1988 / Method A.

[0039] Haze was measured on a 300 µm cast film according to ASTM D1003, and is expressed as a percentage.

[0040] More preferably, the water vapor transmission rate (WVTR) of the polypropylene composition in the cast film according to the invention (measured according to ISO 15106-3:2003 on a 300 µm cast film) is 0 to 1.0 g / m. 2 More preferably, the concentration is 0.10 to 0.85 g / m³. 2 The optimal concentration is 0.20 to 0.75 g / m³. 2 sky.

[0041] process

[0042] The polypropylene composition described herein is preferably obtained through a multi-stage polymerization process, including the following steps:

[0043] (a0) Optionally, the zigler-Natta catalyst is modified, preferably with a polymer nucleating agent, more preferably with a vinyl polymer, and propylene is prepolymerized in a prepolymerization reactor;

[0044] a) Propylene is polymerized in the first polymerization reactor (R1) in the presence of a Ziegler-Natta catalyst to obtain the first polymerization product;

[0045] b) The first polymerization product is transferred to the second polymerization reactor (R2) to obtain the final polymerization product;

[0046] c) Optionally, the final polymerization product obtained in step b) is blended with the additive.

[0047] The polymerization process of the polypropylene composition is carried out using multi-stage polymerization as described above, preferably using sequential polymerization. The term "sequential polymerization" means that the propylene homopolymer is produced in at least two reactors connected in series. Therefore, the polymerization system of the present invention comprises at least the first polymerization reactor (R1) described in step a) and the second polymerization reactor (R2) described in step b). The term "polymerization reactor" should indicate that the main polymerization reaction occurs. Therefore, in the case where the process consists of two polymerization reactors, this definition does not exclude the option of including, for example, a prepolymerization step (carried out in a prepolymerization reactor) in the entire system. The term "consisting of" is a closed definition only with respect to the main polymerization reactor.

[0048] Preferably, at least one of the two polymerization reactors (R1) and (R2) is a gas-phase reactor (GPR). More preferably, the second polymerization reactor (R2) is a gas-phase reactor (GPR). The gas-phase reactor (GPR) according to the invention is preferably a fluidized bed reactor, a fast fluidized bed reactor, a fixed bed reactor, or any combination thereof. Therefore, the first polymerization reactor (R1) is preferably a slurry reactor (SR), and can be any continuous stirred tank reactor, simple stirred tank reactor, or loop reactor operating under bulk or slurry conditions. Bulk means polymerization is carried out in a reaction medium containing at least 60% (w / w) monomer. According to the invention, the slurry reactor (SR) is preferably a (bulk) loop reactor (LR).

[0049] Preferably, the propylene homopolymer produced in the first polymerization reactor (R1) (i.e., the fraction produced in the first polymerization reactor (R1), more preferably the fraction produced in the polymer slurry of the loop reactor (LR)) is directly conveyed to the second polymerization reactor (R2), i.e., to the (first) gas-phase reactor (GPR1), without the need for a flash evaporation step between stages. Such a direct conveying method is described in EP 887379 A, ​​EP 887380 A, EP 887381 A and EP 991684 A. "Direct conveying" means the process of directly introducing the contents of the first polymerization reactor (R1) (i.e., the loop reactor (LR)) (the polymer slurry containing the first propylene homopolymer fraction (H-PP1)) into the next stage gas-phase reactor.

[0050] Alternatively, the propylene homopolymer from the first polymerization reactor (R1) (i.e., the fraction produced in the first polymerization reactor (R1)) can be subjected to a flash evaporation step or a further concentration step before being transported to the second polymerization reactor (R2), i.e., to the gas phase reactor (GPR). Therefore, this kind of "indirect transport" refers to the process of transporting the contents (i.e., polymer slurry) of the first polymerization reactor (R1) (loop reactor (LR)) through a reaction medium separation unit and the reaction medium in gaseous form from that separation unit to the second polymerization reactor (R2) and then to the (first) gas phase reactor (GPR).

[0051] More specifically, the second polymerization reactor (R2) can be any mechanically mixed reactor or fluidized bed reactor. Preferably, the gas-phase reactor (GPR) comprises a mechanically stirred fluidized bed reactor with a gas velocity of at least 0.2 m / s. Therefore, it can be understood that the gas-phase reactor is a fluidized bed reactor, preferably a fluidized bed reactor with a mechanical stirrer.

[0052] Therefore, in a preferred embodiment, the first polymerization reactor (R1) is a slurry reactor (SR) (e.g., a loop reactor (LR)), and the second polymerization reactor (R2) is a gas-phase reactor (GPR). Thus, this process uses two polymerization reactors (R1) and (R2) connected in series, namely the slurry reactor (SR) (e.g., a loop reactor (LR)) and the (first) gas-phase reactor (GPR1). If necessary, a pre-polymerization reactor can be installed before the slurry reactor (SR).

[0053] The Ziegler-Natta catalyst (ZN-C) is fed into the first polymerization reactor (R1) and transferred together with the polymer (slurry) obtained in the first polymerization reactor (R1) to a subsequent reactor. If the process also includes a prepolymerization step, it is preferable to feed all the Ziegler-Natta catalyst (ZN-C) into the prepolymerization reactor. The prepolymer product containing the Ziegler-Natta catalyst (ZN-C) is then transferred to the first polymerization reactor (R1).

[0054] Multi-stage processes are preferably "loop-gas phase" processes, such as those developed by the Danish company Borealis (called BORSTAR). ® The technology is described in patent documents such as EP 0887379, WO 92 / 12182, WO 2004 / 000899, WO2004 / 111095, WO 99 / 24478, WO 99 / 24479 or WO 00 / 68315. Another applicable slurry vapor phase process is Basell's Spheripol® process.

[0055] When the temperature in the reactor is carefully selected, particularly excellent results can be obtained.

[0056] Therefore, the operating temperature of the first polymerization reactor (R1) is preferably in the range of 62 to 90°C, more preferably in the range of 70 to 88°C, and even more preferably in the range of 75 to 85°C.

[0057] As a substitute for or supplement to the previous step, the operating temperature of the second polymerization reactor (R2) is preferably in the range of 62 to 90°C, more preferably in the range of 70 to 88°C, and even more preferably in the range of 75 to 85°C.

[0058] Typically, the pressure in the first polymerization reactor (R1) (preferably a loop reactor (LR)) is in the range of 2000 to 8000 kPa, preferably 3000 to 7000 kPa, for example 3500 to 6500 kPa; while the pressure in the second polymerization reactor (R2) (i.e., the (first) gas phase reactor (GPR1)) is in the range of 500 to 5000 kPa, preferably 1500 to 4000 kPa.

[0059] Preferably, hydrogen is added to each polymerization reactor to control the molecular weight, i.e., the melt flow rate MFR2.

[0060] Preferably, the average residence time in polymerization reactors (R1) and (R2) is relatively long. Typically, the average residence time (τ) is defined as the reaction volume (V). R ) and reactor volumetric outflow rate (Q) o The ratio of (i.e., V) R / Q o ), that is, τ = V R / Q o [tau= V R / Q o For a loop reactor, the reaction volume (V) R () equals the reactor volume.

[0061] Therefore, the average residence time (τ) in the first polymerization reactor (R1) is preferably at least 15 minutes, more preferably 15 to 80 minutes, even more preferably 20 to 60 minutes, for example 24 to 50 minutes; and / or the average residence time (τ) in the second polymerization reactor (R2) is preferably at least 70 minutes, more preferably in the range of 70 to 220 minutes, more preferably in the range of 80 to 210 minutes, even more preferably in the range of 90 to 200 minutes, for example in the range of 90 to 190 minutes.

