Patent Application
20230227642
The present invention is related to a new polypropylene composition which combines low sealing initiation temperature (SIT), low xylene cold soluble (XCS) content and thus low overall migration and good optical properties, like low haze.
The present invention is furthermore related to the use of the polypropylene composition and articles, especially films made therefrom.
Polypropylenes are suitable for many applications.
For instance polypropylene (PP) is applicable in areas where sealing properties play an important role, like in the food or medical packing industry.
Heat sealing is the predominant method of manufacturing flexible and semi-rigid packages. An important indication of good sealing performance is inter alia a low sealing initiation temperature (SIT), which is needed to support high speed on packaging machines.
To ensure fast sealing, a low SIT is of advantage. By operating at lower temperature there is the benefit that the article to be sealed is not exposed to high temperature. There are also economic advantages, since lower temperatures are of course cheaper to generate and maintain.
There are further advantages in avoiding high sealing temperatures, especially when temperature sensitive goods are to be packed.
Furthermore, it is also desired to have a packaging material with satisfying optical properties, such as low haze.
In addition, certain regulations have to be fulfilled regarding the use of such materials in food contact applications, thus compliancy to food regulations in terms of overall migration (OM) is a must in advanced packaging applications. Thus, materials with a low content of xylene cold solubles (XCS) are desired.
Furthermore, a higher content of soluble resp. extractable components (like XCS) is also undesirable in the field of medical packaging.
Irrespectively from the polymer type, a polymer composition must fulfil at best all desired end properties and additionally must be easily processable, i.e. must withstand stress. However, end properties and processing properties act often in a conflicting manner.
It frequently turns out that improvement of one of the desired properties is achieved on the expense of the other properties.
For example, in order to improve the sealing behaviour, normally low sealing initiation temperature (SIT) is obtained with higher comonomer content, however causing two problems:
1. High comonomer results in lower Tm, which potentially makes steam sterilization worse or even impossible, and
2. Incorporation of a higher amount of comonomers, especially for PP based on Ziegler-Natta (ZN) type catalysts, causes problems with C6-solubles (FDA) and overall migration.
WO 2019012110 A1 discloses a polypropylene composition comprising a blend of (A) 50.0 to 99.0 wt.-% of a propylene-ethylene random copolymer with an ethylene content in the range of from 0.1 to 12.0 wt.-%, an MFR2 (230° C., 2.16 kg, ISO 1133) in a range of from 0.5 to 60.0 g/10 min and a melting temperature Tm (DSC) is in the range of from 135° C. to 155° C. and (B) 1.0 to 50.0 wt.-% of a propylene-hexene random copolymer with a hexene content in the range of from 0.1 to 12.0 wt.-% and an MFR2 (230° C., 2.16 kg, ISO 1133) in a range of from 0.5 to 60.0 g/10 min and a melting temperature Tm (DSC) is in the range of from 120° C. to 140° C., whereby (i) the melting temperature of the propylene-hexene random copolymer (B) is lower than the melting temperature of the propylene-ethylene random copolymer (A) and (ii) the MFR2 (230° C., 2.16 kg, ISO 1133) of the blend is in a range of from 0.5 to 60.0 g/10 min.
In the examples both components have very high MFR of above 30.0 g/10 min. The limited compatibility of the two component results in a rather high haze of more than 50% for all inventive examples.
EP 3387066 A-1 claims a propylene polymer composition comprising (a) from 40 to 80 wt.-% of a propylene 1-hexene copolymer containing from 5.5 to 9.0 wt.-% of 1-hexene derived units having a MFR (230° C./2.16 kg) from 3.5 to 12.0 g/10 min;
(b) from 20 to 60 wt.-% of a propylene ethylene copolymer containing from 1.5 wt.-% to 6.5 wt.-% of ethylene derived units, having a MFR2 (230° C./2.16 kg) from 3.5 to 12.0 g/10 min; the sum of the amount of a) and b) being 100.
Component b) is made with a Ziegler Natta catalyst and the polymer used in the Examples has a quite high xylene cold soluble (XCS) content of 18.0 wt.-%, which is, as already stated above, not desired for a variety of applications, since higher migration values are to be expected. Sealing initiation temperature (SIT) values are given, but they were determined when 2N are reached. If determined when 5N are reached, the SIT values would be clearly higher.
Although a lot of development work has been done in that field, there is still a need for further improvement and thus to design materials having an improved balance between low sealing initiation temperature SIT, beneficial optical properties and low xylene cold soluble (XCS) content.
The present invention is based on the finding that the above discussed needs for heat sealing applications can be achieved by a specific design of a polypropylene composition.
Thus the present invention is related to a polypropylene composition comprising a blend of
(A) 60.0 to 95.0 wt.-% of a metallocene catalysed propylene-hexene random copolymer with
(B) 5.0 to 40.0 wt.-% of a Ziegler-Natta catalysed propylene-ethylene random copolymer with
It has surprisingly been found out that such compositions have an optimized or improved balance between low sealing initiation temperature SIT, beneficial optical properties, low overall XCS amount and thus low migration.
Additionally, it has surprisingly found out that the sealing initiation temperature SIT of the blend is lower than for the individual components. This is contrary to the situation in EP 3387066, where the sealing initiation temperature SIT of the blend is higher than for the individual components.
In a further embodiment the invention is related to the use of the above defined composition for preparing articles and to the articles themselves. The articles are preferably films, more preferably cast films and even more preferably unoriented monolayer cast films.
In the following the individual components are defined in more detail.
The polypropylene composition of the present inventions comprises a blend of
(A) a propylene-hexene random copolymer and
(B) a propylene-ethylene random copolymer
The propylene-hexene random copolymer has an 1-hexene content in the range of from 1.0 to below 5.5 wt.-%, preferably in the range of from 1.5 to 5.0 wt.-%, more preferably in the range of from 2.0 to 4.5 wt.-%, yet more preferably in the range of from 2.5 to 4.2 wt.-%, and even more preferably in the range of from 2.8 to 4.0 wt.-%.
The MFR2 (230° C., 2.16 kg, ISO1133) of the propylene-hexene random copolymer is in the range of from 1.0 to 20.0 g/10 min, preferably in the range of from 1.5 to 15.0 g/10 min, more preferably in the range of from 2.0 to 12.0 g/10 min, yet more preferably in the range of from 3.0 to 10.0 g/10 min and even more preferably in the range of from 4.0 to 8.0 g/10 min.
The melting temperature Tm of the propylene-hexene random copolymer is in the range of from 130° C. to 160° C., preferably in the range of from 132° C. to 155° C., and more preferably in the range of from 134° C. to 150° C.
The propylene-hexene random copolymer furthermore has a xylene cold soluble (XCS) amount (measured according to ISO 16152, 2005, at 25° C.) in the range of 0.3 to 3.0 wt.-%, preferably in the range of 0.4 to 2.5 wt.-%, more preferably in the range of 0.5 to 2.0 wt.-%.
The propylene-hexene random copolymer as described above is obtained in the presence of a metallocene catalyst.
