HETEROPHASIC PROPYLENE COPOLYMER, UNORIENTED FILM, CONTAINER, AND USE OF A HETEROPHASIC PROPYLENE CO

专利摘要:
heterophasic propylene copolymer, unoriented film, container, and use of a heterophasic propylene copolymer the present invention is directed to a new heterophasic propylene copolymer (raheco) and an unoriented film comprising heterophasic propylene copolymer (raheco), as well as a container comprising the unoriented film. The present invention is further directed to the use of heterophasic (raheco) propylene copolymer to improve the balance between softness and turbidity of the unoriented film.
公开号:BR112016017227B1
申请号:R112016017227-2
申请日:2015-02-03
公开日:2021-06-29
发明作者:Jingbo Wang；Pavel SHUTOV；Johanna LILJA；Markus Gahleitner
申请人:Borealis Ag；
IPC主号:

专利说明:

[001] The present invention is directed to a novel heterophasic propylene copolymer (RAHECO) and an unoriented film comprising the heterophasic propylene copolymer (RAHECO), as well as a container comprising the unoriented film. The present invention is further directed to the use of heterophasic propylene copolymer (RAHECO) to improve the balance between softness and turbidity of the unoriented film.
[002] There is a growing trend in the food packaging industry to use plastic containers, especially pouches containing sterilized or pre-cooked foods. Retort bags offer many advantages over rigid metal packages, such as faster cooking/sterilization time, less shelf space, easier disposal, improved food taste, etc. Typical pouches have a multilayer structure with polyolefins, such as polyethylene or polypropylene, adhesives, barrier outer layers. It is desired that the polyolefin material impart toughness as well as high impact strength to the final packaging material.
[003] The same trend, namely increased use of polyolefin materials, is seen in the medical packaging industry as well. Again, the polymer must impart sufficient toughness as well as high impact strength to the final packaging material. In the case of medical applications, softness rather than toughness is a key requirement. Of course, these medical products must also be sterilizable.
[004] It is known that the impact strength of polypropylene can be improved by dispersing a rubber phase within the polymer matrix, thus obtaining a heterophasic polypropylene composition. In particular, heterophasic propylene polymers (impact-modified propylene polymers) provide high impact strength if the amount of rubber dispersed within the matrix is high enough, for example, in pockets that typically stand upright at least. 10.0% by weight or even at least 15.0% by weight.
[005] However, in the field of food and medical packaging soft materials with good optical properties in combination with good mechanical properties are needed.
[006] In addition, for some food packaging applications, such as retort bags or some medical packaging applications, a sterilization treatment is required. The most common sterilization procedures are the use of heat (steam), radiation (beta radiation, electrons, or gamma radiation) or chemicals (usually ethylene oxide). Steam sterilization is generally carried out in a temperature range of about 120 to 130 °C. Of course, treating a polymer according to the sterilization conditions described above can impair its final properties, in particular its optical properties. , such as transparency.
[007] However, it has been found that conventional heterophasic systems significantly change their properties after sterilization. Typically, optical properties such as haze as well as mechanical properties such as softness are undesired impaired.
[008] Considering the disadvantages described above, it is an object of the present invention to provide a soft heterophasic propylene copolymer with an optimized or improved balance between mechanical and optical properties.
[009] The discovery of the present invention is to provide a heterophasic propylene copolymer, in which the elastomeric propylene copolymer (E) dispersed in the matrix (M) of the heterophasic propylene copolymer has a specific glass transition temperature. Furthermore, the discovery of the present invention is that the heterophasic propylene copolymer which has to be produced in the presence of a Ziegler-Natta catalyst containing an internal donor (ID) which does not belong to the phthalic acid ester class. With such a glass transition temperature and catalyst a heterophasic propylene copolymer can be produced having an improved or optimized balance of mechanical and optical properties such as softness, haze and resistance to steam sterilization.
[0010] Therefore, the present invention is directed to a heterophasic propylene copolymer (RAHECO), said heterophasic propylene copolymer (RAHECO) comprises a matrix (M) being a random propylene copolymer (R-PP) and a copolymer of elastomeric propylene (E) dispersed in said matrix (M), wherein the heterophasic propylene copolymer (RAHECO) has a) an MFR2 melt flow (230°C), measured in accordance with ISO 1133 in the range of 2.0 at 10.0 g/10 min, b) a content of cold xylene solubles (XCS) determined according to ISO 16152 (25°C) in the range of 16.0 to 50.0% by weight, preferably in the range from 16.0 to 35.0% by weight c) a comonomer content in the range of 8.5 to 21.0% mol, and wherein preferably the heterophasic propylene copolymer (RAHECO) has at least two transition temperatures glass transition temperature Tg(1), and Tg(2), the first glass transition temperature Tg(1) refers to the matrix (M), while the second glass transition temperature Tg(2) refers to the cup dispersed elastomeric (E) propylene polymer, in which additionally the second glass transition temperature Tg(2) fills the inequality (I) Tg(2) > 21.0 - 2.0 x C(XCS) (I) where Tg(2) is the second glass transition temperature of the heterophasic propylene copolymer (RAHECO); C (XCS) is the comonomer content [in mol %] of the cold soluble xylene fraction of heterophasic propylene copolymer (RAHECO).
[0011] Preferably, the first glass transition temperature Tg(1) is above the second glass transition temperature Tg(2). Even more preferably, the difference between the first glass transition temperature Tg(1) and the second glass transition temperature Tg(2) is at least 40°C, more preferably at least 45°C.
[0012] Preferably, the second glass transition temperature Tg(2) is below -20°C, such as below -35°C, and fulfilling inequality (I) as defined in the present invention. Typically, said glass transition temperature Tg(2) will be greater than -70°C. The first glass transition temperature Tg(1) is preferably in the range of -12 to 2°C.
[0013] It has surprisingly been found that such heterophasic propylene copolymer (RAHECO) has an improved or optimized balance between mechanical or optical properties especially between softness, turbidity and resistance to steam sterilization.
[0014] In one embodiment of the present invention, the fraction soluble in cold xylene (XCS) has i) a comonomer content in the range of 33.0 to 45.0 mol%, and/or ii) an intrinsic viscosity (IV) determined in accordance with DIN ISO 1628/1, (in decalin at 135°C) in the range of 1.0 to 1.8 dl/g.
[0015] In another embodiment of the present invention, the random propylene copolymer (R-PP) has i) an MFR2 melt flow (230°C), measured according to ISO 1133 in the range from 3.0 to 8.0 g/10 min, and/or ii) a comonomer content in the range of 4.4 to 7.3% mol.
[0016] In yet another embodiment of the present invention, the fraction insoluble in cold xylene (XCI) has a relative content of isolate to block ethylene sequences (I(E)) in the range of 50.0 to 65, 0%, where the content of I(E) is defined by equation (II)
where I(E) is the relative content of isolate to block ethylene sequences [in %]; fPEP is the molar fraction of propylene/ethylene/propylene (PEP) sequences in the cold xylene insoluble fraction (XCI) of heterophasic propylene copolymer (RAHECO); fPEE is the molar fraction of propylene/ethylene/ethylene (PEE) and ethylene/ethylene/propylene (EEP) sequences in the cold xylene-insoluble fraction (XCI) of the heterophasic propylene copolymer (RAHECO); fEEE is the molar fraction of ethylene/ethylene/ethylene (EEE) sequences in the cold xylene insoluble fraction (XCI) of the heterophasic propylene copolymer (RAHECO), in which all sequence concentrations are based on a triad statistical analysis of C13-NMR data.
[0017] In yet another embodiment of the present invention, the random propylene copolymer (R-PP) comonomers and/or the elastomeric propylene copolymer (E) comonomers are ethylene and/or α-olefin C4 to C8.
[0018] In one embodiment of the present invention, the heterophasic propylene copolymer (RAHECO) comprises 60 to 95% by weight, such as 60.0 to 870.0% by weight, based on the total weight of the heterophasic propylene copolymer ( RAHECO), of the random propylene copolymer (R-PP) and 5 to 40% by weight, as 13.0 to 40.0% by weight, based on the total weight of the heterophasic propylene copolymer (RAHECO), of the copolymer of elastomeric propylene (E).
[0019] In another embodiment of the present invention, the heterophasic propylene copolymer (RAECO) comprises a nucleating agent, preferably an a-nucleating agent.
[0020] In another embodiment of the present invention, the heterophasic propylene copolymer (RAHECO) is free of phthalic acid esters as well as their respective decomposition products, preferably the heterophasic propylene copolymer (RAHECO) is free of compounds phthalic acid, as well as their respective decomposition products.
[0021] In an embodiment of the present invention, the heterophasic propylene copolymer (RAHECO) was polymerized in the presence of a) a Ziegler-Natta (ZN-C) catalyst comprising the compounds (TC) of a transition metal of Group 4 to 6 of the IUPAC, a Group 2 metal compound (MC) and an internal donor (ID), wherein said internal donor (ID) is a non-phthalic compound, preferably is a non-phthalic acid ester ; b) optionally, a cocatalyst (Co), and c) optionally an external donor (ED).
[0022] It is preferred that: a) the internal donor (ID) is selected from optionally substituted malonates, maleates, succinates, glutarates, cyclohexene-1,2-dicarboxylates, benzoates and derivatives and/or mixtures thereof , preferably the internal donor (ID) is a citraconate; and/or b) the molar ratio of cocatalyst (Co) to external donor (ED) [Co/ED] is 5 to 45.
[0023] In yet another embodiment of the present invention, the heterophasic propylene copolymer (RAHECO) comprising a matrix (M) being a random propylene copolymer (R-PP) and an elastomeric propylene copolymer (E) dispersed in the said matrix (M) is produced in a multistage process comprising at least two reactors connected in series.
[0024] It is preferred that (a) in a first reactor of propylene and ethylene and/or α-olefin C4 to C8 are polymerized obtaining a first fraction of propylene copolymer (R-PP1), (b) transfer said first fraction of propylene copolymer (R-PP1) in a second reactor, (c) polymerize in said second reactor in the presence of the first fraction of propylene copolymer (R-PP1) propylene and ethylene and/or α-olefin C4 to C8 obtaining a second fraction of propylene copolymer (R-PP2), said first fraction of propylene copolymer (R-PP1) and said second fraction of propylene copolymer (R-PP2) form the matrix (R-PP), (d ) transferring said matrix (M) into a third reactor, (e) polymerizing in said third reactor in the presence of the matrix (M) propylene and ethylene and/or α-olefin C4 to C8 obtaining an elastomeric propylene copolymer (E), said matrix (M) and said elastomeric propylene copolymer (E) form the heterophasic propylene copolymer (RAHECO).
[0025] In an embodiment of the present invention, the heterophasic propylene copolymer (RAHECO) a) a flexural modulus measured in accordance with ISO 178 in the range of 450 to 800 MPa, and/or b) a transparency in accordance with the ASTM D100300 standard measured on a 1mm thick injection molded sample of at least 75.0%, and/or c) a turbidity according to the ASTM D 1003-00 measured on a 1mm thick sample injection molded of < 50.0%, and/or d) a clarity in accordance with ASTM D1003-00 measured on a 1 mm sample thickness of injection molded samples of at least 90.0%.
[0026] The present invention is also directed to an unoriented film comprising heterophasic propylene copolymer (RAHECO). It is preferred that the film is a cast film or a blown film.
[0027] The present invention is further directed to a container comprising the unoriented film.
[0028] The present invention is further directed to a use of heterophasic propylene copolymer (RAHECO) to improve the balance of softness and transparency of an unoriented film, wherein the improvement is achieved when heterophasic propylene copolymer (RAHECO) has (a) a flexural modulus measured in accordance with ISO 178 in the range of 450 to 800 MPa, and (b) a turbidity in accordance with ASTM D 1003-00 measured on a 1mm thick injection molded sample of below 50.0%.
[0029] In the following, the present invention is described in more detail.
[0030] The present heterophasic propylene copolymer (RAHECO) is mainly characterized by its specific optical and mechanical properties.
