GAHLEITNER MARKUS (AT)
BERNREITNER KLAUS (AT)
LESKINEN PAULI (FI)
WO2020064190A1 | 2020-04-02 | |||
WO2002057342A2 | 2002-07-25 | |||
WO2009019169A1 | 2009-02-12 | |||
WO2013174778A1 | 2013-11-28 | |||
WO2018122134A1 | 2018-07-05 | |||
WO1994014856A1 | 1994-07-07 | |||
WO1995012622A1 | 1995-05-11 | |||
WO2006097497A1 | 2006-09-21 | |||
WO2007116034A1 | 2007-10-18 | |||
WO2002002576A1 | 2002-01-10 | |||
WO2011135004A2 | 2011-11-03 | |||
WO2012084961A1 | 2012-06-28 | |||
WO2012001052A2 | 2012-01-05 | |||
WO2011076780A1 | 2011-06-30 | |||
WO2013007650A1 | 2013-01-17 | |||
WO2015158790A2 | 2015-10-22 | |||
WO2018122134A1 | 2018-07-05 | |||
WO2019179959A1 | 2019-09-26 | |||
WO2015011135A1 | 2015-01-29 |
US6388040B1 | 2002-05-14 | |||
JP2000136274A | 2000-05-16 | |||
EP3620486A1 | 2020-03-11 | |||
US6388040B1 | 2002-05-14 | |||
EP3192817A1 | 2017-07-19 |
CAS , no. 693- 36-7
CAS, no. 112926- 00-8
Claims 1. A cast film made from an ethylene-propylene-1-butene terpolymer including a) units derived from ethylene in an amount of 0.2 to 2.4 mol-% with respect the total terpolymer; and b) units derived from propylene in an amount of 91.0 to 95.9 mol-% with respect the total terpolymer; and c) units derived from 1-butene in an amount of 3.9 to 6.6 mol-% with respect the total terpolymer, d) whereby the units derived from ethylene, propylene and 1-butene add up to 100 mol-% and e) a total amount of units derived from ethylene and 1-butene of 4.5 to 8.5 mol-%, and f) 2.1 regioinversions in an amount of 0.2 to 0.6 mol-% as determined by 13C-NMR analysis (as described in the experimental part); and g) a melt flow rate MFR2 (230°C / 2.16 kg) measured according to ISO 1133 in the range from 8 to 14.5 g/10min, and h) a melting temperature Tm measured by differential scanning calorimetry (DSC) following the equation Tm ≥ [150 – 1.6*(defects) – 0.12*(defects)²]°C, whereby ‘defects’ denote the sum of units derived from ethylene, units derived from 1-butene and 2.1 regioinversions, all values in mol- %, and whereby the cast film has a sealing initiation temperature (SIT) (as determined by a method described in the experimental part) below 117°C. 2. Cast film according to claim 1, wherein the ethylene-propylene-1-butene terpolymer has units derived from ethylene in an amount of 0.2 to 1.2 mol-% with respect the total terpolymer. 3. Cast film according to claim 1 or 2, wherein the ethylene-propylene-1-butene terpolymer has units derived from 1-butene in an amount of 4.5 to 5.2 mol-% with respect the total terpolymer. 4. Cast film according to any of the preceeding claims, wherein the ethylene- propylene-1-butene terpolymer has a total amount of units derived from ethylene and 1-butene of 4.8 to 6.5 mol-%. 5. Cast film according to any of the preceeding claims, wherein the ethylene- propylene-1-butene terpolymer has 2.1 regioinversions in an amount of 0.36 to 0.55 mol-% as determined by 13C-NMR analysis (as described in the experimental part). 6. Cast film according to any one of the precedings claims, whereby the ethylene-propylene-1-butene terpolymer includes a) units derived from ethylene in an amount of 0.2 to 1.2 mol-% with respect the total terpolymer; and b) units derived from propylene in an amount of 93.6 to 95.3 mol-% with respect the total terpolymer; and c) units derived from 1-butene in an amount of 4.5 to 5.2 mol-% with respect the total terpolymer, d) whereby the units derived from ethylene, propylene and 1-butene add up to 100 mol-% and e) a total amount of units derived from ethylene and 1-butene of 4.8 to 6.5 mol-%, and f) 2.1 regioinversions in an amount of 0.36 to 0.55 mol-% as determined by 13C-NMR analysis (as described in the experimental part); and g) a melt flow rate MFR2 (230°C / 2.16 kg) measured according to ISO 1133 in the range from 10 to 14.5 g/10min, and h) a melting temperature Tm measured by differential scanning calorimetry (DSC) following the equation Tm ≥ [150 – 1.6*(defects) – 0.12*(defects)²]°C, whereby defects denote the sum of units derived from ethylene, units derived from 1-butene and 2.1 regioinversions, all values in mol-%, whereby the film has a sealing initiation temperature (SIT) (as determined by a method described in the experimental part) below 112°C, particularly from 105 to 111°C. 7. Cast film according to any one of the preceding claims, characterized in that a test specimen cast film having a thickness of 50 μm has a tensile modulus determined according to ISO 527-3 at 23°C in machine direction (MD) of 200 to 800 MPa, preferably 520 to 620 MPa. 8. Cast film according to any one of the preceding claims, wherein the xylene cold soluble (XCS) fraction determined according to ISO 16152 is in the range of 0.5 to 5.0 wt.