[0062] Polypropylene (Pre-PP) is produced in a prepolymerization reactor (PR). Prepolymerization is carried out in the presence of a Ziegler-Natta catalyst (ZN-C). According to this embodiment, the Ziegler-Natta catalyst (ZN-C), cocatalyst (Co), and external donor (ED) are all introduced into the prepolymerization step. However, this should not preclude the option of adding, for example, additional cocatalyst (Co) and / or external donor (ED) to the polymerization process in subsequent stages (e.g., to the first reactor (R1)). In one embodiment, if prepolymerization is used, the Ziegler-Natta catalyst (ZN-C), cocatalyst (Co), and external donor (ED) are added only in the prepolymerization reactor (PR).

[0063] The prepolymerization reaction is usually carried out at a temperature of 0 to 60°C, preferably at a temperature of 15 to 50°C, and more preferably at a temperature of 20 to 45°C.

[0064] The pressure in the prepolymerization reactor is not critical, but it must be high enough to keep the reaction mixture in the liquid phase. Therefore, the pressure can be between 2000 and 8000 kPa, for example, 3000 to 7000 kPa.

[0065] In a preferred embodiment, prepolymerization is carried out as bulk slurry polymerization in the form of liquid propylene, i.e., the liquid phase mainly contains propylene, wherein an inert component may optionally be dissolved.

[0066] Other components can also be added during the prepolymerization stage. Therefore, as is known in the art, hydrogen can be added to the prepolymerization stage to control the molecular weight of polypropylene (Pre-PP). Furthermore, antistatic additives can be used to prevent particles from adhering to each other or to the reactor walls.

[0067] Precise control of prepolymerization conditions and reaction parameters is a skill required in this field.

[0068] Based on the prepolymerization process conditions defined above, a mixture (MI) of Ziegler-Natta catalyst (ZN-C) and polypropylene (Pre-PP) produced in the prepolymerization reactor (PR) is preferably obtained. Preferably, the Ziegler-Natta catalyst (ZN-C) is (finely) dispersed in the polypropylene (Pre-PP). In other words, the Ziegler-Natta catalyst (ZN-C) particles introduced into the prepolymerization reactor (PR) break down into smaller fragments, which are uniformly distributed in the grown polypropylene (Pre-PP). The size of the introduced Ziegler-Natta catalyst (ZN-C) particles and the size of the resulting fragments are not critical factors of this invention and fall within the scope of knowledge in the art.

[0069] As described above, if prepolymerization is used, after the prepolymerization, the mixture (MI) of polypropylene (Pre-PP) produced in the Ziegler-Natta catalyst (ZN-C) and the prepolymerization reactor (PR) is transferred to the first reactor (R1). Typically, the total amount of polypropylene (Pre-PP) in the final propylene copolymer (R-PP) is relatively low, and generally does not exceed 5.0% by weight, more preferably not exceeding 4.0% by weight, and even more preferably in the range of 0.5% to 4.0% by weight, for example in the range of 1.0% to 3.0% by weight.

[0070] As mentioned above, the Ziegler-Natta catalyst (ZN-C) can be modified in the prepolymerization step a0). Details of this modification are as follows.

[0071] catalyst

[0072] In a preferred embodiment, the catalyst is a solid Ziegler-Natta catalyst, comprising:

[0073] a) Compounds of IUPAC group 4 to 6 transition metals;

[0074] b) Compounds of IUPAC Group 2 metals;

[0075] c) An internal donor, wherein the internal donor is a non-phthalic acid compound, preferably a non-phthalic acid ester;

[0076] d) co-catalysts; and

[0077] e) Optional external donors.

[0078] The catalyst comprises: a compound of a transition metal (e.g., titanium) from Groups 4 to 6 of IUPAC (TC); a compound of a metal (e.g., magnesium) from Group 2 (MC); and an internal donor (ID), which is a non-phthalic acid compound, preferably a non-phthalic acid ester, more preferably a diester of a non-phthalic acid dicarboxylic acid, as detailed below. Therefore, in a preferred embodiment, the catalyst is completely free of unwanted phthalic acid compounds. Furthermore, the solid catalyst is self-supporting and contains no external support material (e.g., silica or MgCl2).

[0079] The Ziegler-Natta catalyst can be further defined by the manner in which it is obtained. Therefore, the Ziegler-Natta catalyst is preferably obtained by a process comprising the following steps:

[0080] a)

[0081] a1) Optionally in an organic liquid reaction medium, provide a solution of at least one Group 2 metal alkoxide (Ax), which is a reaction product of a Group 2 metal compound (MC) and a monohydric alcohol (A), and the monohydric alcohol (A) contains at least one ether moiety in addition to the hydroxyl moiety; or

[0082] a2) Optionally in an organic liquid reaction medium, a solution of at least one Group 2 metal alkoxide (Ax'), which is a reaction product of a Group 2 metal compound (MC) and an alcohol mixture of a monohydric alcohol (A) and a monohydric alcohol (B) of the formula ROH; or

[0083] a3) Optionally in an organic liquid reaction medium, provide a solution of a mixture of a Group 2 alkoxide (Ax) and a Group 2 metal alkoxide (Bx), and the Group 2 metal alkoxide (Bx) is a reaction product of a Group 2 metal compound (MC) and a monohydric alcohol (B); or

[0084] a4) Provide a solution of a Group 2 alkoxide of the formula M(OR1) n (OR2) m X 2-n-m , or a mixture of a Group 2 alkoxide M(OR1) n’ X 2-n’ and M(OR2) m’ X 2-m’ , where M is a Group 2 metal, X is a halogen, R1 and R2 are different alkyl groups with C2 to C 16 carbon atoms, and 0 < n < 2, 0 < m < 2 and n + m+(2 - n - m)=2, provided that n and m ≠ 0, 0 < n' ≤ 2 and 0 < m' ≤ 2;

[0085] b) Add the solution from step a) to a compound (TC) of at least one transition metal of Groups 4 to 6; and

[0086] c) Obtain solid catalyst component particles;

[0087] At any step before step c), add an internal electron donor (ID), preferably a non-phthalic acid type internal donor (ID).

[0088] Therefore, it is preferred to add the internal donor (ID) or its precursor to the solution of step a), or add it to the transition metal compound before adding it to the solution of step a).

[0089] According to the above procedure, the Ziegler-Natta catalyst (ZN-C) can be obtained by precipitation or emulsion-solidification, depending on the physical conditions, particularly the temperatures used in steps b) and c). In this application, the emulsion is also referred to as a liquid / liquid two-phase system.

[0090] In both methods (precipitation or emulsion-solidification), the catalyst chemistry is the same.

[0091] In the precipitation method, the solution from step a) is combined with at least one transition metal compound (TC) from step b), and the entire reaction mixture is maintained at a temperature range of at least 50°C, more preferably 55 to 110°C, and more preferably 70 to 100°C, to ensure that the catalyst component is completely precipitated in the form of solid particles (step c).

[0092] In the emulsion-curing process of step b), the solution from step a) is typically added to at least one transition metal compound (TC) at a relatively low temperature (e.g., -10 to below 50°C, preferably -5 to 30°C). During emulsion stirring, the temperature is typically maintained at -10 to below 40°C (preferably -5 to 30°C). Droplets of the emulsion dispersion form an active catalyst composition. Curing of the droplets (step c) is suitably carried out by heating the emulsion to a temperature of 70 to 150°C (preferably 80 to 110°C).

[0093] The present invention preferably uses a catalyst prepared by an emulsion-curing method.

[0094] In a preferred embodiment of step a), a solution of a2) or a3) is used (i.e., a solution of (Ax'), or a solution of a mixture of (Ax) and (Bx), particularly a solution of a2).