[0031] Therefore, it is preferred that the heterophasic propylene copolymer (RAHECO) has a flexural modulus measured in accordance with ISO 178, in the range of 450 to 800 MPa. For example, heterophasic propylene copolymer (RAHECO) has a flexural modulus measured according to ISO 178 in the range of 480 to 750 MPa, or in the range of 500 to 720 MPa.
[0032] With regard to optical properties, it is preferable that the heterophasic propylene copolymer (RAHECO) has (a) a transparency in accordance with ASTM D100300 measured on a 1 mm thick injection molded sample of at least 75.0%, preferably in the range of 75.0 to 95.0% and more preferably in the range of 75.0 to 90.0%, and/or (b) a turbidity in accordance with ASTM D 1003-00 measured on a 1mm thick injection molded sample of <50.0%, more preferably in the range of 10.0 to 50.0%, and most preferably in the range of 25.0 to 50.0%, and/ or d) a clarity in accordance with ASTM D1003-00 measured on a 1mm thick injection molded sample of at least 90.0%, preferably in the range of 90.0 to 99.0% and more preferably in the range from 92.0 to 98.0%.
[0033] In an embodiment of the present invention, the heterophasic propylene copolymer (RAHECO) has a) a flexural modulus measured in accordance with ISO 178, in the range of 450 to 800 MPa, preferably in the range of 480 to 750 MPa , and more preferably in the range of 500 to 720 MPa, and b) a transparency in accordance with ASTM D100300 measured on a 1 mm thick injection molded sample of at least 75.0%, preferably in the range of 75.0 to 95.0% and more preferably in the range of 75.0 to 90.0%, and/or c) a turbidity in accordance with ASTM D 1003-00 measured on a 1 mm thick injection molded sample of < 50.0%, more preferably in the range of 10.0 to 50.0%, and most preferably in the range of 25.0 to 50.0%, and d) a clarity in accordance with ASTM D1003-00 measured in an injection molded 1mm thick sample of at least 90.0%, preferably in the range of 90.0 to 99.0% and more preferably in the range of 92.0 to 98.0%.
[0034] Additionally or alternatively, the heterophasic propylene copolymer (RAHECO) has a) a turbidity before sterilization determined in accordance with ASTM D 1003-00 measured on a molded film of 50 µm below 5%, preferably below 3 .5%, and/or b) a turbidity after sterilization determined in accordance with ASTM D 1003-00 measured on a cast film of 50 µm below 10% preferably below 6%.
[0035] Preferably, not only the heterophasic propylene copolymer (RAHECO) is characterized by the specific values of flexural modulus, transparency, turbidity and clarity, but also the unoriented film comprising the heterophasic propylene copolymer (RAHECO) and container which comprises the unoriented film when measured under the same conditions as indicated above. Therefore, the above values of flexural modulus, transparency, haze and clarity, are equally applicable for the unoriented film and container.
[0036] The heterophasic propylene copolymer (RAHECO) according to the present invention comprises a matrix (M) being a random propylene copolymer (R-PP) and dispersed therein an elastomeric propylene copolymer (E). Thus, matrix (M) contains (finely) dispersed inclusions which are not part of matrix (M) and said inclusions contain elastomeric propylene copolymer (E). The term inclusion indicates that the matrix (M) and the inclusion form different phases within the heterophasic propylene copolymer (RAHECO). The presence of second phases or so-called inclusions is, for example, visible by high-resolution microscopy, such as electron microscopy or atomic force microscopy, or by dynamic-mechanical thermal analysis (DMTA). Specifically in DMTA the presence of a multiphase structure can be identified by the presence of at least two different glass transition temperatures.
[0037] Preferably, the heterophasic propylene copolymer (RAHECO) according to the present invention comprises as polymeric components only the random propylene copolymer (R-PP) and the elastomeric propylene copolymer (E). In other words, the heterophasic propylene copolymer (RAHECO) may contain other additives, but no other polymer in an amount greater than 5.0% by weight, more preferably greater than 3.0% by weight, such as greater than 1.0 % by weight, based on total heterophasic propylene copolymer (RAHECO). An additional polymer that can be present in such low amounts is a polyethylene, which is a by-product of the reaction obtained by preparing the heterophasic propylene copolymer (RAHECO). Therefore, it is particularly appreciated that the present heterophasic propylene copolymer (RAHECO) contains only random propylene copolymer (PP-R), elastomeric propylene copolymer (E) and optionally polyethylene in amounts as mentioned in this paragraph .
[0038] The heterophasic propylene copolymer (RAHECO) according to this invention is characterized by a moderate melt flow rate. Consequently, the heterophasic propylene copolymer (RAHECO) has an MFR2 melt flow (230°C) in the range of 2.0 to 10.0 g/10 min, preferably in the range of 2.5 to 8.0 g/10 min, more preferably in the range 3.0 to 5.5 g/10 min.
[0039] Preferably, it is desired that the heterophasic propylene copolymer (RAHECO) is thermomechanically stable. Therefore, it is appreciated that the heterophasic propylene copolymer (RAHECO) has a melting temperature of at least 135°C, more preferably in the range of 135 to 160°C, even more preferably in the range of 137 to 155°C.
[0040] Typically, the heterophasic propylene copolymer (RAHECO) has a rather low crystallization temperature, i.e. not more than 110°C, more preferably in the range of 95 to 110°C, even more preferably in the range of 100 to 108°C.
[0041] However, in the case the heterophasic propylene copolymer (RAHECO) comprises a nucleating agent, such as an α-nucleating agent, the heterophasic propylene copolymer (RAHECO) preferably has a crystallization temperature being above the temperature of crystallization of the non-nucleate heterophasic propylene copolymer (RAHECO®), i.e. from more than 110°C, more preferably in the range of 110 to 125°C, even more preferably in the range of 110 to 122°C.
[0042] The heterophasic propylene copolymer (RAHECO) comprises in addition to propylene also comonomers. Preferably, the heterophasic propylene copolymer (RAHECO) comprises in addition to ethylene propylene and/or C4 to C8 α-olefins. Therefore, the term "propylene copolymer" according to this invention is understood as a polypropylene comprising, preferably consisting of, units derivable from (a) propylene and (b) ethylene and/or α-olefins C4 to C8.
[0043] Thus, the heterophasic propylene copolymer (RAHECO), that is, the random propylene copolymer (R-PP), such as the first fraction of propylene copolymer (R-PP1) and the second fraction of propylene copolymer (R-PP2), as well as elastomeric propylene copolymer (E), comprises monomers copolymerizable with propylene, for example, comonomers such as ethylene and/or α-olefins C4 to C8, in particular ethylene and/or α-olefins C4 to C8, for example 1-butene and/or 1-hexene. Preferably, the heterophasic propylene copolymer (RAHECO) according to the present invention especially comprises consisting of monomers copolymerizable with propylene from the group consisting of ethylene, 1-butene and 1-hexene. More specifically, the heterophasic propylene copolymer (RAHECO) of the present invention comprises - in addition to propylene - units derivable from ethylene and/or 1-butene. In a preferred embodiment, the heterophasic propylene copolymer (RAHECO) according to the present invention comprises units derivable from only ethylene and propylene. Even more preferably, random propylene copolymer (R-PP), i.e. the first fraction of propylene copolymer (R-PP1) and the second fraction of propylene copolymer (R-PP2), as well as the propylene copolymer elastomeric (E) heterophasic propylene copolymer (RAHECO) contain the same comonomers as ethylene.
[0044] Consequently, the elastomeric propylene copolymer (E) is preferably an ethylene propylene rubber (EPR), while the random propylene copolymer (R-PP) is a random ethylene propylene copolymer (PP-R).
[0045] Furthermore, it is appreciated that the heterophasic propylene copolymer (RAHECO) preferably has a moderate total comonomer content which contributes to the softness of the material. Thus, it is necessary that the comonomer content of the heterophasic propylene copolymer (RAHECO) is in the range of 8.5 to 21.0 mol%, preferably in the range of 0 to 18.0 mol%, more preferably in the range of 10, 0 to 15.0 mol%.
[0046] The cold soluble fraction in xylene (XCS) measured in accordance with ISO 16152 (25°C) of the heterophasic propylene copolymer (RAHECO) is in the range of 16.0 to 50.0% in weight, preferably in the range of 16.0 to 350% by weight, more preferably in the range of 16.0 to 30.0% by weight, even more preferably in the range of 16.0 to 25% by weight or 17.0 to 25.0% by weight.
[0047] Furthermore, it is understood that the cold xylene soluble fraction (XCS) of the heterophasic propylene copolymer (RAHECO) is specified by its intrinsic viscosity. A low intrinsic viscosity (IV) value reflects a low weight average molecular weight. For the present invention it is considered that the cold xylene soluble fraction (XCS) of the heterophasic propylene copolymer (RAHECO) has an intrinsic viscosity (IV) measured according to ISO 1628/1 (at 135°C in decalin) in the range from 1.0 to below 1.8 dl/g, preferably in the range from 1.0 to 1.5 dl/g, more preferably in the range from 1.1 to below 1.6 dl/g.
[0048] Furthermore, it is preferred that the comonomer content, i.e., ethylene content, of the cold xylene soluble fraction (XCS) of the heterophasic propylene copolymer (RAHECO) is not more than 45.0 mol%, more preferably in the range of 33.0 to 45.0 mol%, even more preferably in the range of 35.0 to 44.0 mol%, even more preferably in the range of 37.0 to 43.0 mol%. The comonomers present in the cold soluble xylene fraction (XCS) are as defined above for the random propylene copolymer (R-PP) and the elastomeric propylene copolymer (E), respectively. In a preferred embodiment the comonomer is just ethylene.
[0049] The heterophasic propylene copolymer (RAHECO) can be further defined by its individual components, that is, the random propylene copolymer (R-PP) and the elastomeric propylene copolymer (E).
[0050] Random propylene copolymer (R-PP) comprises monomers copolymerizable with propylene, for example, comonomers such as ethylene and/or α-olefins C4 to C8, in particular ethylene and/or α-olefins C4 to C8, for example 1-butene and/or 1-hexene. Preferably, the random propylene copolymer (R-PP) according to the present invention especially comprises consisting of monomers copolymerizable with propylene from the group consisting of ethylene, 1-butene and 1-hexene. More specifically, the random propylene copolymer (R-PP) of the present invention comprises - in addition to propylene - units derivable from ethylene and/or 1-butene. In a preferred embodiment, the random propylene copolymer (R-PP) comprises units derivable from only ethylene and propylene.
[0051] As mentioned above, the heterophasic propylene copolymer (RAHECO) is characterized by a moderate comonomer content. Therefore, the comonomer content of the random propylene copolymer (R-PP) is in the range 4.4 to 7.3% mol, even more preferably in the range 8 to 7.0 mol%, even more preferably in the range from 5.0 to 6.5% mol.
[0052] The term "random" indicates the comonomers of random propylene copolymer (R-PP), as well as the first fraction of propylene copolymer (R-PP1) and the second fraction of propylene copolymer (R-PP2) are randomly distributed within the propylene copolymers. The term random is understood in accordance with IUPAC (Glossary of Basic Terms in Polymer Science; IUPAC 1996 Recommendations).
[0053] The random propylene copolymer (R-PP) preferably comprises at least two polymer fractions, such as two or three polymer fractions, all of which are propylene copolymers. Even more preferred the random propylene copolymer (R-PP) preferably comprises consists of a first propylene copolymer fraction (R-PP1) and a second propylene copolymer fraction (R-PP2). It is preferred that the first propylene copolymer fraction (R-PP1) is the lean comonomer fraction while the second propylene copolymer fraction (R-PP2) is the rich comonomer fraction.
[0054] With regard to the comonomers used for the first fraction of propylene copolymer (R-PP1) and second fraction of propylene copolymer (R-PP2) reference is made to the random propylene copolymer (R-PP) comonomers . Preferably, the first propylene copolymer fraction (R-PP1) and the second propylene copolymer fraction (R-PP2) contain the same comonomers as ethylene.
[0055] It is preferred that the random propylene copolymer (R-PP) is characterized by its relative content of isolate to block ethylene sequences (I(E)). According to the present invention, the isolate to block the ethylene sequences (I(E)) of the random propylene copolymer (R-PP) is measured in the cold insoluble xylene fraction (XCI) of the heterophasic propylene copolymer (RAHECO) ). Therefore, the cold insoluble xylene fraction (XCI) of the heterophasic propylene copolymer (RAHECO) has an isolate to block ethylene sequences (I(E)) in the range of 50.0 to 65.0%, more preferably in the range of 53.0 to 63.0%, even more preferably in the range of 55.0 to 62.0%.