The metallocene catalyst can be a supported catalyst, using conventional supports or can be free from an external carrier. By free from an external carrier is meant that the catalyst does not contain an external support, such as an inorganic support, for example, silica or alumina, or an organic polymeric support material
Preferably used are metallocene catalysts which are free from an external carrier.
Preferably, the metallocene catalyst comprises (i) a complex of formula (I):
each X independently is a sigma-donor ligand,
L is a divalent bridge selected from —R′2C—, —R′2C—CR′2—, —R′2Si—, —R′2Si—SiR′2—, —R′2Ge—, wherein each R′ is independently a hydrogen atom or a C1-C20-hydrocarbyl group optionally containing one or more heteroatoms of Group 14-16 of the periodic table or fluorine atoms, or optionally two R′ groups taken together can form a ring,
each R1 are independently the same or can be different and are hydrogen, a linear or branched C1-C6-alkyl group, a C7-20 arylalkyl, C7-20 alkylaryl group or C6-20 aryl group or an OY group, wherein Y is a C1-10 hydrocarbyl group, and optionally two adjacent R1 groups can be part of a ring including the phenyl carbons to which they are bonded,
each R2 independently are the same or can be different and are a CH2—R8 group, with R8 being H or linear or branched C1-6-alkyl group, C3-8 cycloalkyl group, C6-10 aryl group,
R3 is a linear or branched C1-C6-alkyl group, C7-20 arylalkyl, C7-20 alkylaryl group or C6-C20-aryl group,
R4 is a C(R9)3 group, with R9 being a linear or branched C1-C6 alkyl group,
R5 is hydrogen or an aliphatic C1-C20 hydrocarbyl group optionally containing one or more heteroatoms from groups 14-16 of the periodic table of elements;
R6 is hydrogen or an aliphatic C1-C20 hydrocarbyl group optionally containing one or more heteroatoms from groups 14-16 of the periodic table of elements; or
R5 and R6 can be taken together to form a 5 membered saturated carbon ring which is optionally substituted by n groups R10, n being from 0 to 4;
each R10 is same or different and may be a C1-C20 hydrocarbyl group, or a C1-C20 hydrocarbyl radical optionally containing one or more heteroatoms belonging to groups 14-16 of the periodic table of elements;
R7 is H or a linear or branched C1-C6-alkyl group or an aryl or heteroaryl group having 6 to 20 carbon atoms optionally substituted by one to 3 groups R1,
(ii) a cocatalyst system comprising a boron containing cocatalyst and/or an aluminoxane cocatalyst and
(iii) optionally a silica support.
Each X independently is a sigma-donor ligand, thus each X may be the same or different, and is preferably a hydrogen atom, a halogen atom, a linear or branched, cyclic or acyclic C1-20-alkyl or -alkoxy group, a C6-20-aryl group, a C7-20-alkylaryl group or a C7-20-arylalkyl group; optionally containing one or more heteroatoms of Group 14-16 of the periodic table.
The term “C1-20 hydrocarbyl group” includes C1-20-alkyl, C2-20-alkenyl, C2-20-alkynyl, C3-20-cycloalkyl, C3-20-cycloalkenyl, C6-20-aryl groups, C7-20-alkylaryl groups or C7-20-arylalkyl groups or of course mixtures of these groups such as cycloalkyl substituted by alkyl. Linear and branched hydrocarbyl groups cannot contain cyclic units. Aliphatic hydrocarbyl groups cannot contain aryl rings.
Unless otherwise stated, preferred C1-20 hydrocarbyl groups are C1-20 alkyl, C4-20 cycloalkyl, C5-20 cycloalkyl-alkyl groups, C7-20 alkylaryl groups, C7-20 arylalkyl groups or C-20 aryl groups, especially C1-10 alkyl groups, C6-10 aryl groups, or C7-12 arylalkyl groups, e.g. C1-8 alkyl groups. Most especially preferred hydrocarbyl groups are methyl, ethyl, propyl, isopropyl, tert-butyl, isobutyl, C5-6-cycloalkyl, cyclohexylmethyl, phenyl or benzyl.
The term “halo” includes fluoro, chloro, bromo and iodo groups, especially chloro or fluoro groups, when relating to the complex definition.
Any group including “one or more heteroatoms belonging to groups 14-16 of the periodic table of elements” preferably means O, S or N. N groups may present as —NH— or —NR″— where R″ is C1-C10 alkyl. There may, for example, be 1 to 4 heteroatoms. The group including one or more heteroatoms belonging to groups 14-16 of the periodic table of elements may also be an alkoxy group, e.g. a C1-C10-alkoxy group.
Preferred complexes for the preparation of the propylene-hexene random copolymer are for example described in WO2019179959.
More preferred complexes are of formula (II)
wherein each R1 are independently the same or can be different and are hydrogen or a linear or branched C1-C6-alkyl group, whereby at least on R1 per phenyl group is not hydrogen,
R′ is a C1-10 hydrocarbyl group, preferably a C1-4 hydrocarbyl group and more preferably a methyl group and
X independently is a hydrogen atom, a halogen atom, C1-6 alkoxy group, C1-6 alkyl group, phenyl or benzyl group.
Most preferably, X is chlorine, benzyl or a methyl group. Preferably, both X groups are the same. The most preferred options are two chlorides, two methyl or two benzyl groups, especially two chlorides.
Specific preferred metallocene catalyst complexes of the invention include:
The ligands required to form the complexes and hence catalysts of the invention can be synthesised 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 WO2007/116034 discloses the necessary chemistry. Synthetic protocols can also generally be found in WO2002/02576, WO2011/135004, WO2012/084961, WO2012/001052, WO2011/076780, WO2015/158790 and WO2018/122134. The examples section also provides the skilled person with sufficient direction.
To form an active catalytic species it is normally necessary to employ a cocatalyst as is well known in the art.
According to the present invention a cocatalyst system comprising a boron containing cocatalyst and/or an aluminoxane cocatalyst is used in combination with the above defined metallocene catalyst complex.
The aluminoxane cocatalyst can be one of formula (III):
where n is usually 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 AlR3, AlR2Y and Al2R3Y3 where R can be, for example, C1-C10 alkyl, preferably C1-C5 alkyl, or C3-10 cycloalkyl, C7-C12 arylalkyl or alkylaryl and/or phenyl or naphthyl, and where Y can be hydrogen, halogen, preferably chlorine or bromine, or C1-C10 alkoxy, preferably methoxy or ethoxy. The resulting oxygen-containing aluminoxanes are not in general pure compounds but mixtures of oligomers of the formula (III).
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 instead of the aluminoxane cocatalyst or the aluminoxane cocatalyst can be used in combination with a boron containing cocatalyst.
It will be appreciated by the skilled man that where boron based cocatalysts are employed, it is normal to pre-alkylate the complex by reaction thereof with an aluminium alkyl compound, such as TIBA. This procedure is well known and any suitable aluminium alkyl, e.g. Al(C1-6-alkyl)3. can be used. Preferred aluminium alkyl compounds are triethylaluminium, tri-isobutylaluminium, tri-isohexylaluminium, tri-n-octylaluminium and tri-isooctylaluminium.