[0095] Preferably, the Group 2 metal (MC) is magnesium.

[0096] The magnesium alkoxy compound defined above can be prepared in situ in the first step (step a) of the catalyst preparation process by reacting the magnesium compound as described above with an alcohol. in situ Alternatively, the magnesium alkoxy compound can be a separately prepared magnesium alkoxy compound, or even a commercially available magnesium alkoxy compound that can be directly used in the catalyst preparation process of the present invention.

[0097] An illustrative example of alcohol (A) is ethylene glycol monoether. Alcohol (A) is preferably a C2 to C4 ethylene glycol monoether, wherein the ether moiety comprises 2 to 18 carbon atoms, preferably 4 to 12 carbon atoms. Preferred examples are 2-(2-ethylhexyloxy)ethanol, 2-butoxyethanol, 2-hexyloxyethanol, and 1,3-propanediol monobutyl ether and 3-butoxy-2-propanol, wherein 2-(2-ethylhexyloxy)ethanol, 1,3-propanediol monobutyl ether, and 3-butoxy-2-propanol are particularly preferred.

[0098] An exemplary monohydric alcohol (B) is of the formula ROH, wherein R is a straight-chain or branched C2-C. 16 Alkyl residues, preferably straight-chain or branched C4 to C5. 10 Alkyl residues, more preferably straight-chain or branched C6 to C8 alkyl residues. The most preferred monohydric alcohol is 2-ethyl-1-hexanol or octanol.

[0099] Preferably, a mixture of Mg alkoxy compounds (Ax) and (Bx) or a mixture of alcohols (A) and (B) is used, wherein the molar ratio of Bx:Ax or B:A is 10:1 to 1:10, more preferably 6:1 to 1:6, and most preferably 4.1 to 1:4.

[0100] Magnesium alkoxy compounds can be the reaction products of alcohols and magnesium compounds as defined above, wherein the magnesium compound is selected from dialkylmagnesium, alkylmagnesium alkoxides, magnesium dialkyloxides, alkoxymagnesium halides, and alkylmagnesium halides. Additionally, magnesium dialkyloxides, magnesium diaryloxides, magnesium aryloxy halides, magnesium aryloxides, and magnesium alkylaryloxides may also be used. The alkyl group can be similar or different C1-C. 20 Alkyl groups, preferably C2-C 10 Alkyl groups. When alkyl-alkoxy magnesium compounds are used, representative alkyl-alkoxy magnesium compounds are ethyl magnesium butoxide, butyl magnesium pentoxide, octyl magnesium butoxide, and octyl magnesium octaoxide. Preferably, dialkyl magnesium is used. The most preferred dialkyl magnesium is butyloctyl magnesium or butylethyl magnesium.

[0101] Besides alcohols (A) and (B), magnesium compounds can also react with formula R''(OH). m The polyol (C) is reacted to obtain the magnesium alkoxide compound. If a polyol is used, it is preferably an alcohol, wherein R'' is a straight-chain, cyclic, or branched C2 to C3 group. 10 Hydrocarbon residues, where m is an integer from 2 to 6.

[0102] Therefore, the magnesium alkoxy compound in step a) is selected from magnesium dialkyl oxides, diaryloxymagnesium, alkoxymagnesium halides, aryloxymagnesium halides, alkylmagnesium alkyl oxides, arylmagnesium alkyl oxides, and alkylmagnesium aryl oxides. Alternatively, a mixture of magnesium dihalides and magnesium dialkyl oxides may be used.

[0103] The solvent used to prepare the catalyst of the present invention may be selected from aromatic and aliphatic straight-chain, branched, and cyclic hydrocarbons, or mixtures thereof, having 5 to 20 carbon atoms (more preferably 5 to 12 carbon atoms). Suitable solvents include benzene, toluene, cumene, xylene, pentane, hexane, heptane, octane, and nonane. Hexane and pentane are particularly preferred.

[0104] The reaction for preparing magnesium alkoxy compounds can be carried out at temperatures ranging from 40°C to 70°C. The optimal temperature is selected based on the Mg compound and alcohol used.

[0105] The transition metal compounds of Groups 4 to 6 are preferably titanium compounds, and most preferably titanium halides, such as TiCl4.

[0106] The internal donor (ID) used in the preparation of the catalyst used in this invention is preferably selected from the (di) esters of non-phthalic acid carboxylic (di) acids, 1,3-diethers, and their derivatives and mixtures. Particularly preferred donors are diesters of monounsaturated dicarboxylic acids, particularly selected from esters such as malonic acid esters, maleic acid esters, succinic acid esters, citrate esters, glutaric acid esters, cyclohexene-1,2-dicarboxylic acid esters, benzoic acid esters, and any derivatives and / or mixtures thereof. Preferred examples are, for example, substituted maleic acid esters and citrate esters, with citrate esters being the most preferred.

[0107] In emulsion processes, a two-phase liquid-liquid system can be formed by simple stirring and optionally by adding (additional) solvents and additives (e.g., turbulence minimizing agents (TMAs) and / or emulsifiers and / or emulsion stabilizers, such as surfactants), which are used in a manner known in the art to promote emulsion formation and / or stabilization. Preferably, the surfactant is an acrylic or methacrylic polymer. Particularly preferred are unbranched C... 12 To C 20 (Meth)acrylates, such as poly(hexadecyl)methacrylate, poly(octadecyl)methacrylate, and mixtures thereof. If a turbulence minimizing agent (TMA) is used, the TMA is preferably selected from α-olefin polymers of α-olefin monomers having 6 to 20 carbon atoms, such as polyoctene, polynonene, polydecene, polyundecene, or polydodecene, or mixtures thereof. Polydecene is most preferred.

[0108] The solid particulate product obtained by precipitation or emulsion-solidification can be washed at least once, preferably at least twice, and more preferably at least three times with aromatic hydrocarbons and / or aliphatic hydrocarbons (preferably toluene, heptane, or pentane, or TiCl4). The washing solution may also contain a donor and / or a Group 13 compound, such as trialkylaluminum, haloalkylaluminum compounds, or alkoxyaluminum compounds. An aluminum compound may also be added during catalyst synthesis. The catalyst can be further dried (e.g., by evaporation or nitrogen purging), or it can be slurried into an oily liquid without any drying step.

[0109] The resulting Ziegler-Natta catalyst is preferably in particulate form, with an average particle size typically ranging from 5 to 200 µm, and more preferably from 10 to 100 µm. The particles are dense, have low porosity, and a surface area of ​​less than 20 g / m². 2 More preferably less than 10 g / m 2 Typically, the amount of Ti in the catalyst composition is 1 to 6 wt%, Mg is 10 to 20 wt%, and the donor is 10 to 40 wt%.

[0110] WO 2012 / 007430, EP 2610271, EP 2610270 and EP 2610272 disclose detailed descriptions of catalyst preparation.

[0111] Ziegler-Natta catalysts (ZN-C) are preferably used in combination with alkylaluminum co-catalysts and optional external donors.

[0112] In the polymerization process of this invention, an external donor (ED) is preferably present as an additional component. Suitable external donors (EDs) include certain silanes, ethers, esters, amines, ketones, heterocyclic compounds, and blends thereof. Silanes are particularly preferred. Silanes having the following general formula are most preferred:

[0113] R a p R b q Si(OR c ) (4-p-q)

[0114] In the formula, R a R b and R c Represents a hydrocarbon group, particularly an alkyl or cycloalkyl group, where p and q are numbers in the range of 0 to 3, and the sum of p + q is less than or equal to 3. R a R b and R cThey can be chosen independently of each other and can be the same or different. Specific examples of such silanes include (tert-butyl)2Si(OCH3)2, (cyclohexyl)(methyl)Si(OCH3)2, (phenyl)2Si(OCH3)2, and (cyclopentyl)2Si(OCH3)2, or have the general formula:

[0115] Si(OCH2CH3)3(NR 3 R 4 )

[0116] In the formula, R 3 and R 4 They can be the same or different, and represent hydrocarbon groups with 1 to 12 carbon atoms.