[0056] The content [%] of I(E) is defined by inequality (II)
where I(E) is the relative content of isolate to block ethylene sequences [in %]; fPEP is the molar fraction of the propylene/ethylene/propylene (PEP) sequences cold insoluble xylene (XCI) of heterophasic propylene copolymer (RAHECO); fPEE is the molar fraction of propylene/ethylene/ethylene (PEE) sequences and ethylene/ethylene/propylene (EEP) sequences) cold xylene insoluble fraction (XCI) of the heterophasic propylene copolymer (RAHECO); fEEE is the molar fraction of ethylene/ethylene/ethylene (EEE) sequences in cold xylene insoluble fraction (XCI) of the heterophasic propylene copolymer (RAHECO), in which all sequence concentrations are based on a triad statistical analysis of C13-NMR data.
[0057] The random propylene copolymer (R-PP) according to the present invention has a melt flow MFR2 (230°C/2.16 kg) measured in accordance with ISO 1133 in the range from 3.0 to 8, 0 g/10 min, more preferably in the range 3.2 to 7.0 g/10 min, even more preferably in the range 3.3 and 6.5 g/10 min.
[0058] The heterophasic propylene copolymer (RAHECO) preferably comprises 60 to 95% by weight, such as 65 to 95% by weight, more preferably 60 to 90% by weight, such as 65 to 90% by weight, even more preferably 60 0.0 to 87.0% by weight, (such as 65 to 87% by weight) or 60.0 to 88.0% by weight (such as 65 to 88% by weight) of the random propylene copolymer (R-PP), based on the total weight of the heterophasic propylene copolymer (RAHECO).
[0059] Furthermore, the heterophasic propylene copolymer (RAHECO) preferably comprises as 5 to 40% by weight (such as 5 to 35% by weight), more preferably 10 to 40% by weight, (such as 10 to 35, 0% by weight), even more preferably 12.0 to 40.0% by weight (such as 12 to 35% by weight) or 13.0 to 40% by weight (such as 13 to 35% by weight) of the copolymer of elastomeric propylene (E), based on the total weight of the heterophasic propylene copolymer (RAHECO).
Thus, it is considered that the heterophasic propylene copolymer (RAHECO) preferably comprises, more preferably consists of, 60 to 95% by weight (such as 65.0 to 95.0% by weight), more preferably 60 to 90 % by weight (such as 65 to 90% by weight, even more preferably 60.0 to 87.0% by weight (such as 65 to 87% by weight) or 60.0 to 88.0% by weight (such as 65 to 88 % by weight) of the random propylene copolymer (R-PP) and 5 to 40% by weight (such as 5 to 35% by weight), more preferably 10 to 40% by weight (such as 10 to 35% by weight), further more preferably 12.0 to 40.0% by weight (such as 12 to 35% by weight) or 13.0 to 40% by weight (such as 13 to 35% by weight) of the elastomeric (E) propylene copolymer, based in the total weight of the heterophasic propylene copolymer (RAHECO).
[0061] Therefore, an additional component of the heterophasic propylene copolymer (RAHECO) is the elastomeric propylene copolymer (E) dispersed in the matrix (M). Regarding the comonomers used in the elastomeric propylene copolymer (E), the information provided for the heterophasic propylene copolymer (RAHECO) is referred to. Therefore, the elastomeric propylene copolymer (E) comprises monomers copolymerizable with propylene, for example, comonomers such as ethylene and/or C4 to C8 α-olefins, in particular C4 to C6 α-olefins, for example 1-butene and /or 1-hexene. Preferably, the elastomeric propylene copolymer (E) comprises, in particular, consists of monomers copolymerizable with propylene from the group consisting of ethylene, 1-butene and 1-hexene. More specifically, the elastomeric propylene copolymer (E) comprises - in addition to propylene - units derivable from ethylene and/or 1-butene. Thus, in an especially preferred embodiment, the elastomeric propylene copolymer (E) comprises units derivable from only ethylene and propylene.
[0062] The comonomer content of the elastomeric (E) propylene copolymer is preferably in the range of 35.0 to 55.0 mol%, more preferably in the range of 37.0 to 53.0 mol%, even more preferably in the range from 38.0 to 51.0 mol%.
[0063] As mentioned above multiphase structures can be identified by the presence of at least two different glass transition temperatures. The first upper glass transition temperature (Tg(1) represents the matrix while the second lower glass transition temperature Tg(2) reflects the elastomeric propylene copolymer (E) of the heterophasic propylene copolymer (RAHECO).
[0064] Therefore, it is a preferred requirement of the present invention that the heterophasic propylene copolymer (RAHECO) has a second glass transition temperature Tg(2) that satisfies inequality (I), more preferably inequality (Ia), even more preferably inequality (Ib),
where Tg(2) is the second glass transition temperature of the heterophasic propylene copolymer (RAHECO); C (XCS) is the comonomer content [in mol %] of the cold xylene soluble fraction (XCS) of the heterophasic propylene copolymer (RAHECO).
[0065] Preferably, the second glass transition temperature Tg(2) is less than -20°C, such as below -35°C, more preferably is in the range -65 to -45°C, even more preferably in the range from -62 to -48°C. It is especially preferred that the heterophasic propylene copolymer (RAHECO) has a second glass transition temperature Tg(2), as mentioned in the present paragraph, and fulfills inequality (I) as defined in the present invention.
[0066] It is further appreciated that the heterophasic propylene copolymer (RAHECO) according to the present invention additionally has a first glass transition temperature Tg(1) (which represents the matrix (M) of the heterophasic propylene copolymer ( RAHECO)) in the range of -12 to +2°C, more preferably in the range of -10 to +2°C.
[0067] Therefore, the first glass transition temperature Tg(1) is preferably above the second glass transition temperature Tg(2). Even more preferably, the difference between the first glass transition temperature Tg(1) and the second glass transition temperature Tg(2) is at least 40°C, more preferably at least 45°C, even more preferably in the range of 40 to 55°C, even more preferably in the range 45 to 52°C.
[0068] The heterophasic propylene copolymer (RAHECO) as defined in the present invention may contain up to 5.0% by weight of additives such as nucleating agents and antioxidants as well as slip agents and anti-blocking agents. Preferably, the additive content (without α-nucleating agents) is less than 3.0% by weight, such as less than 1.0% by weight.
[0069] In one embodiment of the present invention, the heterophasic propylene copolymer (RAHECO) comprises a nucleating agent, more preferably an a-nucleating agent. Even more preferred, the present invention is free of e-nucleating agents. The α-nucleating agent is preferably selected from the group consisting of (i) salts of monocarboxylic acids and polycarboxylic acids, for example sodium benzoate or aluminum tert-butyl benzoate, and (ii) dibenzylidenesorbitol (for example , 1,3:2,4 dibenzylidenesorbitol) and C1-C8-alkyl substituted dibenzylidenesorbitol derivatives, such as methyldibenzylidenesorbitol, ethyldibenzylidenesorbitol or dimethyldibenzylidenesorbitol (e.g. 1,3:2.4 di(methylbenzylidene)sorbitol), or nonitol derivatives substituted, such as 1,2,3,-trideoxy-4,6: 5,7-bis-O -[(4-propylphenyl)methylene]-nonitol, and (iii) salts of phosphoric acid diesters, e.g. 2,2'-methylenebis(4,6-di-tert-butylphenyl) sodium or hydroxy-bis[2,2'-methylene-bis(4,6-di-t-butylphenyl)aluminum] phosphate, and (iv) vinylcycloalkane polymer and vinylalkane polymer, and (v) their mixtures.
[0070] Such additives are generally commercially available and are described, for example, in "Plastic Additives Handbook", 5th edition, 2001 by Hans Zweifel.
[0071] Preferably, the heterophasic propylene copolymer (RAHECO) contains up to 2.0% by weight of the a-nucleating agent. In a preferred embodiment, the heterophasic propylene copolymer (RAHECO) does not contain more than 3000 ppm, more preferably between 1 and 3,000 ppm, more preferably 5 to 2000 ppm of an α-nucleating agent, in particular selected from from the group consisting of dibenzylidenesorbitol (eg 1,3:2,4 dibenzylidene sorbitol), dibenzylidenesorbitol derivative, preferably dimethyldibenzylidenesorbitol (eg 1,3:2,4 di(methylbenzylidene)sorbitol), or substituted nonitol derivatives , such as 1,2,3,-trideoxy-4,6:5,7-bis-O-[(4-propylphenyl)methylene]-nonitol, vinylcycloalkane polymer, vinylalkane polymer, and mixtures thereof.
[0072] The heterophasic propylene copolymer (RAHECO) according to the present invention is preferably produced in the presence of (a) a Ziegler-Natta (ZN-C) catalyst comprising the compounds (TC) of a transition metal of the Group 4 to 6 of IUPAC, a Group 2 metal compound (MC) and an internal donor (ID), wherein said internal donor (ID) is a non-phthalic compound, preferably is a non-phthalic acid ester, and further more preferably it is a diester of non-phthalic dicarboxylic acids; (b) optionally, a cocatalyst (Co), and (c) optionally an external donor (ED).
[0073] It is preferred that the internal donor (ID) is selected from optionally substituted malonates, maleates, succinates, glutarates, cyclohexene-1,2-dicarboxylates, benzoates and derivatives and/or mixtures thereof, preferably the donor internal (ID) is a citraconate. Additionally or alternatively, the molar ratio of cocatalyst (Co) to external donor (ED) [Co/ED] is 5 to 45.
[0074] It is thus appreciated that the heterophasic propylene copolymer (RAHECO) is preferably free of phthalic acid esters, as well as their respective decomposition products, i.e., phthalic acid esters, typically used as an internal catalyst donor from Ziegler-Natta (ZN). Preferably, the heterophasic propylene copolymer (RAHECO) is free of phthalic compounds as well as their respective decomposition products, i.e. phthalic compounds typically used as an internal donor of Ziegler-Natta (ZN) catalysts.
[0075] The term "free" from phthalic acid esters, preferably phthalic compounds, in the sense of the present invention refers to a heterophasic propylene copolymer (RAHECO) in which there are no phthalic acid esters as well as no respective decomposition products , preferably no phthalic compounds, as well as no decomposition products thereof in any way, are detectable.
[0076] As the heterophasic propylene copolymer (RAHECO) comprises random propylene copolymer (R-PP) and elastomeric propylene copolymer (E), the individual components are preferably also free of phthalic acid esters, as well as their respective decomposition products, more preferably phthalic compounds, as well as their respective decomposition products.
[0077] The heterophasic propylene copolymer (RAHECO) comprises a matrix (M) being a random propylene copolymer (R-PP) and an elastomeric propylene copolymer (E) dispersed in said matrix (M). Preferably, the propylene random copolymer (R-PP) comprises at least two polymer fractions, such as two or three polymer fractions, all of which are propylene copolymers. Even more preferred the random propylene copolymer (R-PP) comprises, preferably consists of, a first propylene copolymer fraction (R-PP1) and a second propylene copolymer fraction (R-PP2).
[0078] Furthermore, it is preferred that the first fraction of propylene copolymer (R-PP1) and the second fraction of propylene copolymer (R-PP2) have the same melt flow nearby. Therefore, it is preferable that the difference between the melt flow rate of random propylene copolymer (R-PP) and the first fraction of propylene copolymer (R-PP1) [MFR (Pre-R-PP) - MFR(Pre- R-PP1)] is less than +/- 2.5 g/10 min, more preferably +/- 2.0 g/10 min, even more preferably +/- 1.5 g/10 min. Thus, in one embodiment the first propylene copolymer fraction (R-PP1) and the second propylene copolymer fraction (R-PP2) have a melt flow MFR2 (230°C) in the range from 3.0 to 8.5 g/10 min.
[0079] The copolymer content also impacts the content of soluble in xylene. Consequently it is preferred that the first fraction of propylene copolymer (R-PP1) has a cold soluble xylene (XCS) content in the range of 3.0 to 15.0% by weight, more preferably in the range of 3.5 to 12.0% by weight and/or the random propylene copolymer (R-PP) has a cold soluble xylene (XCS) content in the range of 4.0 to 15.0% by weight, more preferably in the range from 4.5 to 12.0% by weight.
[0080] The present invention is not only directed to the present heterophasic propylene copolymer (RAHECO), but also to unoriented films made therefrom. Therefore, in a further embodiment the present invention is directed to non-oriented films, such as molded films or blown films, for example cold air blown films, comprising at least 70.0% by weight, which preferably comprises at least 80.0% by weight, more preferably comprising at least 90% by weight, even more preferably at least 95.0% by weight, even more preferably comprising at least 95.0% by weight, even more preferably comprising at least 99, 0% by weight of the present heterophasic propylene copolymer (RAHECO).