-%. 9. An ethylene-propylene-1-butene terpolymer including a) units derived from ethylene in an amount of 0.2 to 2.4 mol-% with respect the total terpolymer; and b) units derived from propylene in an amount of 91.0 to 95.9 mol-% with respect the total terpolymer; and c) units derived from 1-butene in an amount of 3.9 to 6.6 mol-% with respect the total terpolymer, d) whereby the units derived from ethylene, propylene and 1-butene add up to 100 mol-%, and e) a total amount of units derived from ethylene and 1-butene of 4.5 to 8.5 mol-%, and f) 2.1 regioinversions in an amount of 0.20 to 0.60 mol-%, as determined by 13C-NMR analysis (as described in the experimental part); and g) a melt flow rate MFR2 (230°C / 2.16 kg) measured according to ISO 1133 in the range from 8 to 14.5 g/10min, and h) a melting temperature Tm measured by differential scanning calorimetry (DSC) following the equation Tm ≥ [150 – 1.6*(defects) – 0.12*(defects)²]°C, whereby ‘defects’ denote the sum of units derived from ethylene, units derived from 1-butene and 2.1 regioinversions, all values in mol- %. 10. The ethylene-propylene-1-butene terpolymer according claim 9 having a) units derived from ethylene in an amount of 0.2 to 1.2 mol-% with respect the total terpolymer; and b) units derived from propylene in an amount of 93.6 to 95.3 mol-% with respect the total terpolymer; and c) units derived from 1-butene in an amount of 4.5 to 5.2 mol-% with respect the total terpolymer, d) whereby the units derived from ethylene, propylene and 1-butene add up to 100 mol-% and e) a total amount of units derived from ethylene and 1-butene of 4.8 to 6.5 mol-%, and f) 2.1 regioinversions in an amount of 0.36 to 0.55 mol-% as determined by 13C-NMR analysis (as described in the experimental part); and g) a melt flow rate MFR2 (230°C / 2.16 kg) measured according to ISO 1133 in the range from 10 to 14.5 g/10min, and h) a melting temperature Tm measured by differential scanning calorimetry (DSC) following the equation Tm ≥ [150 – 1.6*(defects) – 0.12*(defects)²]°C, whereby ‘defects’ denote the sum of units derived from ethylene, units derived from 1-butene and 2.1 regioinversions, all values in mol- %. 11. Composition including the ethylene-propylene-1-butene terpolymer according to claim 9 or 10 in an amount of at least 97 wt.-% with respect to the total composition. 12. Composition according to 11, consisting of the ethylene-propylene-1-butene terpolymer according to claim 9 or 10 and additives. |
wherein M is zirconium or hafnium; each X is independently a hydrogen atom, a halogen atom, C 1-6 -alkoxy group, C 1-6 - alkyl, phenyl or benzyl group; L is a divalent bridge selected from -R' 2 C-, -R' 2 C-CR' 2 -, -R' 2 Si-, -R' 2 Si-SiR' 2 -, -R' 2 Ge-, wherein each R' is independently a hydrogen atom, C 1-20 -alkyl, C 3-10 -cycloalkyl, tri(C 1- 20 -alkyl)silyl, C 6-20 -aryl, C 7-20 -arylalkyl or C 7-20 -alkylaryl; each of R 2 or R 2 ' is a C 1-10 -alkyl group; R 5 ' is a C 1-10 alkyl group or Z'R 3 ' group; R 6 is hydrogen or a C 1-10 -alkyl group; R 6 ' is a C 1-10 -alkyl group or C 6-10 -aryl group; preferably a tertiary alkyl group; R 7 is hydrogen, a C 1-6 -alkyl group or ZR 3 group and R 7 ' is hydrogen; Z and Z' are independently O or S; R 3 ' is a C 1-10 -alkyl group, or a C 6-10 -aryl group optionally substituted by one or more halo groups; R 3 is a C 1-10 -alkyl group; each n is independently 0 to 4, e.g.0, 1 or 2; and each R 1 is independently a C 1-20 -hydrocarbyl group, e.g. C 1-10 -alkyl group. Further preferred complexes of use in the invention are of formula (III') or (III):
M is zirconium or hafnium; each X is independently a hydrogen atom, a halogen atom, C 1-6 -alkoxy group, C 1-6 - alkyl, phenyl or benzyl group; L is a divalent bridge selected from -R' 2 C- or -R' 2 Si- wherein each R' is independently a hydrogen atom, C 1-20 -alkyl or C 3-10 -cycloalkyl; R 6 is hydrogen or a C 1-10 -alkyl group; R 6' is a C 1-10 -alkyl group or C 6-10 -aryl group, preferably a tertiary alkyl group; R 7 is hydrogen, C 1-6 -alkyl or OC 1-6 -alkyl; Z' is O or S; R 3' is a C 1-10 -alkyl group, or C6-10-aryl group optionally substituted by one or more halo groups; n is independently 0 to 4, e.g.0, 1 or 2; and each R 1 is independently a C 1-10 -alkyl group. Further preferred complexes of use in the invention are of formula (IV') or (IV):