Alternatively, when a borate cocatalyst is used, the metallocene catalyst complex is in its alkylated version, that is for example a dimethyl or dibenzyl metallocene catalyst complex can be used.
Boron based cocatalysts of interest include those of formula (IV)
BY3 (IV)
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 methyl, propyl, isopropyl, isobutyl or trifluoromethyl, unsaturated groups such as aryl or haloaryl like phenyl, tolyl, benzyl groups, p-fluorophenyl, 3,5-difluorophenyl, pentachlorophenyl, pentafluorophenyl, 3,4,5-trifluorophenyl and 3,5-di(trifluoromethyl)phenyl. Preferred options are trifluoroborane, triphenylborane, tris(4-fluorophenyl)borane, tris(3,5-difluorophenyl)borane, tris(4-fluoromethylphenyl)borane, tris(2,4,6-trifluorophenyl)borane, tris(penta-fluorophenyl)borane, tris(tolyl)borane, tris(3,5-dimethyl-phenyl)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 borates are used, i.e. compounds containing a borate 3+ ion. Such ionic cocatalysts preferably contain a non-coordinating anion such as tetrakis(pentafluorophenyl)borate and tetraphenylborate. 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: triethylammoniumtetra(phenyl)borate, tributylammoniumtetra(phenyl)borate, trimethylammoniumtetra(tolyl)borate, tributylammoniumtetra(tolyl)borate, tributylammoniumtetra(pentafluorophenyl)borate, tripropylammoniumtetra(dimethylphenyl)borate, tributylammoniumtetra(trifluoromethylphenyl)borate, tributylammoniumtetra(4-fluorophenyl)borate, N,N-dimethylcyclohexylammoniumtetrakis(pentafluorophenyl)borate, N,N-dimethylbenzylammoniumtetrakis(pentafluorophenyl)borate, N,N-dimethylaniliniumtetra(phenyl)borate, N,N-diethylaniliniumtetra(phenyl)borate, N,N-dimethylaniliniumtetrakis(pentafluorophenyl)borate, N,N-di(propyl)ammoniumtetrakis(pentafluorophenyl)borate, di(cyclohexyl)ammoniumtetrakist(pentafluorophenyl)borate, triphenylphosphoniumtetrakis(phenyl)borate, triethylphosphoniumtetrakis(phenyl)borate, diphenylphosphoniumtetrakis(phenyl)borate, tri(methylphenyl)phosphoniumtetrakis(phenyl)borate, tri(dimethylphenyl)phosphoniumtetrakis(phenyl)borate, triphenylcarbeniumtetrakis(pentafluorophenyl)borate, or ferroceniumtetrakis(pentafluorophenyl)borate.
Preference is given to triphenylcarbeniumtetrakis(pentafluorophenyl) borate, N,N-dimethylcyclohexylammoniumtetrakis(pentafluorophenyl)borate or N,N-dimethylbenzylammoniumtetrakis(pentafluorophenyl)borate.
It has been surprisingly found that certain boron cocatalysts are especially preferred. Preferred borates of use in the invention therefore comprise the trityl ion. Thus the use of N,N-dimethylammonium-tetrakispentafluorophenylborate and Ph3CB(PhF5)4 and analogues therefore are especially favoured.
According to the present invention, the preferred cocatalysts are alumoxanes, more preferably methylalumoxanes, combinations of alumoxanes with AI-alkyls, boron or borate cocatalysts, and combination of alumoxanes with boron-based cocatalysts.
Suitable amounts of cocatalyst will be well known to the skilled man.
The molar ratio of boron to the metal ion of the metallocene may be in the range 0.5:1 to 10:1 mol/mol, preferably 1:1 to 10:1, especially 1:1 to 5:1 mol/mol.
The molar ratio of Al in the aluminoxane to the metal ion of the metallocene may be in the range 1:1 to 2000:1 mol/mol, preferably 10:1 to 1000:1, and more preferably 50:1 to 500:1 mol/mol.
The catalyst can be used in supported or unsupported form, preferably in supported form. The particulate support material used is preferably an organic or inorganic material, such as silica, alumina or zirconia or a mixed oxide such as silica-alumina, in particular silica, alumina or silica-alumina. The use of a silica support is preferred. The skilled person is aware of the procedures required to support a metallocene catalyst.
Especially preferably, the support is a porous material so that the complex may be loaded into the pores of the support, e.g. using a process analogous to those described in WO94/14856 (Mobil), WO95/12622 (Borealis) and WO2006/097497.
The average particle size of the silica support can be typically from 10 to 100 μm. However, it has turned out that special advantages can be obtained if the support has an average particle size from 15 to 80 μm, preferably from 18 to 50 μm.
The average pore size of the silica support can be in the range 10 to 100 nm and the pore volume from 1 to 3 mL/g.
Examples of suitable support materials are, for instance, ES757 produced and marketed by PQ Corporation, Sylopol 948 produced and marketed by Grace or SUNSPERA DM-L-303 silica produced by AGC Si-Tech Co. Supports can be optionally calcined prior to the use in catalyst preparation in order to reach optimal silanol group content.
The use of these supports is routine in the art.
The propylene-hexene random copolymer can be produced in a single polymerization step comprising a single polymerization reactor (R1) or in a sequential polymerization process comprising at least two polymerization reactors (R1) and (R2), whereby in the first polymerization reactor (R1) a first propylene copolymer fraction (R-PP1) is produced, which is subsequently transferred into the second polymerization reactor (R2). In the second polymerization reactor (R2) a second propylene copolymer fraction (R-PP2) is produced in the presence of the first propylene copolymer fraction (R-PP1).
Polymerization processes which are suitable for producing the propylene-hexene random copolymer generally comprises at one or two polymerization stages and each stage can be carried out in solution, slurry, fluidized bed, bulk or gas phase.
The term “polymerization reactor” shall indicate that the main polymerization takes place. Thus in case the process consists of one or two polymerization reactors, this definition does not exclude the option that the overall system comprises for instance a pre-polymerization step in a pre-polymerization reactor. The term “consist of” is only a closing formulation in view of the main polymerization reactors.
The term “sequential polymerization process” indicates that the propylene-hexene random copolymer is produced in at least two reactors connected in series. Accordingly such a polymerization system comprises at least a first polymerization reactor (R1) and a second polymerization reactor (R2), and optionally a third polymerization reactor (R3).
The first, respectively the single, polymerization reactor (R1) is preferably a slurry reactor and can be any continuous or simple stirred batch tank reactor or loop reactor operating in bulk or slurry. Bulk means a polymerization in a reaction medium that comprises of at least 60% (w/w) monomer. According to the present invention the slurry reactor is preferably a (bulk) loop reactor.
In case a “sequential polymerization process” is applied the second polymerization reactor (R2) and the optional third polymerization reactor (R3) are gas phase reactors (GPRs), i.e. a first gas phase reactor (GPR1) and a second gas phase reactor (GPR2). A gas phase reactor (GPR) according to this invention is preferably a fluidized bed reactor, a fast fluidized bed reactor or a settled bed reactor or any combination thereof.