[0081] Distinguish between unoriented and oriented films (see, for example, polypropylene manual, Nello Pasquini, 2nd edition, Hanser). Oriented films are typically monoaxially or biaxially oriented films, while non-oriented films are cast or blown films. In this way an unoriented film is not stretched intensively in the machine and/or in the transverse direction as is done with oriented films. Thus, the unoriented film according to the present invention is not a monoaxially or biaxially oriented film. Preferably, the unoriented film according to the present invention is a blown film or molded film.
[0082] In a specific embodiment the unoriented film is a molded film or a film blown by cold air.
[0083] Preferably, the unoriented film has a thickness of 10 to 1000 µm, more preferably between 20 and 700 µm, such as 40 to 500 µm.
[0084] The present invention is also directed to the use of heterophasic propylene copolymer (RAHECO) in the manufacture of non-oriented films, such as molded films or a blown film, for example by cold air.
[0085] Furthermore, the present invention is directed to a sterilizable or sterilized film, such as an unoriented sterilizable or sterilized film. More preferably, the invention is directed to containers, i.e. pouches, especially to sterilizable or sterilized containers, i.e. pouches, comprising, preferably consisting of, the (non-oriented) film as defined herein. The container is in particular a bag. Furthermore, said container, i.e. pouch, has preferably been subjected to a sterilization treatment.
[0086] Furthermore, the present invention is directed to the use of heterophasic propylene copolymer as defined herein to improve the balance between softness and haze of an unoriented film. In particular, the improvement is achieved when the heterophasic propylene copolymer (RAHECO) has a) a flexural modulus measured according to ISO 178 in the range of 450 to 800 MPa, preferably in the range of 480 to 650 MPa and more preferably 500 to 650 MPa, and/or b) a turbidity in accordance with ASTM D 1003-00 measured on a 1mm thick injection molded sample of <50.0%, preferably in the range of 10.0 to 50.0 % and more preferably in the range of 25.0 to 50.0%. .
[0087] Additionally or alternatively, improvement is achieved when the heterophasic propylene copolymer (RAHECO) has a) a transparency in accordance with ASTM D1003-00 measured on a 1mm thick injection molded sample of hair minus 75.0%, preferably in the range of 75.0 to 95.0% and more preferably in the range of 75.0 to 90.0%, and/or b) a clarity in accordance with measured ASTM D1003-00 in an injection molded 1mm thick sample of at least 90.0%, preferably in the range of 90.0 to 99.0% and more preferably in the range of 92.0 to 98.0%.
[0088] For example, the improvement is achieved when the heterophasic propylene copolymer (RAHECO) has a) a flexural modulus measured in accordance with ISO 178, in the range of 450 to 800 MPa, preferably in the range of 490 to 650 MPa, and more preferably in the range of 500 to 650 MPa, and b) a turbidity in accordance with ASTM D 1003-00 measured on a 1 mm thick injection molded sample < 50.0%, preferably in the range of 10, 0 to 50.0% and more preferably in the range of 25.0 to 50.0%, and c) a transparency in accordance with ASTM D1003-00 measured on a 1mm thick injection molded sample of at least 75 .0%, preferably in the range of 75.0 to 95.0% and more preferably in the range of 75.0 to 90.0%, and b) a clarity in accordance with ASTM D1003-00 measured on a sample of 1 millimeter injection molded thickness of at least 90.0%, preferably in the range of 90.0 to 99.0% and more preferably in the range of 92.0 to 98.0%.
[0089] Additionally or alternatively, the improvement is achieved when the heterophasic copolymer of propylene (RAHECO) has c) a turbidity before sterilization determined in accordance with ASTM D 1003-00 measured on a molded film of 50 µm below 5 %, preferably less than 3%, and/or d) a turbidity after sterilization determined in accordance with ASTM D 1003-00 measured on a cast film of 50 µm below 10% preferably below 6%.
[0090] The present heterophasic propylene copolymer (RAHECO) is preferably produced in a multistage process comprising at least two reactors connected in series a heterophasic propylene copolymer (RAHECO) comprising a matrix (M) being a propylene copolymer random (PP) and an elastomeric propylene copolymer (E) dispersed in said matrix (M),
[0091] Furthermore, the weight ratio between the first fraction of propylene copolymer (R-PP1) and second fraction of propylene copolymer (R-PP2) is preferably from 20:80 to 80:20, more preferably 25: 75 to 75:25, even more preferably 30:70 to 70:30.
[0092] Preferably, the heterophasic propylene copolymer (RAHECO) is obtained by a sequential polymerization process comprising the steps of (a) polymerization in a first reactor of propylene and ethylene and/or α-olefin C4 to C8 obtaining thus a first fraction of propylene copolymer (R-PP1), (b) transferring said first fraction of propylene copolymer (R-PP1) to a second reactor, (c) polymerization in said second reactor in the presence of the first fraction of propylene copolymer (R-PP1) propylene and ethylene and/or α-olefin C4 to C8 obtaining a second propylene copolymer fraction (R-PP2), said first propylene copolymer fraction (R-PP1) and said second fraction of propylene copolymer (R-PP2) form the matrix (PP), (d) transfer said matrix (M) into a third reactor, (e) polymerization in said third reactor in the presence of the matrix (M) propylene and ethylene and/or α-olefin C4 to C8 obtaining an elastomeric propylene copolymer (E ), said matrix (M) and said elastomeric propylene copolymer (E) form the heterophasic propylene copolymer (RAHECO).
[0093] For preferred embodiments of heterophasic propylene copolymer (HECO), random propylene copolymer (R-PP), the first fraction propylene copolymer (R-PP1), the second fraction propylene copolymer (R -PP2), and the elastomeric copolymer (E) is referred to the definitions given above.
[0094] The term "sequential polymerization process" indicates that heterophasic propylene copolymer (HECO) is produced in at least two, such as three, reactors connected in series. Thus, the present process comprises at least a first reactor, a second reactor, and optionally a third reactor. The term "polymerization process" will indicate that the main polymerization takes place. Thus, in case the process consists of three polymerization reactors, this definition does not exclude the option that the total process comprises, for example, a prepolymerization step in a prepolymerization reactor. The term "consists of" is just a closing formulation, taking into account the main polymerization process.
[0095] The first reactor is preferably a suspension reactor and can be any simple stirred batch tank reactor or closed loop reactor operating in bulk or in suspension. Mass means a polymerization in a reaction medium that comprises at least 60% (w/w) of monomer. According to the present invention, the suspension reactor is preferably a closed-loop (bulk) reactor.
[0096] The second reactor and the third reactor are preferably gas phase reactors. Such gas phase reactors can be any mechanically mixed or fluid bed reactors. Preferably, the gas phase reactors comprise a mechanically stirred fluidized bed reactor with gas velocities of at least 0.2 m/sec. Thus, the gas phase reactor is considered to be a fluidized bed type reactor preferably with a mechanical stirrer.
[0097] Thus, in a preferred embodiment the first reactor is a suspension reactor, as a closed loop reactor, while the second reactor and the third reactor (R3) are gas phase reactors (GPR). Therefore, for the present process, at least three, preferably three polymerization reactors, i.e. a suspension reactor as closed loop reactor, a first gas phase reactor and a second gas phase reactor are connected in series they're used. If necessary, before the suspension reactor a pre-polymerization reactor is placed.
[0098] A preferred multi-phase process is a "closed loop gas phase" process as developed by Borealis A/S, Denmark (known as BORSTAR® technology) described for example in the patent literature such as in EP 0 887 379, WO 92/12182, WO 2004/000899, WO 2004/111095, WO 99/24478, WO 99/24479 or in WO 00/68315.
[0099] An additional suitable gas-phase suspension process is the Spheripol® process from Basell.
[00100] Preferably, in the present process to produce the heterophasic propylene copolymer (RAHECO) as defined above the conditions for the first reactor, that is, the suspension reactor, as a closed loop reactor, may be as follows: - the temperature is within the range of 50°C to 110°C, preferably between 60°C and 100°C, more preferably between 68 and 95°C, - the pressure is within the range of 2 MPa to 8 MPa (20 bar to 80 bar), preferably between 4 MPa to 7 MPa (40 bar and 70 bar), - hydrogen, can be added to control the molar mass in a manner known per se.
[00101] Subsequently, the reaction mixture from the first reactor is transferred to the second reactor, i.e. gas phase reactor, where the conditions are preferably as follows: - the temperature is within the range of 50°C to 130° C, preferably between 60°C and 100°C, - the pressure is in the range of 0.5 MPa to 5 MPa (5 bar to 50 bar), preferably between 1.5 MPa and 3.5 MPa (15 bar and 35 bar), - hydrogen, can be added to control the molar mass in a way known per se.
[00102] The condition in the third reactor is similar to that in the second reactor.
[00103] Residence time may vary in the three reactor zones.
[00104] In an embodiment of the process for the production of heterophasic propylene copolymer (RAHECO) the residence time in the bulk reactor, for example, closed circuit is in the range of 0.1 to 2.5 hours, for example , 0.15 to 1.5 hours and the residence time in the gas phase reactor will generally be 0.2 to 6.0 hours, such as 0.5 to 4.0 hours.
[00105] If desired, polymerization can be carried out in a known manner under supercritical conditions in the first reactor, that is, in the suspension reactor, as in the closed loop reactor, and/or as a condensate mode in gas phase reactors .
[00106] Preferably, the process also comprises a prepolymerization with the catalyst system, as described in detail below, comprising a Ziegler-Natta precatalyst, an external donor and optionally a cocatalyst.
[00107] In a preferred embodiment, the prepolymerization is carried out as bulk suspension polymerization in liquid propylene, i.e., the liquid phase mainly comprises propylene, with a smaller amount of other reactants and, optionally, inert components , dissolved there.
[00108] The prepolymerization reaction is typically carried out at a temperature from 10 to 60°C, preferably from 15 to 50°C, and more preferably from 20 to 45°C.
[00109] The pressure in the prepolymerization reactor is not critical, but it should be high enough to keep the reaction mixture in liquid phase. Thus, the pressure can be from 2 to 10 MPa (20 to 100 bar), for example 3 to 7 MPa (30 to 70 bar).
[00110] The catalyst components are preferably all introduced to the prepolymerization step. However, where the solid catalyst component (i) and the cocatalyst (ii) can be fed separately, it is possible that only a part of the cocatalyst is introduced into the prepolymerization stage and the remainder into subsequent polymerization steps. Furthermore, in such cases, it is necessary to introduce so much cocatalyst to the prepolymerization stage that a sufficient polymerization reaction is obtained therein.
[00111] It is possible to add other components also to the pre-polymerization phase. In this way, hydrogen can be added at the prepolymerization stage to control the molecular weight of the prepolymer as is known in the art. In addition, antistatic additive can be used to prevent particles from adhering to each other or to the reactor walls.
[00112] Precise control of prepolymerization conditions and reaction parameters is within the skill of the art.
[00113] According to the invention, the heterophasic propylene copolymer (RAHECO) is obtained by a multistage polymerization process, as described above, in the presence of a catalyst system.
[00114] As noted above, in the specific process for the preparation of the heterophasic propylene copolymer (RAHECO) as defined above, a specific Ziegler-Natta (ZN-C) catalyst must be used. Therefore, the Ziegler-Natta (ZN-C) catalyst will now be described in more detail.
[00115] The catalyst used in the present invention is a solid Ziegler-Natta (ZN-C) catalyst, which comprises the compounds (TC) of a transition metal from Group 4 to 6 of the IUPAC, such as titanium, a compound of Group 2 metal (MC), such as a magnesium and an internal donor (ID) being a non-phthalic compound, preferably a non-phthalic acid ester, even more preferably being a non-phthalic dicarboxylic acid diester, as described in more detail below. Thus, the catalyst is totally free from unwanted phthalic compounds. Furthermore, the solid catalyst is free of any external support material, such as silica or MgCl 2 , but the catalyst is self-supporting.