[0117] R 3 and R 4 Independently selected from straight-chain aliphatic hydrocarbon groups having 1 to 12 carbon atoms, branched aliphatic hydrocarbon groups having 1 to 12 carbon atoms, and cyclic aliphatic hydrocarbon groups having 1 to 12 carbon atoms. Particularly preferred, R 3 and R 4 It is independently selected from methyl, ethyl, n-propyl, n-butyl, octyl, decyl, isopropyl, isobutyl, isopentyl, tert-butyl, tert-pentyl, neopentyl, cyclopentyl, cyclohexyl, methylcyclopentyl, and cycloheptyl.

[0118] More preferably, R 3 and R 4 They are the same; more preferably, R 3 and R 4 All are ethyl.

[0119] Particularly preferably, the external donor (ED) is an pentyl dimethoxysilane donor (D-donor) or a cyclohexylmethyl dimethoxysilane donor (C-donor).

[0120] In addition to the Ziegler-Natta catalyst (ZN-C) and optional external donors (ED), a co-catalyst may also be used. The co-catalyst is preferably a compound of Group 13 of the periodic table (IUPAC), such as an organoaluminum compound, such as an aluminum compound, such as an alkylaluminum, aluminum halide, or aluminum alkyl halide compound. Thus, in one specific embodiment, the co-catalyst (Co) is a trialkylaluminum, such as triethylaluminum (TEAL), dialkylaluminum chloride, alkylaluminum dichloride, or a mixture thereof. In one specific embodiment, the co-catalyst (Co) is triethylaluminum (TEAL).

[0121] Advantageously, the hydride content (expressed as AlH3) of triethylaluminum (TEAL) is less than 1.0% by weight relative to triethylaluminum (TEAL). More preferably, the hydride content is less than 0.5% by weight, and most preferably, the hydride content is less than 0.1% by weight.

[0122] Preferably, the ratio of cocatalyst (Co) to external donor (ED) [Co / ED] and / or the ratio of cocatalyst (Co) to transition metal (TM) [Co / TM] should be carefully selected.

[0123] Therefore, the molar ratio of the cocatalyst (Co) to the exogenous donor (ED) [Co / ED] must be in the range of 5 to 45, preferably in the range of 5 to 35, and more preferably in the range of 5 to 25; optionally, the molar ratio of the cocatalyst (Co) to the titanium compound (TC) [Co / TC] must be in the range of above 80 to 500, preferably in the range of 100 to 350, and more preferably in the range of 120 to 300.

[0124] As described above, it is preferable to modify the Ziegler-Natta catalyst (ZN-C) during the aforementioned prepolymerization step to introduce a polymer nucleating agent. Further details of such modifications can be found in EP 1183307, EP 2960279 and EP 3184587.

[0125] As mentioned above, such polymer nucleating agents can be vinyl polymers, such as vinyl polymers derived from monomers of the following formula:

[0126] CH2=CH-CHR1R2

[0127] In the formula, R1 and R2 together with the carbon atoms they are attached to form an optionally substituted saturated or unsaturated or aromatic ring or fused ring system, wherein the ring or fused ring portion contains 4 to 20 carbon atoms (preferably a 5 to 12 member saturated or unsaturated or aromatic ring or fused ring system), or independently represents a straight chain or a branched chain C4-C. 30 Alkanes, C4-C 20 Cycloalkanes or C4-C 20 Aromatic ring. Preferably, R1 and R2 together with the carbon atoms they are attached to form a five- or six-membered saturated or unsaturated or aromatic ring, or independently represent a lower alkyl group containing 1 to 4 carbon atoms. According to the invention, vinyl compounds, particularly vinylcycloalkanes, are preferred for preparing polymer nucleating agents, especially vinylcyclohexane (VCH), vinylcyclopentane, vinyl-2-methylcyclohexane, 3-methyl-1-butene, 3-ethyl-1-hexene, 3-methyl-1-pentene, 4-methyl-1-pentene, or mixtures thereof. VCH is a particularly preferred monomer.

[0128] In the modification step of the polymerization catalyst, the weight ratio of the vinyl compound to the polymerization catalyst is preferably 0.3 or more and up to 40 (e.g., 0.4 to 20), more preferably 0.5 to 15 (e.g., 0.5 to 2.0).

[0129] The polymerization of vinyl compounds (such as VCH) can be carried out in an inert fluid in which the polymer formed (such as polyVCH) is not dissolved. It is important to ensure that the viscosity of the final catalyst / polymerized vinyl compound / inert fluid mixture is high enough to prevent catalyst particles from settling during storage and transportation.

[0130] The viscosity of the mixture can be adjusted before or after the polymerization of the vinyl compound. For example, polymerization can be carried out in a low-viscosity oil, and the viscosity can be adjusted after the polymerization of the vinyl compound by adding a high-viscosity substance. Such a high-viscosity substance can be a "wax," such as an oil, or a mixture of oil with a solid or high-viscosity substance (oil-grease). The viscosity of such a viscous substance at room temperature is typically 1,000 to 15,000 cP. The advantage of using waxes is that they can improve the storage and delivery of the catalyst to the process. The activity of the catalyst can be maintained because there is no need for washing, drying, sieving, and transfer.

[0131] The weight ratio of oil to solids or high-viscosity polymers is preferably less than 5:1.

[0132] In addition to viscous substances, liquid hydrocarbons (such as isobutane, propane, pentane, and hexane) can also be used as media in the modification step.

[0133] Polypropylene produced using catalysts modified with polymerized vinyl compounds is substantially free of free (unreacted) vinyl compounds. This means that the vinyl compounds should be completely reacted during the catalyst modification step. In this regard, the weight ratio of the (added) vinyl compound to the catalyst should be in the range of 0.05 to 10, preferably less than 3, more preferably about 0.1 to 2.0, and particularly preferably about 0.1 to 1.5. It should be noted that excessive use of vinyl compounds is not beneficial.

[0134] Furthermore, the reaction time for catalyst modification via the polymerization of vinyl compounds should be sufficient to allow the vinyl monomers to react completely, i.e., polymerization should continue until the amount of unreacted vinyl compounds in the reaction mixture (including the polymerization medium and reactants) is less than 0.5% by weight, particularly less than 2000 ppm (by weight) (as determined by analysis). Therefore, when the prepolymerized catalyst contains up to about 0.1% by weight of vinyl compounds, the final vinyl compound content in the polypropylene will be below the detection limit of GC-MS (<0.01 ppm, by weight). Typically, when operating on an industrial scale, the polymerization time needs to be at least 30 minutes, preferably at least 1 hour, and particularly preferably at least 5 hours. Polymerization times in the range of 6 to 50 hours can even be used. Modification can be carried out at temperatures from 10 to 70°C, preferably from 35 to 65°C.

[0135] According to the present invention, when the catalyst is modified in the presence of a strongly coordinating external donor, a nucleated, highly rigid propylene polymer can be obtained.

[0136] WO 00 / 6831 also discloses general conditions for catalyst modification, which are incorporated herein by reference regarding the modification of polymerization catalysts.

[0137] The preferred embodiments of vinyl compounds previously described in this application also apply to the polymerization catalyst of the present invention and the preferred polypropylene compositions according to the present invention.

[0138] Besides oils, suitable media for the modification step include low-viscosity aliphatic inert organic solvents, such as pentane and heptane. Additionally, a small amount of hydrogen can be used during the modification process.