A preferred multistage process is a “loop-gas phase”-process, such as developed by Borealis (known as BORSTAR® technology) described e.g. in patent literature, such as in EP 0 887 379, WO 92/12182, WO 2004/000899, WO 2004/111095, WO 99/24478, WO 99/24479 or in WO 00/68315.
A further suitable slurry-gas phase process is the Spheripol® process of Basell.
The propylene-hexene random copolymer can be unimodal or multimodal, like bimodal, in view of comonomer content and/or MFR2.
If the propylene-hexene random copolymer is unimodal, it is preferably produced in a single polymerization step in one polymerization reactor (R1). Alternatively a unimodal propylene-hexene random copolymer can be produced in a sequential polymerization process using the same polymerization conditions in all reactors.
If the propylene-hexene random copolymer is multimodal, it is preferably produced in a sequential polymerization process using different polymerization conditions (amount of comonomer, hydrogen amount, etc.) in the reactors.
Preferably the propylene-hexene random copolymer used according to the present invention is bimodal, especially in view of MFR and/or 1-hexene content.
In this case, the propylene-hexene random copolymer, comprises two polymer fractions (R-PP1) and (R-PP2).
Preferably, the propylene-hexene random copolymer consists of
25.0 to 50.0 wt.-%, preferably 30.0 to 48.0 wt.-%, more preferably 35.0 to 45.0 wt.-% of polymer fraction (R-PP1) having
Fraction (R-PP1) may be further characterized by an amount of xylene cold soluble (XCS) in the range of 0.3 to 3.0 wt.-%, preferably in the range of 0.4 to 2.5 wt.-% and more preferably in the range of 0.5 to 2.0 wt.-%, and Fraction (R-PP2) may be further characterized by an amount of xylene cold soluble (XCS) in the range of 0.3 to 3.0 wt.-%, preferably in the range of 0.4 to 2.5 wt.-% and more preferably in the range of 0.5 to 2.0 wt.-%.
The propylene-hexene random copolymer as defined in the instant invention may contain up to 5.0 wt.-% additives, like a-nucleating agents and antioxidants, as well as slip agents and antiblocking agents. Preferably, the additive content (without a-nucleating agents) is below 3.0 wt.-%, like below 1.0 wt.-%.
The propylene-ethylene random copolymer has an ethylene content in the range of from 0.5 to 8.0 wt.-%, preferably in the range of from 0.8 to 7.0 wt.-%, more preferably in the range of from 1.0 to 6.0 wt.-%, yet more preferably in the range of from 1.2 to 5.0 wt.-% and even more preferably in the range of from 1.4 to 4.5 wt.-%.
The MFR2 (230° C., 2.16 kg, ISO1133) of the propylene-ethylene random copolymer is in the range of from 1.0 to 20.0 g/10 min, preferably in the range of from 1.5 to 16.0 g/10 min, more preferably in the range of from 2.0 to 12.0 g/10 min, yet more preferably in the range of from 3.0 to 10.0 g/10 min.
The melting temperature Tm of the propylene-ethylene random copolymer is in the range of from 125° C. to 160° C., preferably in the range of from 130° C. to 158° C., more preferably of from 140 to 155° C.
In order to be suitable for food or pharmaceutical packaging applications it is furthermore desirable that the propylene-ethylene random copolymer has a limited amount of soluble and/or extractable substances.
It is therefore further preferred that the content of xylene cold solubles (XCS) of the propylene-ethylene random copolymer is from greater than 2.5 to 10.0 wt.-%, more preferred from 3.0 to 9.0 wt.-% and even more preferably from 3.5 to 8.0 wt.-%.
The propylene-ethylene random copolymer can be produced in a single polymerization step comprising a single polymerization reactor (R1) or in a sequential polymerization process comprising at least two polymerization reactors (R1) and (R2), whereby in the first polymerization reactor (R1) a first propylene copolymer fraction (R-PP1) is produced, which is subsequently transferred into the second polymerization reactor (R2). In the second polymerization reactor (R2) a second propylene copolymer fraction (R-PP2) is then produced in the presence of the first propylene copolymer fraction (R-PP1).
The term “polymerization reactor” is defined as described above for Component (A).
The term “sequential polymerization process” is defined as described above for Component (A).
Polymerization processes which are suitable for producing the propylene-ethylene random copolymer generally comprises one or two polymerization stages and each stage can be carried out in solution, slurry, fluidized bed, bulk or gas phase.
The propylene-ethylene random copolymer can be unimodal or multimodal, like bimodal, in view of comonomer content and/or MFR2.
If the propylene-ethylene random copolymer is unimodal, it is preferably produced in a single polymerization step in one polymerization reactor (R1). Alternatively a unimodal propylene-ethylene random copolymer can be produced in a sequential polymerization process using the same polymerization conditions in all reactors.
If the propylene-ethylene random copolymer is multimodal, it is preferably produced in a sequential polymerization process using different polymerization conditions (amount of comonomer, hydrogen amount, etc.) in the reactors.
The propylene-ethylene random copolymer (B) according to this invention has been produced in the presence of a Ziegler-Natta catalyst.
The Ziegler-Natta catalyst is fed into the first, respectively the single, polymerization reactor (R1) and is optionally transferred with the polymer (slurry) obtained in the first polymerization reactor (R1) into the subsequent reactors, if the propylene-ethylene random copolymer is produced in a sequential polymerization process.
If the process covers also a pre-polymerization step it is preferred that all of the Ziegler-Natta catalyst is fed in the pre-polymerization reactor. Subsequently the pre-polymerization product containing the Ziegler-Natta catalyst is transferred into the first, respectively the single, polymerization reactor (R1).
This Ziegler-Natta catalyst can be any stereo-specific Ziegler-Natta catalyst for propylene polymerization, which preferably is capable of catalysing the polymerization and copolymerization of propylene and comonomers at a pressure of 500 to 10000 kPa, in particular 2500 to 8000 kPa, and at a temperature of 40 to 110° C., in particular of 60 to 110° C. Preferably, the Ziegler-Natta catalyst (ZN-C) comprises a high-yield Ziegler-Natta type catalyst including an internal donor component, which can be used at high polymerization temperatures of 80° C. or more.
Such high-yield Ziegler-Natta catalyst (ZN-C) can comprise a succinate, a diether, a phthalate etc., or mixtures therefrom as internal donor (ID), and are for example commercially available for example from LyondellBasell under the Avant ZN trade name.
Further useful solid catalysts are also those disclosed in WO-A-2003/000757, WO-A-2003/000754, WO-A-2004/029112 and WO2007/137853. These catalysts are solid catalysts of spherical particles with compact structure and low surface area of the particles. Further, these catalysts are featured by a uniform distribution of catalytically active sites thorough the catalyst particles. Catalysts are prepared by emulsion-solidification method, where no external support is needed. The dispersed phase in the form of liquid droplets of the emulsion forms the catalyst part, which is transformed to solid catalyst particles during the solidification step.