[00116] The Ziegler-Natta (ZN-C) catalyst can be further defined by the way it is obtained. Therefore, the Ziegler-Natta (ZN-C) catalyst is preferably obtained by a process comprising the steps of a) to 1) providing a solution of at least one Group 2 metal (Ax) alkoxy compound which is the reaction product of a Group 2 metal (MC) compound and an alcohol (A) comprising, in addition to the hydroxyl portion, at least an ether portion, optionally in an organic liquid reaction medium; or a2) a solution of at least one Group 2 metal alkoxy compound (Ax') which is the reaction product of a Group 2 metal compound (MC) and an alcohol mixture of alcohol (A) and a monohydric alcohol (B) of formula ROH, optionally in an organic liquid reaction medium; or a3) provide a solution of a mixture of a Group 2 alkoxy compound (Ax) and a Group 2 metal alkoxy compound (Bx) which is the reaction product of a Group 2 metal compound (MC) and the alcohol monohydric (B), optionally in an organic liquid reaction medium; and b) adding said solution from step a) with at least one compound (TC) of a Group 4 to 6 transition metal and c) obtaining the solid catalyst component particles, and adding a non-phthalic internal electron donor ( ID) at any step before step c).
[00117] The internal donor (ID) or a precursor thereof is preferably added to the solution of step a).
[00118] According to the above procedure the Ziegler-Natta (ZN-C) catalyst can be obtained through the precipitation method or through emulsion (liquid/liquid two-phase system) - solidification method, depending on the conditions especially the temperature used in steps b) and c).
[00119] In both methods (precipitation or emulsion-solidification) the chemistry of the catalyst is the same.
[00120] In combination of the solution precipitation method of step a) with at least one transition metal compound (TC) in step b) is performed and the entire reaction mixture is kept at least at 50°C, more preferably in the temperature range of 55 to 110°C, more preferably in the range of 70 to 100°C, to ensure complete precipitation of the catalyst component in solid particulate form (step c).
[00121] In the emulsion-solidification method in step b) the solution from step a) is typically added to at least one transition metal (TC) compound at a lower temperature, such as from -10 to lower than 50°C , preferably from -5 to 30°C. During stirring of the emulsion the temperature is typically maintained between -10 to below 40°C, preferably -5 to 30°C. Droplets from the dispersed phase of the emulsion form the active catalyst composition. Solidification (step c) of the droplets is suitably carried out by heating the emulsion to a temperature of 70 to 150°C, preferably 80 to 110°C.
[00122] The catalyst prepared by the emulsion-solidification method is preferably used in the present invention.
[00123] In a preferred embodiment, in step a) the solution of a2) or a3) are used, that is, a solution of (Ax') or a solution of a mixture of (Ax) and (Bx).
[00124] Preferably, the Group 2 metal (MC) is magnesium.
[00125] The magnesium alkoxy compounds (AX), (AX') and (Bx) can be prepared in situ in the first step of the catalyst preparation process, step a), by reacting the magnesium compound with the alcohol (s ) as described above, or said magnesium alkoxy compounds can be separately prepared magnesium alkoxy compounds and or they can be further commercially available as magnesium alkoxy compounds, ready and used as such in the process of preparing the catalyst of the invention.
[00126] Illustrative examples of alcohols (A) are dihydric alcohol monoethers (glycol monoethers). Preferred alcohols (A) are C2 to C4 glycol monoethers, wherein the ether moieties comprise from 2 to 18 carbon atoms, preferably from 4 to 12 carbon atoms. Preferable examples are 2-(2-ethylhexyloxy)ethanol, 2-butyloxy ethanol, 2-hexyloxy ethanol and 1,3-propylene glycol monobutyl ether, 3-butoxy-2-propanol, with 2-(2- ethylhexyloxy)ethanol and 1,3-propylene glycol monobutyl ether, 3-butoxy-2-propanol being particularly preferred.
[00127] Illustrative monohydric alcohols (B) are of formula ROH, wherein R is a C6-C10 straight or branched chain alkyl residue. The most preferred monohydric alcohol is 2-ethyl-1-hexanol or octanol.
[00128] Preferably, a mixture of alkoxy compounds of Mg (Ax) and (Bx) or mixture of alcohols (A) and (B), respectively, are used and employed in a molar ratio of Bx:Ax or B:A from from 8:1 to 2:1, more preferably from 5:1 to 3:1.
[00129] Magnesium alkoxy compound can be a reaction product of alcohol(s) as defined above, and a magnesium compound selected from dialkyl magnesiums, alkyl magnesium alkoxides, magnesium dialkoxides, alkoxy magnesium halides and magnesium alkyl halides. The alkyl groups can be similar or different C1-C20 alkyl, preferably C2-C10 alkyl. Typical alkyl alkoxy magnesium compounds, when used, are ethyl magnesium butoxide, butyl magnesium pentoxide, octyl magnesium butoxide and octyl magnesium octoxide. Preferably, dialkyl magnesiums are used. Most preferred dialkyl magnesiums are butyl octyl magnesium or butyl ethyl magnesium.
[00130] It is also possible that the magnesium compound may react, in addition to alcohol (A) and alcohol (B), also with a polyhydric alcohol (C) of formula R''(OH)m to obtain a said magnesium alkoxide compounds. Preferred polyhydric alcohols, if used, are the alcohols, where R'' is a straight-chain, cyclic or branched C2 to C10 hydrocarbon residue, and m is an integer from 2 to 6.
[00131] The alkoxy magnesium compounds of step a) are thus selected from the group consisting of magnesium dialkoxides, diaryloxy magnesiums, magnesium alkyloxy halides, magnesium aryloxy halides, magnesium alkyl alkoxides, alkoxides of aryl magnesium and alkyl magnesium aryloxides. In addition, a mixture of magnesium dihalide and a magnesium dialkoxide can be used.
[00132] The solvents to be used for the preparation of the catalyst of the present invention can be selected from aliphatic and aromatic, branched and cyclic straight chain hydrocarbons with 5 to 20 carbon atoms, more preferably 5 to 12 carbon atoms, or its mixtures. Suitable solvents include benzene, toluene, cumene, xylol, pentane, hexane, heptane, octane and nonane. Hexanes and pentanes are particularly preferred.
[00133] Compound Mg is typically supplied as a 10 to 50% by weight solution in a solvent as indicated above. Typical commercially available Mg compound, especially dialkyl magnesium solutions are 20 to 40% by weight of solutions in toluene or heptanes.
[00134] The reaction for the preparation of the magnesium alkoxy compound can be carried out at a temperature of 40° to 70°C. Most suitable temperature is selected depending on the compound of Mg and alcohol(s) used.
The Group 4 to 6 transition metal compound is preferably a titanium compound, more preferably a titanium halide, such as TiCl4.
[00136] The internal donor (ID) used in the preparation of the catalyst used in the present invention is preferably selected from (di)esters of non-phthalic (di)carboxylic acids, 1,3-diethers, their derivatives and mixtures. Especially preferred donors are diesters of monounsaturated dicarboxylic acids, in particular, esters belonging to a group comprising malonates, maleates, succinates, citraconates, glutarates, cyclohexene-1,2-dicarboxylates and benzoates, and any derivatives thereof and/or mixtures thereof. Preferred examples are, for example, substituted maleates and citraconates, more preferably citraconates.
[00137] In the emulsion method, the liquid-liquid two-phase system can be formed by simple agitation and optionally the addition of (more) solvent(s) and additives such as turbulence minimizing agent (TMA) ) and/or emulsifying agents and/or emulsion stabilizers, such as surfactants, which are used in a manner known in the art to facilitate the formation of and/or stabilize the emulsion. Preferably, the surfactants are acrylic or methacrylic polymers. Particularly preferred are unbranched C12 to C20 (meth)acrylates such as poly(hexadecyl)(meth)acrylate and poly(octadecyl)(meth)acrylate and mixtures thereof. Turbulence minimizing agent (TMA), if used, is preferably selected from α-olefin polymers of α-olefin monomers with 6 to 20 carbon atoms, such as polyoctene, polynonene, polydecene, polyundecene or polydodecene or mixtures thereof. Most preferable is polydecene.
[00138] The solid particulate product obtained by the precipitation or emulsion-solidification method can be washed at least once, preferably at least twice, more preferably at least three times with an aromatic and/or aliphatic hydrocarbon, preferably with toluene, heptane or pentane. The catalyst can additionally be dried, such as by evaporation or washing with nitrogen, or it can be suspended with an oily liquid without any drying step.
[00139] The Ziegler-Natta catalyst finally obtained is desirably in the form of particles which generally have an average particle size range of 5 to 200 µm, preferably 10 to 100. The particles are compact with low porosity and have surface area less than 20 g/m2, more preferably less than 10 g/m2. Typically, the amount of Ti is from 1 to 6% by weight, Mg from 10 to 20% by weight and the donor 10 to 40% by weight of the catalyst composition.
[00140] Detailed description of the preparation of catalysts is disclosed in WO 2012/007430, EP2610271, EP 261027 and EP2610272 which are incorporated herein by reference.
The Ziegler-Natta (ZN-C) catalyst is preferably used in association with an alkyl aluminum cocatalyst and optionally external donors.
[00142] As an additional component in the present polymerization process an external donor (ED) is preferably present. Suitable external donors (ED) include certain silanes, ethers, esters, amines, ketones, heterocyclic compounds and mixtures thereof. It is especially preferred to use a silane. It is more preferred to use silanes of the general formula RapRbqSi (ORc) (4-pq) where Ra, Rb and Rc represent a hydrocarbon radical, in particular an alkyl or cycloalkyl group, and where p and q are numbers ranging from 0 to 3 with their sum p + q being equal to or less than 3. Ra, Rb and Rc can be chosen independently of each other and can be the same or different. Specific examples of such silanes are (tert-butyl)2Si(OCH3)2, (cyclohexyl) (methyl) Si(OCH3)2, (phenyl)2Si(OCH3)2 and (cyclopentyl)2Si(OCH3)2, or of general formula Si(OCH2CH3)3(NR3R4) wherein R3 and R4 can be the same or different one represents a hydrocarbon group having 1 to 12 carbon atoms.
[00143] R3 and R4 are independently selected from the group consisting of linear aliphatic hydrocarbon group having 1 to 12 carbon atoms, branched aliphatic hydrocarbon group having 1 to 12 carbon atoms and a cyclic aliphatic hydrocarbon group having 1 to 12 atoms of carbon. It is especially preferred that R3 and R4 are independently selected from the group consisting of methyl, ethyl, n-propyl, n-butyl, octyl, decanyl, iso-propyl, iso-butyl, iso-pentyl, tert-butyl, tercamyl, neopentyl, cyclopentyl, cyclohexyl, methylcyclopentyl and cycloheptyl.
[00144] More preferably, both R1 and R2 are the same, even more preferably both R3 and R4 are an ethyl group.
Especially preferred external donors (ED) are the pentyl dimethoxy silane donor (D-donor) or the cyclohexylmethyl dimethoxy silane donor (C-donor), the latter being especially preferred.
[00146] In addition to the Ziegler-Natta catalyst (ZN-C) and the optional external donor (ED) a cocatalyst can be used. The cocatalyst is preferably a Periodic Table Group 13 (IUPAC) compound, for example organoaluminium, such as an aluminum compound such as aluminum alkyl, aluminum halide or an alkyl aluminum halide compound. Therefore, in a specific embodiment the cocatalyst (Co) is a trialkylaluminum, such as triethylaluminum (TEAL), dialkyl aluminum chloride or alkyl aluminum dichloride or mixtures thereof. In a specific embodiment, the cocatalyst (Co) is triethylaluminum (TEAL).
Advantageously, aluminum triethyl (TEAL) has a hydride content, expressed as AlH3, of less than 1.0% by weight with respect to aluminum triethyl (TEAL). More preferably, the hydride content is less than 0.5% by weight, and more preferably, the hydride content is less than 0.1% by weight.
[00148] 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 chosen.
[00149] Therefore, (a) the molar ratio of cocatalyst (Co) to external donor (ED) [Co/ED] should be in the range of 5 to 45, preferably is in the range of 5 to 35, more preferably is in the range of 5 to 25; and optionally (b) the molar ratio of cocatalyst (Co) to titanium compound (TC) [Co/TC] should be in the range of above 80 to 500, preferably is in the range of 100 to 400, even more preferably it is in the range of 120 to 350.
[00150] In the following the present invention is further illustrated by way of examples. EXAMPLES 1. Measurement methods
[00151] The following definitions of terms and methods of determination apply to the above general description of the present invention, as well as to the examples below, unless otherwise defined.
[00152] Calculation of the comonomer content of the second fraction of propylene copolymer (R-PP2):
where w(PP1) is the fraction by weight [in % by weight] of the first fraction of propylene copolymer (R-PP1), w(PP2) is the fraction by weight [in % by weight] of the second fraction of copolymer of propylene (R-PP2), C(PP1) is the comonomer content [in mol %] of the first fraction of propylene copolymer (R-PP1), C(PP) is the comonomer content [in mol %] of the random propylene copolymer (R-PP), C(PP2) is the calculated comonomer content [in mol %] of the second fraction of propylene copolymer (R-PP2).