[0139] additive

[0140] As described above, based on the total weight of the polypropylene composition, the polypropylene composition may contain at least one additive in an amount of 0 to 5% by weight, more preferably 0 to 3% by weight, and most preferably 0 to 1.5% by weight. Such additives may be selected from antioxidants, acid scavengers, stabilizers, fillers, colorants, nucleating agents, slip agents, anti-blocking agents, and antistatic agents. These additives are generally commercially available and are described, for example, in Hans Zweifel's "Plastic Additives Handbook," pp. 871-873, 5th edition, 2001. More preferably, the polypropylene composition comprises at least one antioxidant and at least one acid scavenger as additives. The antioxidant is selected from self-reactive antioxidants, such as sterically hindered phenols, such as pentaerythritol tetrakis(3-(3',5'-di-tert-butyl-4-hydroxyphenyl)-propionate (CAS No.: 6683-19-8, commercially available Irganox 1010, BASF, Germany). The acid scavenger is selected from metal stearates (e.g., calcium stearate (CAS No.: 1592-23-0)) or layered hydroxycarbonates (e.g., synthetic hydrotalcite (CAS No.: 11097-59-9)). In a more preferred embodiment, the acid scavenger is calcium stearate.

[0141] Cast film

[0142] The thickness of the cast film can be from 100 to 500 µm, and the cast film can be an oriented cast film or a non-oriented cast film, preferably a non-oriented cast film. The film thickness is preferably in the range of 150 to 450 µm, for example, in the range of 200 to 400 µm. The film can be a multilayer film, such as a bilayer or a trilayer film, wherein the layer containing the polymer composition described herein is a core layer. According to a preferred embodiment, the film is a single-layer film.

[0143] Preferably, the cast film of the present invention has:

[0144] - A longitudinal tensile modulus of 500 to 1200 MPa, more preferably 650 to 1000 MPa, and most preferably 700 to 850 MPa, as measured on a 300 µm cast film according to ISO 527-3; and / or

[0145] - Transverse tensile modulus of 500 to 1300 MPa, more preferably 650 to 1100 MPa, and most preferably 700 to 1000 MPa, as measured on a 300 µm cast film according to ISO 527-3.

[0146] Furthermore, the dart impact (DDI) of the membrane, measured at 23°C on a 300 µm cast film according to ISO 7765-1:1988 / Method A, is preferably 350 to 1500 g, more preferably 400 to 1300 g, and most preferably 700 to 1200 g.

[0147] Furthermore, the haze value of the film (measured according to ASTM D1003 on a 300 µm cast film) is preferably 0% to 60%, more preferably 0% to 50%, and most preferably 0% to 40%; and / or the clarity value (measured according to ASTM D1003 on a 300 µm cast film) is 20% to 100%, more preferably 40% to 85%, and most preferably 55% to 80%. These haze and clarity values ​​are particularly preferred because a more transparent film makes the contents of the blister pack more visible, and therefore, it is advantageous to use such a film for blister packs.

[0148] More preferably, the optical mechanical index (OMA) of the cast film according to the present invention is 5000 to 40000 MPa·g / %, more preferably 10000 to 35000 MPa·g / %, and most preferably 20000 to 30000 MPa·g / %. The optical mechanical index (OMA) is the ratio of the polymer's mechanical properties to its optical properties, wherein the mechanical properties are targeted to be as high as possible, while the optical properties (e.g., haze) are targeted to be as low as possible. The optical mechanical index (OMA) is calculated according to the following formula:

[0149]

[0150] In the formula,

[0151] TM is the longitudinal tensile modulus measured in MPa on a 300 µm cast film according to ISO 527-3;

[0152] DDI is the dart impact measured in g on a 300 µm cast film at 23°C according to ISO 7765-1:1988 / Method A.

[0153] Haze was measured on a 300 µm cast film according to ASTM D1003, and is expressed as a percentage.

[0154] The water vapor transmission rate (WVTR) of the membrane according to the present invention (measured according to ISO 15106-3:2003 on a 300 µm cast film) is 0 to 1.0 g / m. 2 More preferably, the concentration is 0.10 to 0.85 g / m³. 2 The optimal concentration is 0.20 to 0.75 g / m³. 2 sky.

[0155] use

[0156] This invention also relates to the use of the cast film described herein in blister packaging (e.g., pharmaceutical packaging, food packaging, or non-food packaging, such as detergent or personal care product packaging). Such blister packaging comprises a thermoformed element (serving as a container for packaging products, such as tablets or capsules) formed from the film according to the invention and an aluminum substrate sheet for a ruptureable portion. The corresponding blister packaging is sealed by sealing the flat portion of the thermoformed element formed from the film of the invention onto the aluminum substrate sheet.

[0157] Other aspects of disclosure

[0158] Other aspects (1) to (14) were also disclosed.

[0159] (1) A polypropylene composition comprising:

[0160] a) A base polymer, based on the total weight of the polypropylene composition, wherein the base polymer comprises 95 to 100% by weight of a propylene homopolymer; and

[0161] b) Optionally, based on the total weight of the polypropylene composition, at least one additive in an amount of 0 to 5% by weight, said additive being selected from antioxidants, acid scavengers, stabilizers, fillers, colorants, nucleating agents, slip agents, antiblocking agents and antistatic agents;

[0162] The polypropylene composition comprises:

[0163] - Melt flow rate MFR2, measured at 230°C and 2.16 kg load according to ISO 1133, ranging from 3.0 to 15.0 g / 10 min;

[0164] - Xylene cold solubles (XCS) content, measured according to ISO 16152, from 0.1 to 3.0% by weight;

[0165] - The melting temperature Tm, measured according to ISO 11357 / Part 3 / Method C2, ranging from 155 to 175 °C; and

[0166] - Crystallization temperature Tc, measured according to ISO 11357 / Part 3 / Method C2, ranging from 105 to 130 °C;

[0167] - pass 13 The pentatonic regularity [mmmm] was measured by C-NMR spectroscopy, ranging from 90 to 99.9 mol%.

[0168] (2) The polypropylene composition according to aspect (1), wherein the polypropylene composition comprises at least one antioxidant and at least one acid scavenger, wherein the antioxidant is selected from self-oxidizing antioxidants (e.g., sterically hindered phenols) and the acid scavenger is selected from metal stearates or layered hydroxy carbonates (e.g., synthetic hydrotalcite).

[0169] (3) The polypropylene composition according to any of the foregoing aspects, wherein the polypropylene composition has:

[0170] a) A melt flow rate MFR2 of 4.5 to 12.0 g / 10 min, more preferably 6.0 to 10.0 g / 10 min, as measured according to ISO 1133 at 230 °C and a load of 2.16 kg; and / or

[0171] b) The content of xylene cold solubles (XCS) is 0.5 to 2.5% by weight, more preferably 1.0 to 2.0% by weight, as determined according to ISO 16152.

[0172] (4) The polypropylene composition according to any of the foregoing aspects, wherein the ethylene content of the polypropylene composition (according to...) 13 The concentration (measured by C-NMR spectroscopy) is 0 to 0.5% by weight, more preferably 0 to 0.3% by weight, and most preferably 0 to 0.1% by weight.

[0173] (5) The polypropylene composition according to any of the foregoing aspects, wherein the polypropylene composition has:

[0174] a) A longitudinal tensile modulus of 500 to 1200 MPa, more preferably 650 to 1000 MPa, and most preferably 700 to 850 MPa, as measured on a 300 µm cast film according to ISO 527-3; and / or

[0175] b) The transverse tensile modulus, measured on a 300 µm cast film according to ISO 527-3, is 500 to 1300 MPa, more preferably 650 to 1100 MPa, and most preferably 700 to 1000 MPa.