Thus, in an embodiment of the present invention, the solid catalyst component is prepared by a process comprising:
The catalyst particles are obtained after solidifying said droplets of the dispersed phase by heating, preferably at a temperature from 80° C. to 110° C. In said process an aluminium alkyl compound of the formula AlR3-nXn, where R is an alkyl and/or an alkoxy group of 1 to 20, preferably of 1 to 10 carbon atoms, X is a halogen and n is 0, 1 or 2, is added and brought into contact with the droplets of the dispersed phase of the agitated emulsion. Alternatively, the aluminium alkyl compound of the formula AlR3-nXn, is brought into contact with the solidified particles at the washing step before recovering the final solid particles.
Suitable internal electron donors are, among others, (di)esters of aromatic (di)carboxylic acids. Said aromatic carboxylic acid ester or diester can be formed in situ by reaction of an aromatic carboxylic acid chloride or diacid chloride with a C2-C16 alkanol and/or diol, and is preferable di-2-ethyl-hexyl phthalate.
A further suitable catalyst for the present invention is a solid Ziegler-Natta catalyst, which comprises compounds of a transition metal of Group 4 to 6 of IUPAC, like titanium, a Group 2 metal compound, like a magnesium, and an internal donor being a non-phthalic compound, more preferably a non-phthalic acid ester, still more preferably being a diester of non-phthalic dicarboxylic acids as described in more detail below. Thus, the catalyst is fully free of undesired phthalic compounds. Further, the solid catalyst is free of any external support material, like silica or MgCl2, but the catalyst is self-supported.
This Ziegler-Natta catalyst) can be further defined by the way as obtained.
Accordingly, the Ziegler-Natta catalyst is preferably obtained by a process comprising the steps of
a)
a1) providing a solution of at least a Group 2 metal alkoxy compound (Ax) being the reaction product of a Group 2 metal compound and a monohydric alcohol (A) comprising in addition to the hydroxyl moiety at least one ether moiety optionally in an organic liquid reaction medium; or
a2) a solution of at least a Group 2 metal alkoxy compound (Ax′) being the reaction product of a Group 2 metal compound and an alcohol mixture of the monohydric alcohol (A) and a monohydric alcohol (B) of formula ROH, optionally in an organic liquid reaction medium; or
a3) providing a solution of a mixture of the Group 2 alkoxy compound (Ax) and a Group 2 metal alkoxy compound (Bx) being the reaction product of a Group 2 metal compound and the monohydric alcohol (B), optionally in an organic liquid reaction medium; or
a4) providing a solution of Group 2 alkoxide of formula M(OR1)n(OR2)mX2-n-m or mixture of Group 2 alkoxides M(OR1)n′X2-n′ and M(OR2)m′X2-m′, where M is Group 2 metal, X is halogen, R1 and R2 are different alkyl groups with C2 to C16 carbon atoms, and 0<n<2, 0<m<2 and n+m+(2-n-m)=2, provided that both n and m 0, 0<n′<2 and 0<m′<2; and
b) adding said solution from step a) to at least one compound of a transition metal of Group 4 to 6 and
c) obtaining the solid catalyst component particles,
and adding a non-phthalic internal donor, at any step prior to step c).
The internal donor or precursor thereof is added preferably to the solution of step a).
According to the procedure above the Ziegler-Natta catalyst can be obtained via precipitation method or via emulsion (liquid/liquid two-phase system)—solidification method depending on the physical conditions, especially temperature used in steps b) and c).
In both methods (precipitation or emulsion-solidification) the catalyst chemistry is the same.
Further details regarding these methods are described e.g. in WO2019012110
The non-phthalic internal donor that can be preferably used in the preparation of the catalyst is preferably selected from (di)esters of non-phthalic carboxylic (di)acids, 1,3-diethers, derivatives and mixtures thereof. Especially preferred donors are diesters of mono-unsaturated dicarboxylic acids, in particular esters belonging to a group comprising malonates, maleates, succinates, citraconates, glutarates, cyclohexene-1,2-dicarboxylates and benzoates, and any derivatives and/or mixtures thereof. Preferred examples are e.g. substituted maleates and citraconates, most preferably citraconates.
Detailed description of preparation of catalysts are further disclosed in WO 2012/007430, EP2610271, EP 261027 and EP2610272.
The Ziegler-Natta catalyst is preferably used in association with an alkyl aluminum cocatalyst and optionally external donors.
As further component in the instant polymerization process an external donor is preferably present. Suitable external donors include certain silanes, ethers, esters, amines, ketones, heterocyclic compounds and blends of these. It is especially preferred to use a silane. It is most preferred to use silanes of the general formula
RapRbqSi(ORc)(4-p-q)
wherein Ra, Rb and Rc denote a hydrocarbon radical, in particular an alkyl or cycloalkyl group, and wherein 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 from one another 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(NR5R6)
wherein R5 and R6 can be the same or different a represent a hydrocarbon group having 1 to 12 carbon atoms.
R5 and R6 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 cyclic aliphatic hydrocarbon group having 1 to 12 carbon atoms. It is in particular preferred that R5 and R6 are independently selected from the group consisting of methyl, ethyl, n-propyl, n-butyl, octyl, decanyl, iso-propyl, iso-butyl, iso-pentyl, tert.-butyl, tert.-amyl, neopentyl, cyclopentyl, cyclohexyl, methylcyclopentyl and cycloheptyl.
More preferably both R5 and R6 are the same, yet more preferably both R5 and R4 are an ethyl group.
Especially preferred external donors are the dicyclopentyl dimethoxy silane donor (D-donor) or the cyclohexylmethyl dimethoxy silane donor (C-Donor).
In addition to the Ziegler-Natta catalyst and the optional external donor, a co-catalyst can be used. The co-catalyst is preferably a compound of group 13 of the periodic table (IUPAC), e.g. organo aluminum, such as an aluminum compound, like aluminum alkyl, aluminum halide or aluminum alkyl halide compound. Accordingly, in one specific embodiment the co-catalyst is a trialkylaluminium, like triethylaluminium (TEAL), dialkyl aluminium chloride or alkyl aluminium dichloride or mixtures thereof. In one specific embodiment the co-catalyst is triethylaluminium (TEAL).
Preferably the ratio between the co-catalyst (Co) and the external donor (ED) [Co/ED] and/or the ratio between the co-catalyst (Co) and the transition metal (TM) [Co/TM] should be carefully chosen.
Accordingly,
(a) the mol-ratio of co-catalyst (Co) to external donor (ED) [Co/ED] must 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 mol-ratio of co-catalyst (Co) to titanium compound (TC) [Co/TC] must be in the range of above 80 to 500, preferably is in the range of 100 to 350, still more preferably is in the range of 120 to 300.
The propylene-ethylene random copolymer as defined in the instant invention may contain up to 5.0 wt.-% additives, like a-nucleating agents and antioxidants, as well as slip agents and antiblocking agents. Preferably the additive content (without a-nucleating agents) is below 3.0 wt.-%, like below 1.0 wt.-%.