M is zirconium or hafnium; each X is independently a hydrogen atom, a halogen atom, C 1-6 -alkoxy group, C 1-6 - alkyl, phenyl or benzyl group; each R' is independently a hydrogen atom, C 1-20 -alkyl or C 3-7 -cycloalkyl; R 6 is hydrogen or a C 1-10 -alkyl group; R 6' is a C 1-10 -alkyl group or C 6-10 -aryl group, preferably a tertiary alkyl group; R 7 is hydrogen, C 1-6 -alkyl or OC 1-6 -alkyl; Z' is O or S; R 3' is a C 1-10 -alkyl group, or C 6-10 -aryl group optionally substituted by one or more halo groups; n is independently 0, 1 to 2; and each R 1 is independently a C 3-8 -alkyl group. Most preferably, the complex of use in the invention is of formula (V') or (V):
wherein each X is independently a hydrogen atom, a halogen atom, C 1-6 -alkoxy group, C 1-6 -alkyl, phenyl or benzyl group; R' is independently a C 1-6 -alkyl or C 3-10 -cycloalkyl; R 1 is independently C 3-8 -alkyl; R 6 is hydrogen or a C 3-8 -alkyl group; R 6' is a C 3-8 -alkyl group or C 6-10 -aryl group, preferably a tertiary C 4-8 -alkyl group; R 3' is a C 1-6 -alkyl group, or C 6-10 -aryl group optionally substituted by one or more halo groups; and n is independently 0, 1 or 2. Particular compounds of the invention include:
Most preferably rac-anti-Me 2 Si(2-Me-4-(p-tBuPh)-Ind)(2-Me-4-Ph-5-OMe-6-tBu- Ind)ZrCl 2 is used. The ligands required to form the complexes and hence catalysts of the invention can be synthesized by any process and the skilled organic chemist would be able to devise various synthetic protocols for the manufacture of the necessary ligand materials. For Example WO 2007/116034 discloses the necessary chemistry. Synthetic protocols can also generally be found in WO 2002/02576, WO 2011/135004, WO 2012/084961, WO 2012/001052, WO 2011/076780, WO 2013/007650, WO 2015/158790 and WO 2018/122134. The examples section also provides the skilled person with sufficient direction. Cocatalyst To form an active catalytic species it is normally necessary to employ a cocatalyst as is well known in the art. Cocatalysts comprising one or more compounds of Group 13 metals, like organoaluminium compounds or boron containing cocatalysts or combinations therefrom used to activate metallocene catalysts are suitable for use in this invention. In a preferred embodiment of the present invention a cocatalyst system comprising a boron containing cocatalyst, e.g. a borate cocatalyst and an aluminoxane cocatalyst is used. The single-site polymerization catalyst system used in the invention therefore can comprise (i) a complex as defined above and an aluminoxane cocatalyst. The aluminoxane cocatalyst can be one of formula (VI): where n is from 6 to 20 and R has the meaning below. Aluminoxanes are formed on partial hydrolysis of organoaluminum compounds, for example those of the formula AlR 3 , AlR 2 Y and Al 2 R 3 Y 3 where R can be, for example, C 1 -C 10 -alkyl, preferably C 1 -C 5 -alkyl, or C 3 -C 10 -cycloalkyl, C 7 -C 12 -arylalkyl or -alkylaryl and/or phenyl or naphthyl, and where Y can be hydrogen, halogen, preferably chlorine or bromine, or C 1 -C 10 -alkoxy, preferably methoxy or ethoxy. The resulting oxygen- containing aluminoxanes are not in general pure compounds but mixtures of oligomers of the formula (VI). The preferred aluminoxane is methylaluminoxane (MAO). Since the aluminoxanes used according to the invention as cocatalysts are not, owing to their mode of preparation, pure compounds, the molarity of aluminoxane solutions hereinafter is based on their aluminium content. According to the present invention, also a boron containing cocatalyst can be used. Boron containing cocatalysts of interest include those of formula (VII) BY 3 (VII) wherein Y is the same or different and is a hydrogen atom, an alkyl group of from 1 to about 20 carbon atoms, an aryl group of from 6 to about 15 carbon atoms, alkylaryl, arylalkyl, haloalkyl or haloaryl each having from 1 to 10 carbon atoms in the alkyl radical and from 6-20 carbon atoms in the aryl radical or fluorine, chlorine, bromine or iodine. Preferred examples for Y are fluorine, trifluoromethyl, aromatic fluorinated groups such as p-fluorophenyl, 3,5-difluorophenyl, pentafluorophenyl, 3,4,5- trifluorophenyl and 3,5- di(trifluoromethyl)phenyl. Preferred