[00153] Calculation of the cold soluble xylene (XCS) content of the second fraction of propylene copolymer (R-PP2):
where w(PP1) is the fraction by weight [in % by weight] of the first fraction of propylene copolymer (R-PP1), w(PP2) is the fraction by weight [in % by weight] of the second fraction of copolymer of propylene (R-PP2), XS(PP1) is the cold soluble xylene (XCS) content [in % by weight] of the first fraction of propylene copolymer (R-PP1), XS(PP) is the content of Cold soluble xylene (XCS) [in % by weight] of the random propylene copolymer (R-PP), XS(PP2) is the calculated cold soluble xylene (XCS) content [in % by weight] of the second fraction of propylene copolymer (R-PP2), respectively.
[00154] Calculation of the MFR2 melt flow (230°C) of the second fraction of propylene copolymer (R-PP2):
where w(PP1) is the fraction by weight [in % by weight] of the first fraction of propylene copolymer (R-PP1), w(PP2) is the fraction by weight [in % by weight] of the second fraction of copolymer of propylene (R-PP2), MFR (PP1) is the melt flow rate MFR2 (230°C) [in g/10min] of the first fraction of propylene copolymer (R-PP1), MFR (PP) is the flow rate of melting MFR2 (230°C) [in g/10min] of random propylene copolymer (R-PP), MFR (PP2) is the calculated melting rate MFR2 (230°C) [in g/10min] of the second fraction of propylene copolymer (R-PP2).
[00155] Calculation of the comonomer content of the elastomeric propylene copolymer (E), respectively:
where w(PP) is the fraction by weight [in % by weight] of random propylene copolymer (R-PP), i.e. of polymer produced in the first and second reactor (R1 + R2), w(E) is the fraction by weight [in % by weight] of the elastomeric propylene copolymer (E), i.e. of polymer produced in the third and fourth reactor (R3 + R4) C(PP) is the comonomer content [in mol %] of the random propylene copolymer (R-PP), ie the comonomer content [in % by weight] of the polymer produced in the first and second reactor (R1 + R2) , C(RAHECO) is the comonomer content [in % mol] of the propylene copolymer, that is, the comonomer content [in mol %] of the polymer obtained after polymerization in the fourth reactor (R4), C(E) is the calculated comonomer content [in mol %] of the copolymer of elastomeric propylene (E), that is, from the polymer produced in the third and fourth reactors (R3 + R4).
[00156] MFR2 (230°C) is measured according to ISO 1133 (230°C, 2.16 kg load). Microstructure quantification by NMR spectroscopy
[00157] Quantitative nuclear magnetic resonance (NMR) spectroscopy was used to quantify the comonomer content and comonomer sequence distribution of the polymers. Quantitative C13 {H1} NMR spectra were recorded in the solution state using a Bruker Advance III 400 NMR spectrometer operating at 400.15 and 100.62 MHz for H1 and C13, respectively. All spectra were recorded using an optimized C13 10mm probe head extended temperature to 125°C, using nitrogen gas for all tyres. Approximately 200 mg of the material was dissolved in 3 ml of 1,2-tetrachloroethane-d2 (TCE-d2) together with chromium(III) acetylacetonate (Cr(acac)3), resulting in a 65 mM solution of the relaxing agent. in solvent (Singh, G., Kothari, A., Gupta, V., Polymer Testing 28 5 (2009), 475). To ensure a homogeneous solution, after initial sample preparation on a heating block, the NMR tube was further heated in a rotary oven for at least 1 hour. After insertion of the magnet the tube was centrifuged at 10 Hz. This configuration was chosen primarily for the high resolution and quantitatively necessary for accurate quantification of the ethylene content. Standard single-pulse excitation was employed without NOE, using an optimized tip angle, 1 s recycling delay, and a two-level 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, 1128). A total of 6144 (6k) transients were acquired by spectra. Quantitative C13 {H1} NMR spectra were processed, integrated and relevant quantitative properties determined from the integrals using proprietary computer programs. All chemical shifts were indirectly referenced to the central methylene group of the ethylene block (EEE) at 30.00 ppm using the solvent chemical shift. This approach allowed for comparable reference, even when this structural unit was not present. Characteristic signals corresponding to ethylene incorporation have been observed (Cheng, H.N., Macromolecules 17 (1984), 1950).
[00158] With characteristic signs corresponding to 2.1 erythro region defects observed (as described in L. Resconi, L. Cavallo, A. Fait, F. Piemontesi, Chem. Rev. 2000, 100 (4), 1253, in Cheng, HN, Macromolecules 1984, 17, 1950, and in WJ. Wang and S. Zhu, Macromolecules 2000, 33 1157) correction for the influence of region defects on certain properties was necessary. No characteristic signs corresponding to other types of region defects were observed.
[00159] The comonomer fraction was quantified using the method of Wang et. al. (Wang, W-J., Zhu, S., Macromolecules 33 (2000), 1157) by integrating multiple signals from the entire spectral region into the C13 {H1} spectra. This method was chosen for its robust nature and ability to account for the presence of region defects when necessary. Integral regions were slightly adjusted to increase applicability across the range of comonomer contents found.
[00160] For systems in which only ethylene isolated in PPEPP sequences was observed the method of Wang et. al. has been modified to reduce the influence of nonzero integrals from places that are known not to be present. This approach reduces the overestimation of the ethylene content of such systems and was achieved by reducing the number of sites used to determine the absolute ethylene content to: E = 0.5 (Sββ + Sβ + Sβδ + 0.5 (Sαβ + Sαy))
[00161] By using this set of locations the corresponding integral equation becomes: E = 0.5 (IH + IG + 0.5 (IC + ID)) using the same notation used in the article by Wang et. al. (Wang, W-J., Zhu, S., Macromolecules 33 (2000), 1157). Equations used for absolute propylene content were not modified.
[00162] The incorporation of mole percent comonomers was calculated from the mol fraction: E [mol%] = 100 * fE
[00163] The incorporation of comonomer percent by weight was calculated from the mol fraction: E [% by weight] = 100 * (fE * 28.06) / ((fE * 28.06) + ((1-fE ) * 42.08))
[00164] The distribution of the comonomer sequence at the triad level was determined using the analysis method of Kakugo et al. (Kakugo, M., Naito, Y., Mizunuma, K., Miyatake, T. Macromolecules 15 (1982) 1150). This method was chosen for its robust nature and slightly adjusted integration regions to increase the applicability of a wider range of comonomer contents.
[00165] The relative content of isolate to block ethylene incorporation was calculated from the distribution of the triad sequence using the following relationship (equation (I)):
where I(E) is the relative content of isolate to block ethylene sequences [in %]; fPEP is the molar fraction of propylene/ethylene/propylene (PEP) sequences in the sample; fPEE is the molar fraction of propylene/ethylene/ethylene (PEE) sequences and ethylene/ethylene/propylene (EEP) sequences in the sample; fEEE is the molar fraction of ethylene/ethylene/ethylene (EEE) sequences in the sample.
[00166] Intrinsic viscosity is measured according to DIN ISO 1628/1, October 1999 (in decalin at 135°C).
[00167] Solubles in xylene (XCS, % by weight): Content of solubles in cold xylene (XCS) is determined at 25°C according to ISO 16152; first edition; 2005-07-01. The part that remains insoluble is the fraction insoluble in cold xylene (XCI).
[00168] The extractable fraction of hexane is determined according to the FDA method (Federal registration, title 21, chapter 1, part 177, section 1520, n. Annex B) on cast films 100 µm thick mm produced in a monolayer cast film line with a melting temperature of 220°C and a cooling roll temperature of 20°C. The extraction was carried out at a temperature of 50°C and an extraction time of 30 minutes.
[00169] Melting temperature (Tm) and heat of melting (Hf), temperature of crystallization (Tc) and heat of crystallization (Hc): measured with Mettler TA820 differential scanning calorimetry (DSC) on samples from 5 to 10 mg. DSC runs in accordance with ISO 113573:1999 in a heat/cold/heat cycle with a sweep rate of 10°C/min in the temperature range of +23 to +210°C. Crystallization temperature and heat of crystallization (HC) are determined from the cooling step, while the melting temperature and heat of fusion (Hf) are determined from the second heating step.
[00170] The glass transition temperature Tg is determined by dynamic mechanical analysis according to ISO 6721-7. Measurements are made in torsional mode on compression molded samples (40x10x1 mm3) between -100°C and 150°C with a heating rate of 2°C/min and a frequency of 1 Hz.
[00171] Modulus of elasticity in the transverse and machine direction was determined in accordance with ISO 527-3, at 23°C, on 50 µm thick molded films produced in a monolayer molded film line with a temperature of melting 220°C and a cooling roll temperature of 20°C. The test was carried out at a transverse head speed of 1 mm/min. Total penetration energy:
[00172] The impact strength of films is determined by the "Dynatest" method according to ISO 7725-2 on films as described for the modulus of elasticity. The "Wbreak" value [J/mm] represents the total penetration energy per mm of thickness that a film can absorb before breaking. The higher this value, the more resistant the material.
[00173] Transparency, turbidity and clarity were determined according to ASTM D1003-00 on 60x60x1 mm3 injection molded plates according to EN ISO 1873-2 using a melting temperature of 200°C and on cast films of 50 µm thick produced on a monolayer cast film line had a melting temperature of 220°C and a cooling roll temperature of 20°C.
[00174] Flexion Modulus: The flexion modulus was determined at three bending points according to ISO 178 on 80x10x4 mm3 injection molded test bars at 23°C in accordance with EN ISO 1873-2.
[00175] Charpy impact notch resistance is determined in accordance with ISO 179 1eA at 23°, and at -20°C, using 80x10x4 mm3 injection molded test bars in accordance with EN ISO 1873-2 .
[00176] Steam sterilization was performed on a Systec D series machine (Systec Inc., USA). The samples were heated at a heating rate of 5°C/min starting at 23°C. After being held for 30 min at 121°C, they were immediately removed from the steam sterilizer and stored at room temperature until further processed. 2. Examples
[00177] The catalyst used in the polymerization processes for the heterophasic propylene copolymers (RAHECO) of the examples of the invention (IE) was prepared as follows: Chemicals used:
20% solution in toluene of butyl ethyl magnesium (Mg(Bu) (Et), BEM), supplied by Chemtura 2-ethyl-hexanol, supplied by Amphochem 3-butoxy-2-propanol - (DOWANOL™ PNB) , supplied by Dow bis(2-ethylhexyl citraconate), supplied by SynphaBase TiCl4 supplied by Millenium Chemicals Toluene, supplied by Aspokem Viscoplex® 1-254, supplied by Evonik Heptane, supplied by Chevron Preparation of a Mg Alkoxy Compound
[00179] Magnesium alkoxide solution was prepared by adding, with stirring (70 rpm), in 11 kg of a 20% by weight solution in toluene of butyl ethyl magnesium (Mg(Bu)(Et)), a mixture of 4.7 kg of 2-ethylhexanol and 1.2 kg of butoxypropanol in a 20 liter stainless steel reactor. During the addition, the reactor contents were kept below 45°C. After the addition was complete, mixing (70 rpm) the reaction mixture was continued at 60°C for 30 minutes. After cooling to room temperature 2.3 kg g of bis(2-ethylhexyl) citraconate donor was added and the holding temperature of the Mg alkoxide solution less than 25°C. Mixing was continued for 15 minutes under stirring (70 rpm). Solid catalyst component preparation
[00180] 20.3 kg of TiCl4 and 1.1 kg of toluene were added to a 20 liter stainless steel reactor. Under mixing at 350 rpm and maintaining the temperature at 0°C, 14.5 kg of the Mg alkoxy compound prepared in Example 1 was added over 1.5 hours. 1.7 L of Viscoplex® 1254 and 7.5 kg of heptane were added and after 1 hour of mixing at 0°C, the temperature of the formed emulsion was raised to 90°C within 1 hour. After 30 minutes, mixing was stopped, catalyst drops were solidified and the formed catalyst particles were allowed to settle. After decanting (1 hour), the supernatant liquid was siphoned. Then, the catalyst particles were washed with 45 kg of toluene at 90°C for 20 minutes, followed by two washes with heptane (30 kg, 15 min). During the first wash with heptane the temperature was lowered to 50°C and during the second wash to room temperature.
[00181] The catalyst thus obtained was used together with triethylaluminum (TEAL) as cocatalyst and cyclohexylmethyl dimethoxy silane (C-donor) as donor.
[00182] The aluminum to donor ratio, the aluminum to titanium ratio and the polymerization conditions are shown in Table 1.
[00183] The catalyst used in the polymerization processes of Comparative Example (CE1) was the catalyst of the example section of WO 2010009827 A1 (see pages 30 and 31), together with triethylaluminum (TEAL) as cocatalyst and dicyclopentyl dimethoxy silane (D-donor) as a donor.