[0176] (6) The polypropylene composition according to any of the preceding aspects, wherein the dart impact (DDI) of the polypropylene composition measured at 23°C on a 300 µm cast film according to ISO 7765-1:1988 / Method A is 350 to 1500 g, more preferably 400 to 1300 g, and most preferably 700 to 1200 g.

[0177] (7) The polypropylene composition according to any of the foregoing aspects, wherein the polypropylene composition has:

[0178] a) A haze value of 0% to 60%, more preferably 0% to 50%, and most preferably 0% to 40%, as measured on a 300 µm cast film according to ASTM D1003; and / or

[0179] b) A purity value of 20% to 100%, more preferably 40% to 85%, and most preferably 55% to 80%, as measured on a 300 µm cast film according to ASTM D1003.

[0180] (8) The polypropylene composition according to any of the foregoing aspects, wherein the optical mechanical index (OMA) of the polypropylene composition is 5000 to 40000 MPa·g / %, more preferably 10000 to 35000 MPa·g / %, and most preferably 20000 to 30000 MPa·g / %, wherein the optical mechanical index (OMA) is calculated according to the following formula:

[0181]

[0182] In the formula,

[0183] TM is the longitudinal tensile modulus measured in MPa on a 300 µm cast film according to ISO 527-3;

[0184] DDI is the dart impact measured in g on a 300 µm cast film at 23°C according to ISO 7765-1:1988 / Method A.

[0185] Haze was measured on a 300 µm cast film according to ASTM D1003, and is expressed as a percentage.

[0186] (9) The polypropylene composition according to any of the foregoing aspects, wherein the water vapor transmission rate (WVTR) of the polypropylene composition (measured according to ISO 15106-3:2003 on a 300 µm cast film) is 0 to 1.0 g / m. 2 More preferably, the concentration is 0.10 to 0.85 g / m³. 2 The optimal concentration is 0.20 to 0.75 g / m³. 2 sky.

[0187] (10) A method for obtaining a polypropylene composition according to aspects (1)-(9), by a multi-stage polymerization process comprising the steps of:

[0188] (a0) Optionally, the zigler-Natta catalyst is modified, preferably with a polymer nucleating agent, more preferably with a vinyl polymer, and propylene is prepolymerized in a prepolymerization reactor;

[0189] a) Propylene is polymerized in the first polymerization reactor (R1) in the presence of a Ziegler-Natta catalyst to obtain the first polymerization product;

[0190] b) The first polymerization product is transferred to the second polymerization reactor (R2) to obtain the final polymerization product;

[0191] c) Optionally, the final polymerization product obtained in step b) is blended with the additive.

[0192] (11) The method according to aspect (10), wherein the Ziegler-Natta catalyst comprises:

[0193] a) Compounds of IUPAC group 4 to 6 transition metals;

[0194] b) Compounds of IUPAC Group 2 metals;

[0195] c) An internal donor, wherein the internal donor is a non-phthalic acid compound, preferably a non-phthalic acid ester;

[0196] d) co-catalysts; and

[0197] e) Optional external donors.

[0198] (12) An article (preferably a film) comprising or substantially composed of a polypropylene composition according to aspects (1)-(9).

[0199] (13) The article according to aspect (12), wherein the article is a blown film or cast film with a thickness of 100 to 500 µm.

[0200] (14) Use of the product in pharmaceutical packaging according to aspects (12)-(13).

[0201] A. Measurement Method

[0202] Unless otherwise stated, the properties of the polymers prepared according to the present invention have been characterized according to the methods described herein.

[0203] melt flow rate

[0204] Melt flow rate (MFR) is measured according to ISO 1133 and expressed in g / 10 min. MFR is an indicator of the polymer's flowability and therefore its processability. A higher melt flow rate generally indicates a lower polymer viscosity. The MFR2 of polypropylene was measured at 230°C and a load of 2.16 kg.

[0205] The melt flow rate MFR2 (230°C) of the polymer fraction produced in the second polymerization reactor was calculated using the following formula:

[0206]

[0207] In the formula:

[0208] w(A) is the mass fraction of the first polymer fraction (A) obtained in the first polymerization reactor, expressed as [weight%]; MFR(A) is the melt flow rate MFR2 (230℃) of the first polymer fraction (A) obtained in the first polymerization reactor, expressed as [g / 10 min].

[0209] w(B) is the mass fraction of the second polymer fraction (B) obtained in the second polymerization reactor, expressed as [weight%]; MFR(B) is the melt flow rate MFR2 (230℃) of the second polymer fraction (B) obtained in the second polymerization reactor, expressed as [g / 10 min].

[0210] MFR(C) is the melt flow rate MFR2 (230°C) of the polymer obtained in the second polymerization step (the final polymer, which contains fractions (A) and (B)), expressed in [g / 10 min].

[0211] Xylene cold soluble matter (XCS) content

[0212] The amount of polymer dissolved in xylene was determined at 25°C according to ISO 16152, 5th edition (2005-07-01).

[0213] Ethylene (C2) content and pentagonal regularity

[0214] Quantitative nuclear magnetic resonance (NMR) spectroscopy was used to quantify the comonomer content and distribution of copolymers (especially propylene-co-ethylene copolymers). Quantitative data were recorded in solution using a Bruker Advance III 400 NMR spectrometer. 13 C{ 1 H} NMR spectroscopy (for H} NMR spectroscopy 1 H and 13 C was operated at 400.15 and 100.62 MHz respectively. All spectra were performed using... 13A C-optimized 10 mm selective excitation probe was used for recording at 125 °C, and nitrogen was used for all pneumatic devices. Approximately 200 mg of material was dissolved in 1,2-tetrachloroethane. d 2(TCE- d 2) and chromium acetylacetone (Cr(acac)3) were reacted to obtain a relaxant solution in a 65 mM solvent (Singh, G., Kothari, A., Gupta, V., Polymer Testing 28 5(2009), 475). This apparatus was chosen primarily for the high sensitivity and quantitative spectroscopy required for accurate determination of ethylene content. Standard single-pulse excitation (without NOE) was employed, using an optimized tip angle, a 1-second cyclic delay, and a two-stage WALTZ16 decoupling scheme (Zhou, Z., Kuemmerle, R., Qiu, X., Redwine, D., Cong, R., Taha, A., Baugh, D. Winniford, B., J. Mag. Reson. 187 (2007) 225; Busico, V., Carbonniere, P., Cipullo, R., Pellecchia, R., Severn, J., Talarico, G., Macromol. Rapid Commun. 2007, 28, 11289). A total of 6144 (6k) transient signals were acquired for each spectrum. Quantitative analysis was performed using a dedicated computer program. 13 C{ 1 The ¹H NMR spectra were processed and integrated, and the relevant quantitative properties were determined by integration. All chemical shifts were expressed using the solvent chemical shifts, with the central methylene group of the ethylene block (EEE) at 30.00 ppm as an indirect reference. This method also allows for comparable references when this structural unit is absent.

[0215] Characteristic signals corresponding to regional irregular propylene insertions were observed (Resconi, L., Cavallo, L., Fait, A., Piemontesi, F., Chem. Rev. 2000, 100, 1253).

[0216] Characteristic signals corresponding to ethylene incorporation were observed (Cheng, HN, Macromolecules 17, 1984, 1950). Using the method of Wang et al., by covering the entire 13Multiple signals from the C-spectrum were integrated to calculate the comonomer content as the mole fraction or percentage of incorporated ethylene relative to all monomers in the copolymer (Wang, WJ., Zhu, S., Macromolecules 33, 2000, 1157). This analytical method was chosen for its stability and its ability to account for regionally irregular propylene insertions when necessary. Slight adjustments were made to the integration region to improve applicability across all comonomer content ranges encountered.