options are trifluoroborane, tris(4-fluorophenyl)borane, tris(3,5-difluorophenyl)borane, tris(4- fluoromethylphenyl)borane, tris(2,4,6-trifluorophenyl)borane, tris(penta- fluorophenyl)borane, tris(3,5-difluorophenyl)borane and/or tris (3,4,5- trifluorophenyl)borane. Particular preference is given to tris(pentafluorophenyl)borane. However, it is preferred that as a boron containing cocatalyst borates are used, i.e. compounds containing a borate. These compounds generally contain an anion of formula: (Z) 4 B- (VIII) where Z is an optionally substituted phenyl derivative, said substituent being a halo- C 1-6 -alkyl or halo group. Preferred options are fluoro or trifluoromethyl. Most preferably, the phenyl group is perfluorinated. Such ionic cocatalysts preferably contain a weakly-coordinating anion such as tetrakis(pentafluorophenyl)borate or tetrakis(3,5-di(trifluoromethyl)phenyl)borate. Suitable counterions are protonated amine or aniline derivatives such as methylammonium, anilinium, dimethylammonium, diethylammonium, N- methylanilinium, diphenylammonium, N,N-dimethylanilinium, trimethylammonium, triethylammonium, tri-n-butylammonium, methyldiphenylammonium, pyridinium, p- bromo-N,N- dimethylanilinium or p-nitro-N,N-dimethylanilinium. Preferred ionic compounds which can be used according to the present invention include: tributylammoniumtetra(pentafluorophenyl)borate, tributylammoniumtetra(trifluoromethylphenyl)borate, tributylammoniumtetra(4-fluorophenyl)borate, N,N-dimethylcyclohexylammoniumtetrakis(pentafluorophenyl)bor ate, N,N-dimethylbenzylammoniumtetrakis(pentafluorophenyl)borate, N,N-dimethylaniliniumtetrakis(pentafluorophenyl)borate, N,N-di(propyl)ammoniumtetrakis(pentafluorophenyl)borate, di(cyclohexyl)ammoniumtetrakist(pentafluorophenyl)borate, triphenylcarbeniumtetrakis(pentafluorophenyl)borate, or ferroceniumtetrakis(pentafluorophenyl)borate. Preference is given to triphenylcarbeniumtetrakis(pentafluorophenyl) borate, N,N-dimethylaniliniumtetrakis(pentafluorophenyl)borate, N,N- dimethylcyclohexylammoniumtetrakis(pentafluorophenyl)borate or N,N- dimethylbenzylammoniumtetrakis(pentafluorophenyl)borate According to the present invention, it is especially preferred to use an aluminoxane cocatalyst, like MAO, together with a boron containing cocatalyst, like borate cocatalyst. Suitable amounts of co-catalyst will be well known to the skilled person. Preferably, the amount of cocatalyst is chosen to reach molar ratios defined below. The molar ratio of feed amounts of boron (B) to the metal ion (M) (preferably zirconium) of the metallocene boron/M may be in the range 0.1:1 to 10:1 mol/mol, preferably 0.3:1 to 7:1, especially 0.3:1 to 5:1 mol/mol. Even more preferably, the molar ratio of feed amounts of boron (B) to metal ion (M) (preferably zirconium) of the metallocene boron/M is from 0.3:1 to 3:1 The molar ratio of Al from the aluminoxane to the metal ion (M) (preferably zirconium) of the metallocene Al/M may be in the range 1:1 to 2000:1 mol/mol, preferably 10:1 to 1000:1, and more preferably 50:1 to 600:1 mol/mol. Other suitable catalysts systems are described in WO2019179959 being incorporated by reference herewith. In the broadest aspect, the catalyst complex fulfills the following structure.
whereby Mt is Hf or Zr; each X is a sigma-ligand; Each R 1 independently are the same or can be different and are a CH 2 -R 7 group, with R 7 being H or linear or branched C1-6-alkyl group, C3-8 cycloalkyl group, C6- 10 aryl group, Each R 2 is independently a -CH=, -CY=, - CH 2 -, -CHY- or -CY 2 - group, wherein Y is a C1-10 hydrocarbyl group and where n is 2-6, each R 3 and R 4 are independently the same or can be different and are hydrogen, a linear or branched C1i-C6-alkyl group, an OY group or a C7-20 arylalkyl, C7-20 alkylaryl group or C6-20 aryl group, whereby at least one R 3 per phenyl group and at least one R 4 is not hydrogen, and optionally two adjacent R 3 or R 4 groups can be part of a ring including the phenyl carbons to which they are bonded, R 5 is a linear or branched Ci-C6-alkyl group, C7-20 arylalkyl, C7-20 alkylaryl group or C6-C20-aryl group, R 6 is a C(R 8 ) 3 group, with R 8 being a linear or branched C1-C6 alkyl group, Each R is independently a C1-C20-hydrocarbyl, C6-C20-aryl, C7-C20-arylalkyl or C7-C20- alkylaryl. As specific metallocene catalyst complexes the following three embodiments abbreviated MC1, MC2 and MC3 may be mentioned.