[00184] All polymer powders were compounded in a ZSK Coperion 57 co-rotating twin screw extruder at 220 °C with 0.2% by weight Irganox B225 (1:1 mixture of Irganox 1010 (pentaerythryl-tetrakis(3-( 3', 5'-di-tert-butyl-4-hydroxytoluyl)propionate and tris(2,4-di-t-butylphenyl)phosphate)phosphite) from BASF AG, Germany) and 0.1% by weight of stearate calcium. IE4 and CE2 are nucleated versions of IE3 and CE1, respectively, with 0.2% by weight of DMDBS (1.3:2.4 di(methylbenzylidene) sorbitol) commercially available as Millad 3988 from Milliken Chemical, Gent/Belgium. The abbreviations "bs" and "a.§." refer to the states before and after sterilization.

[00185] As can be gathered from Table 2, the examples of the invention show an optimized or improved balance of optical and mechanical properties, i.e. an improved optical performance at comparable toughness level (resp. softness). When α-nucleated (IE 4), this balance of improved property is maintained and even increased; Table 2 also reveals that the impact strength of the examples of the invention is comparable and further enhanced by nucleation. The same can be gathered from Fig. 1, i.e. the examples of the invention exhibit an optimized or improved balance of optical and mechanical properties, i.e., an improved optical performance at a comparable softness level.