The polypropylene composition according to this invention can be obtained by (melt)-mixing the individual fractions, i.e. propylene-hexene random copolymer (A) and propylene-ethylene random copolymer (B). During the melt mixing suitable additives can additionally be added. For mixing, a conventional compounding or blending apparatus, e.g. a Banbury mixer, a 2-roll rubber mill, Buss-co-kneader, a single screw extruder with special mixing segments or a twin screw extruder may be used. The polymer composition recovered from the extruder is usually in the form of pellets.
In the blend for the polypropylene composition according to this invention component (A) is present in an amount of from 60.0 to 95.0 wt.-% and component (B) is present in an amount of from 5.0 to 40.0 wt.-%.
Preferably component (A) is present in an amount of from 65.0 to 92.0 wt.-% and more preferably in an amount of from 70.0 to 90.0 wt.-%.
Thus component (B) is preferably present in an amount of from 8.0 to 35.0 wt.-% and more preferably in an amount of from 10.0 to 30.0 wt.-%.
The overall melt flow rate, i.e. the melt flow rate MFR2 (230° C.) measured according to ISO 1133 of polypropylene composition is in a range of from 1.0 to 20.0 g/10 min, preferably in a range of from 1.5 g/10 min to 16.0 g/10 min, more preferably in a range of from 2.0 g/10 min to 12.0 g/10 min and even more preferably in a range of from 2.5 to 10.0 g/10 min.
It is appreciated that the inventive polypropylene composition has a melting temperature in the range of from 130° C. to 155° C., preferably in the range of from 135° C. to 150° C., and more preferably in the range of from 137° C. to 147° C.
Additionally it is appreciated that the inventive polypropylene composition has a crystallization temperature in the range of from 85° C. to 115° C., preferably in the range of from 90° C. to 110° C. and more preferably in the range of from 95° C. to 105° C.
Furthermore the inventive polypropylene composition is characterized by a low level of xylene cold soluble (XCS) fraction, which is in the range of from 1.0 to 10.0 wt.-% (determined at 25° C. according ISO 16152; 2005), preferably in the range of from 1.3 to 8.0 wt.-% and more preferably in the range from 1.5 to 6.5 wt.-%.
The polypropylene composition as defined in the instant invention may contain up to 5.0 wt.-% additives, like α-nucleating agents and antioxidants, as well as slip agents and antiblocking agents. Preferably the additive content (without a-nucleating agents) is below 3.0 wt.-%, like below 1.0 wt.-%.
The present invention is not only directed to the instant polypropylene composition but also the use of the polypropylene composition for preparing articles and the articles comprising the polypropylene composition.
Suitable articles are films for flexible packaging systems, such as bags or pouches for food and pharmaceutical packaging or medical articles in general.
In an embodiment the present invention is related also to films and film layers, preferably unoriented films or film layers, of multi-layer film constructions comprising the inventive polypropylene composition. Accordingly the present invention is also directed to preferably unoriented films, like cast films or blown films, e.g. air cooled blown films, comprising at least 90.0 wt.-%, preferably comprising at least 95.0 wt.-%, yet more preferably comprising at least 99.0 wt.-%, of the instant polypropylene composition. Most preferred are unoriented monolayer cast films.
It has been found that such polypropylene composition according to the present invention provides the film material made thereof with a combination of low sealing initiation temperature (S.I.T), beneficial optical properties and low amounts of xylene cold solubles.
Films comprising the inventive polypropylene composition shall preferably have a tensile modulus in machine and transverse direction determined on 50 μm cast film in a range of 350 to 800 MPa, more preferably in a range of 380 to 750 MPa, like in a range of 400 to 720 MPa.
Furthermore, films comprising the inventive polypropylene composition shall preferably have a sealing initiation temperature (SIT) in the range of from 90° C. to 125° C., more preferably in the range of from 95° C. to less than 120° C., like in the range of from 100° C. to less than 115° C.
Even further, such an film comprising the inventive polypropylene composition shall preferably have a haze determined on 50 μm cast film in a range of from 0.01 to below 1.0%, preferably in a range of from 0.05 to below 0.50% and more preferably in a range of from 0.10 to below 0.40%.
Further, the invention is also directed to a multi-layer film construction, comprising an unoriented film as defined above as an outermost layer, which serves as a sealing layer in the multi-layer film construction.
A multi-layer film construction comprising at least one layer comprising the inventive polypropylene composition is preferably produced by multi-layer co-extrusion followed by film casting or film blowing. In this case, at least one of the outermost layers of said multi-layer film construction serving as sealing layer(s) shall comprise the inventive polypropylene composition as defined above. The inventive multilayer film construction shall preferably have a thickness in the range of 30 to 500 μm, more preferably in the range of 50 to 400 μm, like in the range of 60 to 300 μm. The sealing layer(s) comprising the inventive polypropylene composition shall preferably have a thickness in the range of 3 to 50 μm, more preferably in the range of 5 to 30 μm, like in the range of 8 to 25 μm.
Films and/or multi-layer film constructions according to the present invention shall preferably be used for flexible packaging systems, such as bags or pouches for food and pharmaceutical packaging or medical articles in general.
In case a film is produced by cast film technology the molten polypropylene composition is extruded through a slot extrusion die onto a chill roll to cool the polypropylene composition to a solid film. Typically the polypropylene composition is firstly compressed and liquefied in an extruder, it being possible for any additives to be already added to the polypropylene composition or introduced at this stage via a masterbatch. The melt is then forced through a flat-film die (slot 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° C. to 50° C., preferably from 15° C. to 40° C.
In the blown film process the polypropylene composition melt is extruded through an annular die and blown into a tubular film by forming a bubble which is collapsed between nip rollers after solidification. The blown extrusion can be preferably effected at a temperature in the range 160° C. to 240° C., and cooled by water or preferably by blowing gas (generally air) at a temperature of 10° C. to 50° C. to provide a frost line height of 0.5 to 8 times the diameter of the die. The blow up ratio should generally be in the range of from 1.5 to 4, such as from 2 to 4, preferably 2.5 to 3.5.
The xylene soluble fraction at room temperature (XCS, wt.-%): The amount of the polymer soluble in xylene is determined at 25° C. according to ISO 16152; 2005.
While comonomer content and XCS of the first polymer fraction (R-PP1) of the propylene-hexene random copolymer (A) can be determined directly on samples taken after the first polymerization step, said values have to be calculated for the second polymer fraction (R-PP2). A simple mixing rule is used for this purpose, giving the formulas
wherein
w(R-PP1) is the weight fraction [in wt.-%] of the polymer fraction R-PP1
w(R-PP2) is the weight fraction [in wt.-%] of the polymer fraction R-PP2,
XCS(R-PP1) is the XCS content [in wt.-%] of the polymer fraction R-PP1,
XCS(A) is the XCS content [in wt.-%] of the propylene-hexene random copolymer (A),
XCS(R-PP2) is the calculated XCS content [in wt.-%] of the polymer fraction R-PP2,
C6(R-PP1) is the 1-hexene content [in wt.-%] of the polymer fraction R-PP1,
C6(A) is the 1-hexene content [in wt.-%] of the propylene-hexene random copolymer (A),
C6(R-PP2) is the calculated 1-hexene content [in wt.-%] of the polymer fraction R-PP2.