rac-anti-dimethylsilanediyl[2-methyl-4,8-bis-(4<'>-ter t-butylphenyl)-1 ,5,6,7- tetrahydro-s- indacen-1 -yl][2-methyl-4-(3’,5’-dimethyl-phenyl)-5-methoxy-6-tert - butylinden-1 -yl] zirconium dichloride (MC-1 ) rac-anti-dimethylsilanediyl[2-methyl-4,8-bis-(3’,5’-dime thylphenyl)-1 ,5,6,7- tetrahydro-s indacen-1 -yl] [2-methyl-4-(3’,5’-dimethylphenyl)-5-methoxy-6-tert- butylinden-1 -yl] zirconium dichloride (MC-2) rac-anti-dimethylsilanediyl[2-methyl-4,8-bis-(3’,5’-dime thylphenyl)-1 ,5,6,7- tetrahydro-s- indacen-1-yl][2-methyl-4-(3’,5’-ditert-butyl-phenyl)-5-m ethoxy-6-tert- butylinden-1-yl] zirconium dichloride (MC-3) including also their corresponding zirconium dimethyl analogues. The polymer composition according to the present invention may be compounded and pelletized using any of the variety of compounding and blending machines and methods well known and commonly used in the resin compounding art. For blending the individual components of the instant composition a conventional compounding or blending apparatus, for example a Banbury mixer, a 2-roll rubber mill, Buss-co- kneader or a twin-screw extruder may be used. The compositions recovered from the extruder/mixer are usually in the form of pellets. These pellets are then further processed and formed into a cast film according to present invention. The compositions according to the present invention preferably include the terpolymer as described herein in an amount of at least 97 wt.-%. More preferably, the compositions according to the present invention consist of the terpolymer as described herein in an amount of at least 97 wt.-% and additives. Preferred additives for this purpose have been described further above. Cast film The cast film according to the present invention is a made from the ethylene- propylene-1-butene terpolymer as described above. All preferred aspects also hold for the cast film. As briefly outline above, the present invention concerns a cast film made from an ethylene-propylene-1-butene terpolymer including a) units derived from ethylene in an amount of 0.2 to 2.4 mol-% with respect the total terpolymer; and b) units derived from propylene in an amount of 91.0 to 95.9 mol-% with respect the total terpolymer; and c) units derived from 1-butene in an amount of 3.9 to 6.6 mol-% with respect the total terpolymer, d) whereby the units derived from ethylene, propylene and 1-butene add up to 100 mol-% and e) a total amount of units derived from ethylene and 1-butene of 4.5 to 8.5 mol-%, and f) 2.1 regioinversions in an amount of 0.20 to 0.60 mol-% as determined by 1 3 C-NMR analysis (as described in the experimental part); and g) a melt flow rate MFR 2 (230°C / 2.16 kg) measured according to ISO 1133 in the range from 8 to 14.5 g/10min, and h) a melting temperature Tm measured by differential scanning calorimetry (DSC) following the equation Tm ≥ [150 – 1.6*(defects) – 0.12*(defects)²]°C, whereby ‘defects’ denote the sum of units derived from ethylene, units derived from 1-butene and 2.1 regioinversions, all values in mol-%, and whereby the cast film has a sealing initiation temperature (SIT) (as determined by a method described in the experimental part) below 117°C. The films in accordance with the present invention can be obtained by converting the polymer compositions in accordance with the present invention into film with conventional film technology, for example cast film technology. Preferably, the molten polymer is extruded though a slit extrusion die onto a chill roll to cool the polymer to a solid film. Typically, the polymer is firstly compressed and liquefied in an extruder, preferably a single-screw extruder, it being possible for any additives to be already added to the polymer or introduced at this stage via a masterbatch. The melt is then forced through a flat-film die (slit die), and the extruded film is taken off on one or more take-off rolls, during which it cools and solidifies. It has proven particularly favorable to keep the take-off roll or rolls, by means of which the extruded film is cooled and solidified, at a temperature from 10 to 50°C, preferably from 15 to 40°C. Auxiliary devices like an air knife and/or a vacuum box may be used to improve the film quality. The cast film according to the present invention is preferably made from an ethylene-propylene-1-butene terpolymer having units derived from ethylene in an amount of 0.2 to 1.2 mol-% with respect the total terpolymer. In another preferred aspect, the cast film according to the present invention is preferably made from an ethylene-propylene-1-butene terpolymer having units derived from 1-butene in an amount of 4.5 to 5.2 mol-% with respect the total terpolymer. It is also preferred that the cast film according to the present invention is made from an ethylene-propylene-1-butene terpolymer having a total amount of units derived from ethylene and 1-butene of 4.8 to 6.5 mol-%. It is also preferred that the cast film according to the present invention is made from an ethylene-propylene-1-butene terpolymer having 2.1 regioinversions in an amount of 0.36 to 0.55 mol-% as determined by 13 C-NMR analysis (as described in the experimental