[0217] For systems where only isolated ethylene incorporation (PPEPP) is observed, the method of Wang et al. was modified to reduce the influence of non-zero integrals used for quantifying higher-order comonomer sequences. In this case, the absolute ethylene content value is determined solely based on the following:

[0218] or

[0219] E = 0.5(IH +IG + 0.5(I C + I D )),

[0220] The same notation as that used by Wang et al. (Wang, WJ., Zhu, S., Macromolecules 33, 2000, 1157) is used. The terminology used for absolute propylene content (P) has not been modified, and the mole fraction of ethylene is calculated as follows:

[0221] [E] = E / (E + P).

[0222] The comonomer content (in weight percentage) is calculated in the usual manner from the mole fraction, i.e. .

[0223] The stereoregularity distribution was quantified by integrating the methyl region between 23.6 and 19.7 ppm and correcting for sites unrelated to the target stereo sequence (Busico, V., Cipullo, R., Prog. Polym. Sci. 26(2001) 443; Busico, V., Cipullo, R., Monaco, G., Vacatello, M., Segre, AL, Macromolecules 30 (1997) 6251). Specifically, the influence of regional defects and comonomers on the quantification of stereoregularity distribution was corrected by subtracting representative regional defects and comonomer integrals from specific integrated regions of the stereo sequence.

[0224] Isothelic regularity was determined at the quintet level and reported as the percentage of isothelic quintet (mmmm) sequences out of all quintet sequences:

[0225]

[0226] Melting temperature Tm and crystallization temperature Tc

[0227] Melting temperature Tm and crystallization temperature Tc were determined using a TA Instruments Q2000 differential scanning calorimeter (DSC) on samples ranging from 5 to 7 mg. DSC was performed according to ISO 11357 / Part 3 / Method C2 (heating / cooling / heating cycles, scan rate of 10 °C / min, temperature range of -30 to +225 °C).

[0228] The crystallization temperature Tc is determined by the cooling step, while the melting temperature Tm is determined by the second heating step.

[0229] Molecular weight distribution

[0230] The molar mass averages (Mw and Mn) and molecular weight distribution (MWD) (i.e., Mw / Mn) were determined by gel permeation chromatography (GPC) according to ISO 16014-4:2003 and ASTM D 6474-99 using the following formula:

[0231]

[0232]

[0233] In the formula, Ai and Mi represent the chromatographic peak slice area and the molecular weight (MW) of the polyolefin.

[0234] A PolymerChar GPC instrument equipped with an infrared (IR) detector, 3 x Olexis and 1 x OlexisGuard columns (from Polymer Laboratories), and 1,2,4-trichlorobenzene (TCB, stabilized with 250 mg / L of 2,6-di-tert-butyl-4-methylphenol) as solvent (at a constant flow rate of 1 ml / min at 160 °C) were used for each analysis. 200 µL of sample solution was injected for each analysis. The column set was calibrated using a universal calibration method (according to ISO 16014-2:2003) with polystyrene (PS) standards of at least 15 narrow MWDs (ranging from 0.5 kg / mol to 11500 kg / mol). The Mark-Houwink constants for PS, PE, and PP were as described in ASTM D 6474-99. All samples were prepared as follows: 5.0 to 9.0 mg of polymer was dissolved in 8 ml of stabilized TCB (same as the mobile phase) and gently shaken at 160 °C for 2.5 hours in the autosampler of the GPC instrument.

[0235] Tensile modulus

[0236] The longitudinal and transverse tensile moduli were determined on a 300 μm cast film according to ISO 527-3.

[0237] Dart Impact

[0238] Dart impact (DDI) was determined on a 300 µm cast film at 23 °C according to ISO 7765-1:1988 / Method A.

[0239] Haze and clarity

[0240] Haze and clarity were measured on a 300 μm cast film according to ASTM D1003.

[0241] Water vapor transmission rate (WVTR)

[0242] Water vapor transmission rate (WVTR) was measured on a 300 µm cast film according to ISO 15106-3:2003.

[0243] Instrument: Mocon Aquatran

[0244] Temperature: 38℃ ± 0.3℃

[0245] Relative humidity: 0 / 100%

[0246] Sample area: 5 cm² 2

[0247] B. Example

[0248] The base polymer used for producing polypropylene compositions IE1 and IE2 is the same, PP1. Production is carried out using a Ziegler-Natta catalyst (described below), and the polymerization conditions are provided in Table 1. Production was conducted in a Borstar pilot plant with a prepolymerization reactor, a slurry loop reactor, and a gas-phase reactor. The solid catalyst was used in conjunction with triethylaluminum (TEAL) (as a cocatalyst) and dicyclopentyldimethoxysilane (D-donor) (as a donor).

[0249] 1a) Catalyst preparation

[0250] 3.4 L of 2-ethylhexanol and 810 mL of propylene glycol butyl monoether (molar ratio 4:1) were added to a 20 L reactor. Then, 7.8 L of a 20% BEM (butylethyl magnesium) toluene solution supplied by Crompton GmbH was slowly added to the well-stirred alcohol mixture. The temperature was maintained at 10 °C during the addition. After the addition, the temperature of the reaction mixture was raised to 60 °C, and stirring was continued at this temperature for 30 minutes. Finally, after cooling to room temperature, the resulting magnesium alkoxide was transferred to a storage container.

[0251] The 21.2 g of Mg alkoxide prepared above was mixed with 4.0 ml of bis(2-ethylhexyl) citrate for 5 min. Immediately after mixing, the resulting magnesium complex was used for the preparation of catalyst components.

[0252] At 25°C, 19.5 ml of titanium tetrachloride was placed in a 300 ml reactor equipped with a mechanical stirrer. The mixing speed was adjusted to 170 rpm. Maintaining the temperature at 25°C, 26.0 g of the magnesium complex prepared above was added over 30 minutes. 3.0 ml of Viscoplex 1-254 and 24.0 ml of heptane were added to form an emulsion. Mixing was continued at 25°C for another 30 minutes. The reactor temperature was then increased to 90°C over 30 minutes. The reaction mixture was stirred at 90°C for another 30 minutes. Stirring was then stopped, and the reaction mixture was allowed to stand at 90°C for 15 minutes.

[0253] The solid material was washed with 100 ml of toluene, 30 ml of TiCl4, and 100 ml of toluene, and then washed twice with 60 ml of heptane. 1 ml of the donor was added during the first two washes. The washing was performed by stirring at 170 rpm for 30 minutes at 80°C. After stirring was stopped, the reaction mixture was allowed to stand for 20–30 minutes, and then siphoned.

[0254] Wash the solid material five times: wash at 80°C and 170 rpm for 30 minutes. After stopping stirring, let the reaction mixture stand for 20-30 minutes, then siphon it.

[0255] Wash 1: Washing was performed with a mixture of 100 ml toluene and 1 ml donor.

[0256] Washing 2: Washing was performed with a mixture of 30 ml TiCl4 and 1 ml donor.

[0257] Washing 3: Wash with 100 ml of toluene.

[0258] Washing 4: Wash with 60 ml of heptane.

[0259] Washing 5: Wash with 60 ml of heptane (stir for 10 minutes).

[0260] Then stop stirring, let the reaction mixture stand for 10 minutes, lower the temperature to 70°C, then siphon it, and then purge with nitrogen for 20 minutes to obtain an air-sensitive powder.