MFR2 (230° C.) is measured according to ISO 1133 (230° C., 2.16 kg load)
The melt flow rate is measured as the MFR2 in accordance with ISO 1133 15 (230° C., 2.16 kg load) for polypropylene. The MFR is an indication of the flowability, and hence the processability, of the polymer. The higher the melt flow rate, the lower the viscosity of the polymer.
wherein
w(R-PP1) is the weight fraction [in wt.-%] of the polymer fraction R-PP1
w(R-PP2) is the weight fraction [in wt.-%] of the polymer fraction R-PP2,
MFR(R-PP1) is the melt flow rate MFR2 (230° C.) [g/10 min] of the polymer fraction R-PP1,
MFR(A) is the melt flow rate MFR2 (230° C.) [g/10 min] of the propylene-hexene random copolymer (A),
MFR(R-PP2) is the calculated melt flow rate MFR2 (230° C.) [g/10 min] of the polymer fraction R-PP2.
Quantitative nuclear-magnetic resonance (NMR) spectroscopy was further used to quantify the comonomer content and comonomer sequence distribution of the polymers. Quantitative 13C{1H} NMR spectra were recorded in the solution-state using a Bruker Advance III 400 NMR spectrometer operating at 400.15 and 100.62 MHz for 1H and 13C respectively. All spectra were recorded using a 13C optimised 10 mm extended temperature probehead at 125° C. using nitrogen gas for all pneumatics. Approximately 200 mg of material was dissolved in 3 ml of 1,2-tetrachloroethane-d2 (TCE-d2) along with chromium-(Ill)-acetylacetonate (Cr(acac)3) resulting in a 65 mM solution of relaxation agent in solvent (Singh, G., Kothari, A., Gupta, V., Polymer Testing 28 5 (2009), 475). To ensure a homogenous solution, after initial sample preparation in a heat block, the NMR tube was further heated in a rotatary oven for at least 1 hour. Upon insertion into the magnet the tube was spun at 10 Hz. This setup was chosen primarily for the high resolution and quantitatively needed for accurate ethylene content quantification. Standard single-pulse excitation was employed without NOE, using an optimised tip angle, 1 s recycle delay and a bi-level WALTZ16 decoupling scheme (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 (6 k) transients were acquired per spectra. Quantitative 13C{1H} 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 chemical shift of the solvent. This approach allowed comparable referencing even when this structural unit was not present. Characteristic signals corresponding to the incorporation of ethylene were observed Cheng, H. N., Macromolecules 17 (1984), 1950).
With characteristic signals corresponding to 2,1 erythro regio defects observed (as described in L. Resconi, L. Cavallo, A. Fait, F. Piemontesi, Chem. Rev. 2000, 100 (4), 1253, in Cheng, H. N., Macromolecules 1984, 17, 1950, and in W-J. Wang and S. Zhu, Macromolecules 2000, 33 1157) the correction for the influence of the regio defects on determined properties was required. Characteristic signals corresponding to other types of regio defects were not observed.
The comonomer fraction was quantified using the method of Wang et. al. (Wang, W-J., Zhu, S., Macromolecules 33 (2000), 1157) through integration of multiple signals across the whole spectral region in the 13C{1H} spectra. This method was chosen for its robust nature and ability to account for the presence of regio-defects when needed. Integral regions were slightly adjusted to increase applicability across the whole range of encountered comonomer contents. For systems where only isolated ethylene in PPEPP sequences was observed the method of Wang et. al. was modified to reduce the influence of non-zero integrals of sites that are known to not be present. This approach reduced the overestimation of ethylene content for such systems and was achieved by reduction of the number of sites used to determine the absolute ethylene content to:
E=0.5(Sββ+Sβγ+Sβγ+0.5(Sαβ+Sαγ))
Through the use of this set of sites the corresponding integral equation becomes:
E=0.5(IH+IG+0.5(IC+ID))
using the same notation used in the article of Wang et. al. (Wang, W-J., Zhu, S., Macromolecules 33 (2000), 1157). Equations used for absolute propylene content were not modified.
The mole percent comonomer incorporation was calculated from the mole fraction:
E[mol %]=100*fE
The weight percent comonomer incorporation was calculated from the mole fraction:
E[wt %]=100*(fE*28.06)/((fE*28.06)+((1−fE)*42.08))
The comonomer sequence distribution 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 integration regions slightly adjusted to increase applicability to a wider range of comonomer contents.
Quantitative 13C{1H} NMR spectra recorded in the molten-state using a Bruker Avance III 500 NMR spectrometer operating at 500.13 and 125.76 MHz for 1H and 13C respectively. All spectra were recorded using a 13C 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. (Klimke, K., Parkinson, M., Piel, C., Kaminsky, W., Spiess, H. W., Wilhelm, M., Macromol. Chem. Phys. 2006; 207:382., Parkinson, M., Klimke, K., Spiess, H. W., Wilhelm, M., Macromol. Chem. Phys. 2007; 208:2128., Castignolles, P., Graf, R., Parkinson, M., Wilhelm, M., Gaborieau, M., Polymer 50 (2009) 2373). Standard single-pulse excitation was employed utilising the NOE at short recycle delays of 3 s (Klimke, K., Parkinson, M., Piel, C., Kaminsky, W., Spiess, H. W., Wilhelm, M., Macromol. Chem. Phys. 2006; 207:382., Pollard, M., Klimke, K., Graf, R., Spiess, H. W., Wilhelm, M., Sperber, O., Piel, C., Kaminsky, W., Macromolecules 2004; 37:813.). and the RS-HEPT decoupling scheme (Filip, X., Tripon, C., Filip, C., J. Mag. Resn. 2005, 176, 239., Griffin, J. M., Tripon, C., Samoson, A., Filip, C., and Brown, S. P., Mag. Res. in Chem. 2007 45, S1, S198). A total of 16384 (16 k) transients were acquired per spectra.
Quantitative 13C{1H} 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-hexene were observed and the comonomer content quantified in the following way.
The amount of 1-hexene incorporated in PHP isolated sequences was quantified using the integral of the αB4 sites at 44.2 ppm accounting for the number of reporting sites per comonomer:
H=IαB4/2
The amount of 1-hexene incorporated in PHHP double consecutive sequences was quantified using the integral of the ααB4 site at 41.7 ppm accounting for the number of reporting sites per comonomer:
HH=2*IααB4
When double consecutive incorporation was observed the amount of 1-hexene incorporated in PHP isolated sequences needed to be compensated due to the overlap of the signals αB4 and αB4B4 at 44.4 ppm:
H=(IαB4−2*IααB4)/2
The total 1-hexene content was calculated based on the sum of isolated and consecutively incorporated 1-hexene:
Htotal=H+HH
When no sites indicative of consecutive incorporation observed the total 1-hexen comonomer content was calculated solely on this quantity:
Htotal=H
Characteristic signals indicative of regio 2,1-erythro defects were observed (Resconi, L., Cavallo, L., Fait, A., Piemontesi, F., Chem. Rev. 2000, 100, 1253).