part). In a particularly preferred embodiment, the cast film according to the present invention is made from an the ethylene-propylene-1-butene terpolymer including a) units derived from ethylene in an amount of 0.2 to 1.2 mol-% with respect the total terpolymer; and b) units derived from propylene in an amount of 93.6 to 95.3 mol-% with respect the total terpolymer; and c) units derived from 1-butene in an amount of 4.5 to 5.2 mol-% with respect the total terpolymer, d) whereby the units derived from ethylene, propylene and 1-butene add up to 100 mol-% and e) a total amount of units derived from ethylene and 1-butene of 4.8 to 6.5 mol-%, and f) 2.1 regioinversions in an amount of 0.36 to 0.55 mol-% as determined by 1 3 C-NMR analysis (as described in the experimental part); and g) a melt flow rate MFR2 (230°C / 2.16 kg) measured according to ISO 1133 in the range from 10 to 14.5 g/10min, and h) a melting temperature Tm measured by differential scanning calorimetry (DSC) following the equation Tm ≥ [150 – 1.6*(defects) – 0.12*(defects)²]°C, whereby ‘defects’ denote the sum of units derived from ethylene, units derived from 1-butene and 2.1 regioinversions, all values in mol-% whereby the cast film has a sealing initiation temperature (SIT) (as determined by a method described in the experimental part) below 112°C, particularly from 105 to 111°C. The cast film of the present invention preferably has a tensile modulus determined according to ISO 527-3 at 23°C on a film with a thickness of 50 μm in machine direction, preferably as well as in transverse direction, in the range of 200 to 800 MPa, preferably in the range of 400 to 700 MPa, more preferably in the range of 520 to 620 MPa In another aspect, the cast film according to the present invention is preferably made from an ethylene-propylene-1-butene terpolymer which is bimodal as to the butene content and/or is bimodal as to the molecular weight It shall be mentioned that film thickness is not limited to 50 micrometer. A 50 micrometer thick film is merely used as a test specimen for easier comparison. In a preferred embodiment the cast films according the present invention are made from an ethylene-propylene-1-butene terpolymer having a hexane solubility (FDA) of 0.80 wt.-% or less, preferably of 0.70 wt.-% or less, more preferably of 0,65 or less, like in a range of 0.65 to 0.01 wt.%. Furthermore, a preferred cast film of the present invention has a xylene cold soluble (XCS) fraction determined in line with ISO 16152 in the range of 0.5 to 22.0 wt.-%. In a further preferred embodiment, the cast film of the present invention has a xylene cold soluble (XCS) fraction determined in line with ISO 16152 in the range of 0.5 to 5.0 wt.-%, more preferably in the range of 0.6 to 2.5 wt.-% and even more preferably in the range of 1.0 to 2.0 wt.-%. The cast film of the present invention preferably has a haze determined according to ASTM D1003-00 on a film with a thickness of 50 ^m of below 3.0 %, preferably in the range of 0.1 to 0.9 % and more preferably in the range of 0.2 to 0.5 %. Experimental Part A. Measuring methods The following definitions of terms and determination methods apply for the above general description of the invention as well as to the below examples unless otherwise defined. a) MFR 2 (230 °C) was measured according to ISO 1133 (230°C, 2.16 kg load). b) Quantification of microstructure by NMR spectroscopy Quantitative nuclear-magnetic resonance (NMR) spectroscopy was used to quantify the comonomer content of the polymers. Quantitative 13 C{ 1 H} NMR spectra recorded in the molten-state using a Bruker Avance III 500 NMR spectrometer operating at 500.13 and 125.76 MHz for 1 H and 13 C respectively. All spectra were recorded using a 13 C optimised 7 mm magic-angle spinning (MAS) probehead at 180°C using nitrogen gas for all pneumatics. Approximately 200 mg of material was packed into a 7 mm outer diameter zirconia MAS rotor and spun at 4 kHz. This setup was chosen primarily for the high sensitivity needed for rapid identification and accurate quantification {klimke06, parkinson07, castignolles09}. Standard single-pulse excitation was employed utilising the NOE at short recycle delays of 3 s {pollard04, klimke06} and the RS- HEPT decoupling scheme {fillip05,griffin07}. A total of 1024 (1k) transients were acquired per spectra. Quantitative 13 C{ 1 H} NMR spectra were processed, integrated and relevant quantitative properties determined from the integrals. All chemical shifts are internally referenced to the methyl isotactic pentad (mmmm) at 21.85 ppm. Characteristic signals corresponding to the incorporation of 1-butene were observed {brandolini01} and the comonomer content quantified. The amount of isolated 1-butene incorporated in PBP sequences was quantified using the integral of the ^B2 sites at 43.6 ppm accounting for the number of reporting sites per comonomer: B = I αB2 / 2 The amount of consecutively incorporated 1-butene in PBBP sequences was quantified using the integral of the ααB2B2 site at 40.5 ppm accounting for the number of reporting sites per comonomer: BB = 2 *IααB2B2 In presence of BB the value of B must be corrected