[0261] 1b) VCH modification of catalysts

[0262] At room temperature and under inert conditions, 35 ml of mineral oil (liquid paraffin PL68) was added to a 125 ml stainless steel reactor, followed by the addition of 0.82 g of triethylaluminum (TEAL) and 0.33 g of dicyclopentyldimethoxysilane (donor D). After 10 minutes, 5.0 g of the catalyst prepared in step 1a (Ti content 1.4 wt%) was added, followed by 5.0 g of vinylcyclohexane (VCH) after another 20 minutes. The temperature was raised to 60 °C over a 30-minute period and maintained for 20 hours. Finally, the temperature was lowered to 20 °C, and the concentration of unreacted VCH in the oil / catalyst mixture was analyzed and found to be 120 ppm (wt).

[0263] Table 1: Polymerization conditions of the base polymer PP-1

[0264]

[0265] Calculated value Measured values

[0266] The base polymer PP-1 produced according to Table 1 was then mixed with different additives in a high-intensity mixer, and IE1 and IE2 were prepared in a co-rotating twin-screw extruder. Table 2 provides the formulations and some properties measured on the pellets, where AO1 is an antioxidant (Irganox 1010 supplied by BASF, Germany), AO2 is an antioxidant (Irgafos 168 supplied by BASF, Germany), AS1 is an acid scavenger (synthetic hydrotalcite supplied by Kisuma Chemicals, Netherlands), and AS2 is an acid scavenger (calcium stearate Ceasit FI supplied by Baerlocher, Germany).

[0267] Table 2: Formulation and properties of polypropylene compositions IE1 and IE2

[0268]

[0269] Comparative Example CE1 contains DM55pharm as the base polymer. DM55pharm is a commercially available polypropylene homopolymer (sold by Borealis) with a melt flow rate (MFR2) of 2.8 g / 10 min and a density of 905 kg / m³. 3 The melting temperature Tm is 163℃, the crystallization temperature Tc is 116℃, and the xylene cold solubles (XCS) content (measured according to ISO 16152) is 3.0 wt%.

[0270] Cast films were prepared on a Collin laboratory-scale casting film production line using IE1 and CE1 at a melt temperature of 220°C, a cooling roller temperature of 20°C, and a production capacity of 8 kg / h. The resulting film had a thickness of 300 µm. The films were then characterized, and the results are shown in Table 3 below.

[0271] Table 3: Membrane Performance

[0272]

[0273] As shown in Table 3, compared with the membrane made from polypropylene composition CE1, the membranes made from polypropylene compositions IE1 and IE2 exhibit improved mechanical properties in terms of longitudinal tensile modulus, transverse tensile modulus, and dart impact resistance. It can also be seen that the membranes made from IE1 and IE2 have lower haze and higher clarity compared to the membrane made from CE1. Therefore, the optical mechanical index (OMA) of the membranes made from IE1 and IE2 is significantly higher than that of the membrane made from CE1. Furthermore, the water vapor transmission rate of the membrane made from IE1 is lower than that of the membrane made from CE1.

Claims

1. A cast film comprising a polypropylene composition, said polypropylene composition comprising: a) A base polymer, based on the total weight of the polypropylene composition, wherein the base polymer comprises 95 to 100% by weight of a propylene homopolymer; and b) Optionally, based on the total weight of the polypropylene composition, at least one additive in an amount of 0 to 5% by weight, said additive being selected from antioxidants, acid scavengers, stabilizers, fillers, colorants, nucleating agents, slip agents, antiblocking agents and antistatic agents; in, The polypropylene composition has the following characteristics: - Melt flow rate MFR2, measured at 230°C and 2.16 kg load according to ISO 1133, is 6.0 to 10.0 g / 10 min. - Content of xylene cold solubles (XCS) of 1.0 to 2.0% by weight, as determined by ISO 16152; - The melting temperature Tm, measured according to ISO 11357 / Part 3 / Method C2, is between 155 and 175 °C. - Crystallization temperature Tc, measured according to ISO 11357 / Part 3 / Method C2, ranging from 105 to 130 °C; - pass 13 The pentatonic regularity [mmmm] was measured by C-NMR spectroscopy, ranging from 90 to 99.9 mol%.

2. The cast film according to claim 1, wherein, The polypropylene composition comprises at least one antioxidant and at least one acid scavenger, wherein the antioxidant is selected from self-oxidizing antioxidants, such as sterically hindered phenols, and the acid scavenger is selected from metal stearates or layered hydroxy carbonates, such as synthetic hydrotalcite.

3. The cast film according to any one of the preceding claims, wherein, The polypropylene composition according to 13 The ethylene content, as determined by C-NMR spectroscopy, is 0 to 0.5% by weight, more preferably 0 to 0.3% by weight, and most preferably 0 to 0.1% by weight.

4. The cast film according to any one of the preceding claims, wherein, The polypropylene composition has the following characteristics: a) A longitudinal tensile modulus of 500 to 1200 MPa, more preferably 650 to 1000 MPa, and most preferably 700 to 850 MPa, as measured on a 300 µm cast film according to ISO 527-3; and / or b) The transverse tensile modulus, measured in accordance with ISO 527-3 on a 300 µm cast film, is 500 to 1300 MPa, more preferably 650 to 1100 MPa, and most preferably 700 to 1000 MPa.

5. The cast film according to any one of the preceding claims, wherein, The dart impact (DDI) of the polypropylene composition, measured at 23°C on a 300 µm cast film according to ISO 7765-1:1988 / Method A, is preferably 350 to 1500 g, more preferably 400 to 1300 g, and most preferably 700 to 1200 g.

6. The cast film according to any one of the preceding claims, wherein, The polypropylene composition has the following characteristics: a) A haze value of 0% to 60%, more preferably 0% to 50%, and most preferably 0% to 40%, as measured on a 300 µm cast film according to ASTM D1003; and / or b) A purity value of 20% to 100%, more preferably 40% to 85%, and most preferably 55% to 80%, as measured on a 300 µm cast film according to ASTM D1003.

7. The cast film according to any one of the preceding claims, wherein, The optical mechanical index (OMA) of the polypropylene composition is 5000 to 40000 MPa·g / %, more preferably 10000 to 35000 MPa·g / %, and most preferably 20000 to 30000 MPa·g / %. The optical mechanical index (OMA) is calculated according to the following formula: ， In the formula, TM is the longitudinal tensile modulus measured in MPa on a 300 µm cast film according to ISO 527-3; DDI is the dart impact measured in g on a 300 µm cast film at 23°C according to ISO 7765-1:1988 / Method A. Haze was measured on a 300 µm cast film according to ASTM D1003, and is expressed as a percentage.

8. The cast film according to any one of the preceding claims, wherein, The polypropylene composition, measured according to ISO 15106-3:2003 on a 300 µm cast film, has a water vapor transmission rate (WVTR) of 0 to 1.0 g / m. 2 More preferably, the concentration is 0.10 to 0.85 g / m³. 2 The optimal concentration is 0.20 to 0.75 g / m³. 2 sky.

9. The cast film according to any one of the preceding claims, wherein, The polypropylene composition is obtained through a multi-stage polymerization process, which includes the following steps: (a0) Optionally, the zigler-Natta catalyst is modified, preferably with a polymer nucleating agent, more preferably with a vinyl polymer, and propylene is prepolymerized in a prepolymerization reactor; a) Propylene is polymerized in the first polymerization reactor (R1) in the presence of a Ziegler-Natta catalyst to obtain the first polymerization product; b) The first polymerization product is transferred to the second polymerization reactor (R2) to obtain the final polymerization product; c) Optionally, the final polymerization product obtained in step b) is blended with the additive.

10. The cast film according to any one of the preceding claims, wherein, The thickness of the cast film is 100 to 500 µm.

11. Use of the cast film according to any one of the preceding claims in pharmaceutical packaging.

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