权利要求:
Claims (19)
[0001]
1. Heterophasic propylene copolymer (RAHECO), said heterophasic propylene copolymer (RAHECO) comprises a matrix (M) being a random propylene copolymer (R-PP) and an elastomeric propylene copolymer (E) dispersed in said matrix ( M), said heterophasic propylene copolymer (RAHECO) comprises in addition to ethylene propylene and/or α-olefins C4 to C8, characterized in that the heterophasic propylene copolymer (RAHECO) has a) an MFR2 melt flow (230° C) measured in accordance with ISO 1133 in the range of 2.0 to 10.0 g/10 min, b) a cold soluble xylene (XCS) content determined in accordance with ISO 16152 (25°C) in the range of 16 ,0 to 35.0% by weight, c) a comonomer content in the range of 8.5 to 21.0% mol, and wherein the heterophasic propylene copolymer (RAHECO) has at least two glass transition temperatures Tg (1) and Tg(2), the first glass transition temperature Tg(1) refers to the matrix (M), while the second glass transition temperature Tg(2) refers to to dispersed elastomeric propylene copolymer (E), in which additionally the second glass transition temperature Tg(2) fills the inequality (I), Tg(2) > 21.0 - 2.0 x chalks) (I) where Tg(2) is the second glass transition temperature of the heterophasic propylene copolymer (RAHECO); and C (XCS) is the comonomer content [in mol %] of the cold soluble xylene fraction (XCS) of the heterophasic propylene copolymer (RAHECO), where the heterophasic propylene copolymer (RAHECO) is free of acid esters phthalic acid as well as their respective decomposition products.
[0002]
2. Heterophasic propylene copolymer (RAHECO) according to claim 1, characterized in that the first glass transition temperature Tg(1) is above the second glass transition temperature Tg(2), preferably the difference between the first glass transition temperature Tg(1) and the second glass transition temperature Tg(2) is at least 40°C.
[0003]
3. Heterophasic propylene copolymer (RAHECO) according to claim 1 or 2, characterized in that (a) first glass transition temperature Tg(1) is in the range of -12 to +2°C; and/or (b) the second glass transition temperature Tg(2) is in the range from above -70 to below -20°C.
[0004]
4. Heterophasic propylene copolymer (RAHECO) according to any one of claims 1 to 3, characterized in that the cold soluble xylene (XCS) content has i) a comonomer content in the range of 33.0 to 45 0.0% mol, and/or ii) an intrinsic viscosity (IV) determined according to DIN ISO 1628/1, (in decalin at 135°C) in the range of 1.0 to 1.8 dl/g.
[0005]
5. Heterophasic propylene copolymer (RAHECO) according to any one of claims 1 to 4, characterized in that the random propylene copolymer (R-PP) has i) an MFR2 melt flow (230°C), measured according to ISO 1133 in the range from 3.0 to 8.0 g/10 min, and/or ii) a comonomer content in the range from 4.4 to 7.3% mol.
[0006]
6. Heterophasic propylene copolymer (RAHECO) according to any one of claims 1 to 5, characterized in that the cold xylene-insoluble fraction (XCI) of the heterophasic propylene copolymer (RAHECO) has a relative isolated content for block ethylene (I(E)) sequences in the range of 50.0 to 65.0%, where the content of I(E) is defined by equation (II)
[0007]
7. Heterophasic propylene copolymer (RAHECO) according to any one of claims 1 to 6, characterized in that the random propylene copolymer (R-PP) comonomers and/or the elastomeric propylene copolymer comonomers (E) are ethylene and/or C4 to C8 α-olefin.
[0008]
8. Heterophasic propylene copolymer (RAHECO) according to any one of claims 1 to 7, characterized in that the heterophasic propylene copolymer (RAHECO) comprises 65.0 to 88.0% by weight, based on the total weight of heterophasic propylene copolymer (RAHECO), random propylene copolymer (R-PP) and 12.0 to 35.0% by weight, based on the total weight of heterophasic propylene copolymer (RAHECO), elastomeric propylene copolymer (AND).
[0009]
9. Heterophasic propylene copolymer (RAHECO) according to any one of claims 1 to 8, characterized in that the heterophasic propylene copolymer (RAHECO) comprises a nucleating agent, preferably an a-nucleating agent.
[0010]
10. Heterophasic propylene copolymer (RAHECO) according to any one of claims 1 to 9, characterized in that the heterophasic propylene copolymer (RAHECO) is free of phthalic compounds as well as their respective decomposition products.
[0011]
11. Heterophasic propylene copolymer (RAHECO) according to any one of claims 1 to 10, characterized in that the heterophasic propylene copolymer (RAHECO) was polymerized in the presence of a) a Ziegler-Natta (ZN-C) catalyst ) which comprises the compounds (TC) of an IUPAC Group 4 to 6 transition metal, a Group 2 metal compound (MC) and an internal donor (ID), wherein said internal donor (ID) is a non-phthalic compound, preferably is a non-phthalic acid ester; b) optionally, a cocatalyst (Co), and c) optionally an external donor (ED).
[0012]
12. Heterophasic propylene copolymer (RAHECO) according to claim 11, characterized in that a) the internal donor (ID) is selected from malonates, maleates, succinates, glutarates, cyclohexene-1,2- optionally substituted dicarboxylates, benzoates and derivatives and/or mixtures thereof, preferably the internal donor (ID) is a citraconate; b) the molar ratio of cocatalyst (Co) to external donor (ED) [Co/ED] is 5 to 45.
[0013]
13. Heterophasic propylene copolymer (RAHECO) according to any one of claims 1 to 12, characterized in that the heterophasic propylene copolymer (RAHECO) comprising a matrix (M) being a random propylene copolymer (R-PP ) and an elastomeric propylene copolymer (E) dispersed in said matrix (M) is produced in a multi-phase process comprising at least two reactors connected in series.
[0014]
14. Heterophasic propylene copolymer (RAHECO) according to claim 13, characterized in that (a) in a first reactor, propylene and ethylene and/or α-olefin C4 to C8 are polymerized to obtain a first copolymer fraction of propylene (R-PP1), (b) transferring said first fraction of propylene copolymer (R-PP1), into a second reactor, (c) polymerization in said second reactor in the presence of the first fraction of propylene copolymer (R -PP1) propylene and ethylene and/or α-olefin C4 to C8 obtaining a second fraction of propylene copolymer (R-PP2), said first fraction of propylene copolymer (R-PP1) and said second fraction of copolymer of propylene (R-PP2) form the matrix (R-PP), (d) transfer said matrix (M) into a third reactor, (e) polymerization in said third reactor in the presence of matrix (M) propylene and ethylene and/ or α-olefin C4 to C8 obtaining an elastomeric propylene copolymer (E), said matrix (M) and said elastomeric propylene copolymer (E) form the heterophasic propylene copolymer (RAHECO).
[0015]
15. Heterophasic propylene copolymer (RAHECO) according to any one of claims 1 to 14, characterized in that the heterophasic propylene copolymer (RAHECO) has a) a flexural modulus measured according to ISO 178 in the range of 480 at 800 MPa, and/or b) a transparency in accordance with ASTM D1003-00 measured on a 1mm thick injection molded sample of at least 75.0%, and/or c) a turbidity in accordance with ASTM D 1003 -00 measured on a 1mm thick sample of the injection molded sample of <50.0%, and/or d) a clarity in accordance with ASTM D1003-00 measured on a 1mm thick injection molded sample of at least 90.0%.
[0016]
16. Unoriented film comprising a heterophasic propylene copolymer (RAHECO), characterized in that it is as defined in any one of claims 1 to 15.
[0017]
17. Unoriented film according to claim 16, characterized in that the film is a molded film or a blown film.
[0018]
18. Container, characterized in that it comprises the unoriented film as defined in claim 16 or 17.
[0019]
19. Use of a heterophasic propylene copolymer (RAHECO) as defined in any one of claims 1 to 15, characterized in that it is to improve the balance between softness and turbidity of an unoriented film, in which the enhancement is Achieved when heterophasic propylene copolymer (RAHECO) has a) flexural modulus measured in accordance with ISO 178 in the range of 480 to 800 MPa, and b) a turbidity in accordance with ASTM D 1003-00 measured on a 1 mm sample of injection molded thickness of <50.0%.

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法律状态:
2019-12-31| B06U| Preliminary requirement: requests with searches performed by other patent offices: procedure suspended [chapter 6.21 patent gazette]|

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2021-05-11| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|

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2021-06-29| B16A| Patent or certificate of addition of invention granted [chapter 16.1 patent gazette]|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 03/02/2015, OBSERVADAS AS CONDICOES LEGAIS. |

优先权:

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申请号 | 申请日 | 专利标题

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EP14154116.9|2014-02-06|

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EP14154116|2014-02-06|

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PCT/EP2015/052178|WO2015117948A1|2014-02-06|2015-02-03|Soft and transparent impact copolymers|

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