for the influence of the αB2 sites resulting from BB: B = (I αB2 / 2) – BB/2 The total 1-butene content was calculated based on the sum of isolated and consecutively incorporated 1-butene: B total = B + BB Characteristic signals corresponding to the incorporation of ethylene were observed {brandolini01} and the comonomer content quantified. The amount of isolated ethylene incorporated in PEP sequences was quantified using the integral of the Sββ sites at 24.3 ppm accounting for the number of reporting sites per comonomer: E = I Sββ If characteristic signals corresponding to consecutive incorporation of ethylene in PEE sequence was observed the Sβδ site at 27.0 ppm was used for quantification: EE = I Sβδ Characteristic signals corresponding to regio defects were observed {resconi00}. The presence of isolated 2,1-erythro regio defects was indicated by the presence of the two methyl sites at 17.7 and 17.2 ppm, by the methylene site at 42.4 ppm and confirmed by other characteristic sites. The presence of 2,1 regio defect adjacent an ethylene unit was indicated by the two inequivalent Sαβ signals at 34.8 ppm and 34.4 ppm respectively and the Tγγ at 33.7 ppm. The amount of isolated 2,1-erythro regio defects (P 21e isolated ) was quantified using the integral of the methylene site at 42.4 ppm (I e9 ): P 21e isolated = I e9 If present the amount of 2,1 regio defect adjacent to ethylene (P E21 ) was quantified using the methine site at 33.7 ppm (I Tγγ ): P E21 = I Tγγ The total ethylene content was then calculated based on the sum of ethylene from isolated, consecutively incorporated and adjacent to 2,1 regio defects: E total = E + EE + P E21 The amount of propene was quantified based on the S ^ ^ methylene sites at 46.7 ppm including all additional propene units not covered by S ^ ^ e.g. the factor 3*P 21e isolated accounts for the three missing propene units from isolated 2,1-erythro regio defects: P total = I Sαα + 3*P 21e isolated + B + 0.5*BB + E + 0.5*EE + 2*P E21 The total mole fraction of 1-butene and ethylene in the polymer was then calculated as: fB = B total / ( E total + P total + B total ) fE = E total / ( E total + P total + B total ) The mole percent comonomer incorporation was calculated from the mole fractions: B [mol%] = 100 * fB E [mol%] = 100 * fE The weight percent comonomer incorporation was calculated from the mole fractions: B [wt.-%] = 100 * ( fB * 56.11 ) / ( (fE * 28.05) + (fB * 56.11) + ((1-(fE+fB)) * 42.08) ) E [wt.-%] = 100 * ( fE * 28.05 ) / ( (fE * 28.05) + (fB * 56.11) + ((1-(fE+fB)) * 42.08) ) The mole percent of isolated 2,1-erythro regio defects was quantified with respect to all propene: [21e] mol% = 100 * P 21e isolated / P total The mole percent of 2,1 regio defects adjacent to ethylene was quantified with respect to all propene: [E21] mol% = 100 * P E21 / P total The total amount of 2,1 defects was quantified as following: [21] mol% = [21e] + [E21] Characteristic signals corresponding to other types of regio defects (2,1-threo, 3,1 insertion) were not observed {resconi00}. Literature (as referred to above): c) DSC analysis, melting temperature (Tm) and crystallization temperature (Tc): was measured with a TA Instrument Q2000 differential scanning calorimetry (DSC) on 5 to 7 mg samples. DSC was run according to ISO 11357 / part 3 / method C2 in a heat / cool / heat cycle with a scan rate of 10°C/min in the temperature range of - 30°C to +225°C. Crystallization temperature (Tc) and crystallization enthalpy (Hc) were determined from the cooling step, while melting temperature (Tm) and melting enthalpy (Hm) were determined from the second heating step. d) Cast films The cast film properties (except hexane solubles and tensile modulus) were determined on a cast film produced from a single screw extruder with a barrel diameter of 30 mm and a slit die of 200 x 0.5 mm in combination with a chill- and take-up roll. The melt temperature was 260 °C in the die. The chill roll and the take- up roll were kept at 15°C and the film thickness was 50 µm. e) Haze was determined according to ASTM D1003-00 on the cast test films of 50 micrometer thickness. g) Sealing initiation temperature (SIT); sealing end temperature (SET), Sealing initiation temperature (SIT); sealing end temperature (SET), sealing range: The method determines the sealing temperature range (sealing range) of polypropylene films, in particular blown films or cast films according to ASTM F1921 - 12. Seal pressure, cool time and peel speed were modified as stated below. The sealing temperature range is the temperature range, in which the films can be sealed according to conditions given below. The lower limit (heat sealing initiation temperature (SIT)) is the sealing temperature at which a sealing strength of > 5 N is achieved. The upper limit (sealing end temperature (SET)) is reached, when the films stick to the sealing device. The sealing range was determined on a J&B Universal Sealing Machine Type 3000 with a cast film of 50 μm thickness with the following further parameters: Specimen width: 25.4 mm Seal Pressure: 0.1 N/mm<2> Seal Time: 0.1 sec Cool time: 99 sec Peel Speed: 10 mm/sec Start temperature: 80°C