The presence of 2,1-erythro regio defects was indicated by the presence of the Pαβ (21e8) and Pαγ (21e6) methyl sites at 17.7 and 17.2 ppm and confirmed by other characteristic signals.
The total amount of secondary (2,1-erythro) inserted propene was quantified based on the αα21e9 methylene site at 42.4 ppm:
P21=Iαα21e9
The total amount of primary (1,2) inserted propene was quantified based on the main Sαα methylene sites at 46.7 ppm and compensating for the relative amount of 2,1-erythro, αB4 and ααB4B4 methylene unit of propene not accounted for (note H and HH count number of hexene monomers per sequence not the number of sequences):
P12=ISαα+2*P21+H+HH/2
The total amount of propene was quantified as the sum of primary (1,2) and secondary (2,1-erythro) inserted propene:
Ptotal=P12+P21=ISαα+3*Iαα21e9+(IαB4−2*IααB4)/2+IααB4
This simplifies to:
Ptotal=ISαα+3*Iαα21e9+0.5*IαB4
The total mole fraction of 1-hexene in the polymer was then calculated as:
fH=Htotal/(Htotal+Ptotal)
The full integral equation for the mole fraction of 1-hexene in the polymer was:
fH=(((IαB4−2*IααB4)/2)+(2*IααB4))/((ISαα+3*Iαα21e9+0.5*IαB4)+((IαB4−2*IααB4)/2)+(2*IααB4))
This simplifies to:
fH=(IαB4/2+IααB4)/(ISαα+3*Iαα21e9+IαB4+IααB4)
The total comonomer incorporation of 1-hexene in mole percent was calculated from the mole fraction in the usual manner:
H[mol %]=100*fH
The total comonomer incorporation of 1-hexene in weight percent was calculated from the mole fraction in the standard manner:
H[wt %]=100*(fH*84.16)/((fH*84.16)+((1−fH)*42.08))
Crystallization temperature and heat of crystallization (Hc) are determined from the cooling step, while melting temperature and heat of fusion (Hf) are determined from the second heating step.
Haze was determined according to ASTM D1003-00 on cast films 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.
Tensile modulus in machine and transverse direction were determined according to ISO 527-3 at 23° C. on the films as produced indicated below. Testing was performed at a cross head speed of 1 mm/min.
The method determines the sealing temperature range (sealing range) of polypropylene films. 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+/−0.5 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 of the multilayer films as produced indicated below with the following parameters:
Specimen width: 25.4 mm
Cool time: 99 sec
Peel Speed: 10 mm/sec
Start temperature 80° C.
End temperature: 150° C.
specimen is sealed A to A at each seal bar temperature and seal strength (force) is determined at each step. The temperature is determined at which the seal strength reaches 5 N.
The metallocene complex has been produced as described in WO2019/179959 for MC-2.
A steel reactor equipped with a mechanical stirrer and a filter net was flushed with nitrogen and the reactor temperature was set to 20° C. Next silica grade DM-L-303 from AGC Si-Tech Co, pre-calcined at 600° C. (5.0 kg) was added from a feeding drum followed by careful pressuring and depressurising with nitrogen using manual valves. Then toluene (22 kg) was added. The mixture was stirred for 15 min. Next 30 wt.-% solution of MAO in toluene (9.0 kg) from Lanxess was added via feed line on the top of the reactor within 70 min. The reaction mixture was then heated up to 90° C. and stirred at 90° C. for additional two hours. The slurry was allowed to settle and the mother liquor was filtered off. The catalyst was washed twice with toluene (22 kg) at 90° C., following by settling and filtration. The reactor was cooled off to 60° C. and the solid was washed with heptane (22.2 kg). Finally MAO treated SiO2 was dried at 600 under nitrogen flow for 2 hours and then for 5 hours under vacuum (−0.5 barg) with stirring. MAO treated support was collected as a free-flowing white powder found to contain 12.2% Al by weight.
30 wt.-% MAO in toluene (0.7 kg) was added into a steel nitrogen blanked reactor via a burette at 20° C. Toluene (5.4 kg) was then added under stirring. Metallocene MC-2 (93 g) was added from a metal cylinder followed by flushing with 1 kg toluene. The mixture was stirred for 60 minutes at 20° C. Trityl tetrakis(pentafluorophenyl) borate (91 g) was then added from a metal cylinder followed by a flush with 1 kg of toluene. The mixture was stirred for 1 h at room temperature. The resulting solution was added to a stirred cake of MAO-silica support prepared as described above over 1 hour. The cake was allowed to stay for 12 hours, folled by drying under N2 flow at 60° C. for 2 h and additionally for 5 h under vacuum (−0.5 barg) under stirring.
Dried catalyst was sampled in the form of pink free flowing powder containing 13.9% Al and 0.11% Zr.
As component (A) a propylene-hexene random copolymer was produced in a Borstar® pilot plant with a prepolymerization reactor and one slurry loop reactor.
As Component (B) RD804CF, a propylene-ethylene random copolymer, commercially available from Borealis has been used.
RD804CF has been produced with a phthalate free Ziegler Natta catalyst. MFR2 (230° C.) is 8.0 g/10 min, C2 content 2.0 wt.-%, XCS content ˜ 5.0 wt.-%, Tm 150° C.
Component (A) and Component (B) and blends therefrom were compounded in a co-rotating twin-screw extruder Coperion TSE 16 at 220° C. with 0.15 wt.-% antioxidant (Irganox B215FF from BASF AG, Germany; this is a 1:2-mixture of Pentaerythrityl-tetrakis(3-(3′,5′-di-tert. butyl-4-hydroxyphenyl)-propionate, CAS-no. 6683-19-8, and Tris (2,4-di-t-butylphenyl) phosphite, CAS-no. 31570-04-4); 0.05 wt.-% of Ca-stearate (CAS-no. 1592-23-0, commercially available from Faci, Italy).
The inventive and comparative Examples were converted to monolayer cast films with a thickness of 50 μm on a PM30 cast line (type laboratory extruder provided by Plastik Maschinenbau GmbH., Germany).The equipment consists of an extruder, chill roll with air knife and a winder.
A PP 3-zone screw with a diameter of 30 mm, 25 D length, 200 mm die, die gap 0.5 mm is applied in combination with a coat-hanger slit die assembly. The extrusion parameters were as follows: Extruder temperature profile: 220° C./240° C./250° C./260° C./260° C. (Melt temperature 220° C.; melt pressure 61 bar), Extruder speed: 50 rpm, Chill roll temperature: 20° C., take-off speed: 10.2 m/min
From the above table it can be clearly seen that the inventive polymer blend are characterised by an advantageous combination of sealing performance, low amounts of XCS and excellent optical properties.
| Number | Date | Country | Kind |
|---|---|---|---|
| 20175210.2 | May 2020 | EP | regional |
| Filing Document | Filing Date | Country | Kind |
|---|---|---|---|
| PCT/EP2021/062802 | 5/14/2021 | WO |