End temperature: 150°C Increments: 10°C Specimen is sealed A to A at each sealbar temperature and seal strength (force) was determined at each step. The temperature was determined at which the seal strength reaches 5 N. h) Hexane (C6) extractables The hexane extractable fraction was determined according to the FDA method (federal registration, title 21, Chapter 1, part 177, section 1520, s. Annex B). The measurements were carried out according to FDA section 177.1520 with 1 g of a polymer film of 100 μm thickness being added to 400 ml hexane at 50°C for 2 hours while stirring with a reflux cooler. After 2 hours, the mixture is immediately filtered on a filter paper. The precipitate is collected in an aluminium recipient and the residual hexane is evaporated on a steam bath under N2 flow. The amount of hexane solubles is determined by the formula ((wt. sample + wt. crucible) - (wt crucible)) / (wt. sample) x 100%. The film used in the test had been produced on a Collin cast film lab line, with melt temperature of 230°C, output rate of 8kg/h, chill roll temperature 40°C. i) Tensile Modulus Tensile Modulus in machine and transverse direction are determined according to ISO 527-3 at 23°C on a cast film test specimen of 50 μm thickness produced on a monolayer cast film line with a melt temperature of 220°C and a chill roll temperature of 20°C with a thickness of 50 μm produced as indicated above. Testing was performed at a cross head speed of 1 mm/min. m) Xylene cold solubles (XCS) The xylene soluble (XS) fraction as defined and described in the present invention was determined in line with ISO 16152 as follows: 2.0 g of the polymer were dissolved in 250 ml p-xylene at 135°C under agitation. After 30 minutes, the solution was allowed to cool for 15 minutes at ambient temperature and then allowed to settle for 30 minutes at 25 +/- 0.5°C. The solution was filtered with filter paper into two 100 ml flasks. The solution from the first 100 ml vessel was evaporated in nitrogen flow and the residue dried under vacuum at 90°C until constant weight is reached. The xylene soluble fraction (percent) can then be determined as follows: XS% = (100*m*V 0 )/(m 0 *v); m 0 = initial polymer amount (g); m = weight of residue (g); V 0 = initial volume (ml); v = volume of analysed sample (ml). B. Examples Preparation of the catalyst system for examples IE1-IE3 The metallocene (MC1) (rac-anti-dimethylsilandiyl(2-methyl-4-phenyl-5-methoxy-6- tert-butyl-indenyl)(2-methyl-4-(4-tert-butylphenyl)indenyl)z irconium dichloride) has been synthesized as described in WO 2013/007650. The catalyst used in the examples IE1 to IE3 was prepared from MC1 as described in detail in WO 2015/011135 A1 (metallocene complex MC1 with methylaluminoxane (MAO) and borate resulting in Catalyst 3 described in WO 2015/011135 A1) with the proviso that the surfactant is 2,3,3,3-tetrafluoro-2-(1,1,2,2,3,3,3-heptafluoropropoxy)- 1-propanol. Preparation of the catalyst system for examples CE1-CE2 For Comparative Examples CE1 and CE2 a Ziegler Natta catalyst commercially available from Lyondell Basell under the tradename Avant ZN180 was used. As cocatalyst TEAL, with feeding rate of 150 g/t C3, was used and dicyclopentyldimethoxysilane (= donor D, CAS No.126990-35-0) was used as external donor with a feeding rate of 40 g/t C3. Polymerization and Pelletization Terpolymers IE1 – IE3 were produced in a Borstar pilot plant comprising a prepolymerization reactor, one loop reactor and a gas phase reactor coupled in series. The polymerization conditions as well as the results of polymer characterization are indicated in Table 1. IE1 – IE 3 were made with metallocene catalyst system as described above and CE1 – CE 2 were made with ZN catalyst as described above. Table 1: Polymerization process conditions for IEs and CEs.
It can be seen that carefully tailring the amount of units derived from ethylene, the total amount of units derived from ethylene and butene, as well as the control of 2.1 regioinversions results in relatively low melting temperature for a given amount of total defects. Simultaneously the hexane solubility is also very low. The obtained polymers were compounded in a co-rotating twin-screw extruder Coperion ZSK 57 at 220°C with 1500 ppm antioxidant (Irganox B215, commercially available from BASF) and 500 ppm Ca-stearate. The final MFR2 of the final composition was reached via visbreaking in the twin-screw extruder using an appropriate amount (350 ppm for all examples) of (tert.-butylperoxy)-2,5- dimethylhexane (Trigonox 101, distributed by Akzo Nobel, Netherlands). The characteristics of the cast films made from the terpolymers are provided below in Table 2. Table 2: Characteristics of the polymer compositions and cast films As can be gathered from Table 2 the terpolymer according to the present invention (IE1 to IE3) the films made of these materials show a lower sealing initiation temperature in contrast to the examples CE1 and CE2. In addition, the optical and mechanical properties of the films in accordance with the present invention have very good mechanical and optical properties.
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