COMPOSITION OF PROPYLENE / 1-HEXEN COPOLYMER WITH LOW SEALING TEMPERATURE, ITS PREPARATION PROCESS,

专利摘要:
propylene / 1-hexene copolymer composition with low sealing temperature. the present invention relates to the propylene copolymer composition (p) comprising (a) a propylene copolymer (a) having a comonomer content of at least 1.0% by weight, the comonomers are c <sym> ac < sym> <244> -olefins, and (b) a propylene copolymer (b) having a comonomer content of 4.0 to 20.0% by weight, the comonomers are c <sym> ac <sym> <244> -olefins, where also (i) the comonomer content in the propylene copolymer (a) is lower compared to the comonomer content in the propylene copolymer (b), (ii) the propylene copolymer composition (p) has a content from a comonomer of 2.0 to 10.0% by weight, the chromonomers are c <sym> ac <sym> <244 <-olefins, (iii) the weight ratio of the propylene copolymer (a) to the propylene copolymer ( b) is the range from 30/70 to 80/20.
公开号:BR112012026909B1
申请号:R112012026909-7
申请日:2011-04-18
公开日:2020-03-10
发明作者:Juha Paavilainen；Petar Doshev；Kristin Reichelt
申请人:Borealis Ag；
IPC主号:

专利说明:

Invention Patent Descriptive Report for "PROPYLENE / 1-HEXEN COPOLYMER COMPOSITION WITH LOW SEALING TEMPERATURE, ITS PREPARATION PROCESS, FILM, AND EXTRUSION COATED SUBSTRATE".
[001] The present invention relates to a new composition of propylene copolymer, its production and use.
[002] Polypropylenes are suitable for many applications. For example, polypropylene is applicable in areas where sealing properties play an important role, such as in the food packaging industry. Regardless of the type of polymer, a polymer must at best satisfy all the desired final properties and must additionally be easily processed, that is, it must withstand stress. However, final properties and processing properties often act in a conflicting manner.
[003] In many cases, the seal that is formed between the surfaces to be sealed is placed under load, while it is still hot. These mechanisms in which the heat-bonding properties of polypropylene are crucial to ensure a strong seal are formed even before cooling. But not only should the heat adhesion intensity be quite high, but the heat sealing start temperature must also be quite low. By operating at a 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 certainly cheaper to generate and maintain.
[004] In addition to the sealing properties in the food industry, low amounts of extractables are also required.
[005] In addition, the impact performance of the polymer must satisfy the demands of the food packaging industry. [006] Therefore, the aim of the present invention is to provide a polypropylene composition with high heat adhesion intensity, low heat seal initiation temperature (SIT) and good impact performance.
[007] The finding of the present invention is to provide a composition of propylene copolymer with quite high comonomer content, the comonomers are long chain α-olefins, and said propylene copolymer composition comprises two different fractions, said fractions differ in the comonomer content.
[008] Therefore, the present invention is directed to a propylene copolymer composition (P) comprising (a) a propylene copolymer (a) having a comonomer content of at least 1.0% by weight, the comonomers are C5 to C12 α-olefins, and (b) a propylene copolymer (B) having a comonomer content of 4.0 to 20.0% by weight, the comonomers are C5 to C12 α-olefins, where also (i ) the comonomer content in the propylene copolymer (a) is lower compared to the comonomer content in the propyl-no copolymer (B), (ii) the propylene copolymer composition (P) has a comonomer content of at least 2 , 0% by weight, the comonomers are C5 to C12 α-olefins, (iii) the weight ratio of the propylene copolymer (a) to the propylene copolymer (B) is in the range 20/80 to 80/20, preferably in the range 25/75 to 75/25, more preferably in the range 30/70 to 70/30.
[009] Preferably, the propylene copolymer composition (P) comprises the propylene copolymer (a) and the propylene copolymer (B) as the polymer components only.
[0010] It has surprisingly been found that such a propylene (P) copolymer composition has a low heat seal initiation temperature (SIT) and excellent impact properties (see, example section) [0011] In the following, invention is defined in more detail.
[0012] The propylene (P) copolymer composition according to this invention is characterized by a very high comonomer content. The quite high comonomer content is obtained due to the fact that the inventive propylene copolymer composition (P) comprises two fractions of propylene copolymer as defined here. A "comonomer" according to this invention is a polymerizable unit other than propylene. Therefore, the propylene (P) copolymer composition according to this invention will have a comonomer content of at least 2.0% by weight, more preferably at least 2.4% by weight, more preferably at least 3 0. 0% by weight, even more preferably at least 3.5% by weight, such as at least 3.8% by weight. Thus, it is preferred that the propylene (P) copolymer composition according to this invention has a comonomer content in the range of 2.0 to 10.0% by weight, more preferably in the range of 2.4 to 8, 0% by weight, even more preferably in the range of 3.0 to 8.0% by weight, even more preferably in the range of 3.5 to 8.0% by weight, as in the range of 3.5 to 6.5 % by weight.
[0013] The comonomers of the propylene (P) copolymer composition are C5 to C12 α-olefins, for example, 1-hexene and / or 1-octene. The propylene (P) copolymer composition of the present invention can contain more than one type of comonomer. Thus, the propylene (P) copolymer composition of the present invention may contain one, two or three different comonomers, the comonomers are selected from the group of C5 α-olefin, Ce α-olefin, C7 α-olefin, Cs α-olefin, C9 α-olefin, C10 α-olefin, C11 α-olefin, and C12 α-olefin. However, it is preferred that the propylene (P) copolymer composition contains only one type of comonomer. Preferably, the propylene (P) copolymer composition comprises - in addition to propylene - only 1-hexene and / or 1-octene. In an especially preferred embodiment, the comonomer of the propylene (P) copolymer composition is only 1-hexene.
[0014] The propylene copolymer (P) composition as well as the propylene copolymer (a) and the propylene copolymer (B) according to this invention are preferably random propylene copolymers. The term "random copolymer" should preferably be understood according to IUPAC (Pure Appl. Chem., Vol. No. 68, 8, pp. 1591 to 1595, 1996). Preferably, the molar concentration of comonomer dyads, such as 1-hexene dyads, follows the ratio [HH] <[H] 2 [0015] where [0016] [HH] is the molar fraction of adjacent comonomer units, as of adjacent 1-hexene units, and [0017] [H] is the molar fraction of total comonomer units, as of total 1-hexene units, in the polymer.
Preferably, the propylene copolymer composition (P) as well as the propylene copolymer (a) and the propylene copolymer (B) as defined in detail below are isotactic. It is therefore appreciated that the composition of propylene copolymer (P), propylene copolymer (a) and propylene copolymer (B) has a very high isotactic triad concentration, that is, higher than 90%, more preferably higher than 92%, even more preferably higher than 93% and even more preferably higher than 95%, as higher than 97%.
[0019] The molecular weight distribution (MWD) is the relationship between the number of molecules in a polymer and the size of the individual chain. The molecular weight distribution (MWD) is expressed as the ratio of average weight molecular weight (Mw) to number average molecular weight (Mn). The number average molecular weight (Mn) is an average molecular weight of a polymer expressed as the first moment of plotting the number of molecules in each molecular weight range against the molecular weight. In effect, this is the total molecular weight of all molecules divided by the number of molecules. In turn, the average weight molecular weight (Mw) is the first moment of plotting the polymer weight in each molecular weight versus molecular weight range.
[0020] The number average molecular weight (Mn) and the average weight molecular weight (Mw) as well as the molecular weight distribution (MWD) are determined by size exclusion chromatography (SEC) using the Waters Alliance GPCV instrument 2000 with online viscometer. The oven temperature is 140 ° C. Trichlorobenzene is used as a solvent (ISO 16014).
Therefore, it is preferred that the inventive propylene copolymer composition (P) has a weight average molecular weight (Mw) of 100 to 700 kg / mol, more preferably 150 to 400 kg / mol.
[0022] The number average molecular weight (Mn) of the polypropylene is preferably in the range of 25 to 200 kg / mol, more preferably from 30 to 150 kg / mol.
[0023] Also, it is appreciated that the molecular weight distribution (MWD) measured according to ISO 16014 is not more than 4.0, more preferably not more than 3.5, as not more than 3.0. Thus, the molecular weight distribution (MWD) of the propylene (P) copolymer composition is preferably between 2.0 to 4.0, even more preferably in the range of 2.0 to 3.5, such as 2.0 to 3.0.
[0024] Furthermore, it is preferred that the propylene (P) copolymer composition of the present invention has a melt flow rate (MFR) given in a specific range. The melt flow rate measured under a load of 2.16 kg at 230 ° C (ISO 1133) is denoted as MFR2 (230 ° C). Therefore, it is preferred that in the present invention the propylene (P) copolymer composition has an MFR2 melting flow rate (230 ° C) measured according to ISO 1133 in the range of 2.0 to 50.0 g / 10min , more preferably in the range of 3.0 to 25.0 g / 10min, even more preferably in the range of 4.0 to 20.0 g / 10min.
[0025] As mentioned above, the inventive propylene copolymer (P) composition will be especially suitable for the packaging industry. Therefore, good sealing properties are desired, such as very low heat sealing start temperature (SIT) combined with good mechanical properties, such as good impact behavior.
It is therefore preferred that the propylene copolymer composition (P) has a heat sealing initiation temperature (SIT) of not more than 120 ° C, more preferably not more than 110 ° C, yet more preferably in the range of 90 to 120 ° C, even more preferably in the range of 93 to 118 ° C.
[0027] But not only will the heat sealing start temperature (SIT) be quite low, but also the melting temperature (Tm) will be quite high. Therefore, the difference between the melting temperature (Tm) and the heat sealing initiation temperature (SIT) will be quite high. Thus, it is preferred that the propylene copolymer composition (P) satisfies equation (I), more preferably equation (la), Tm - SIT> 22 ° C (I) Tm - SIT> 24 ° C (la) [0028] where [0029] Tm is the melting temperature given in centigrade [° C] of the propylene copolymer composition (P), [0030] SIT is the heat seal initiation temperature (SIT) given in centigrade [° C] of the propylene (P) copolymer composition.
[0031] The melting temperature (Tm) measured according to ISO 11357-3 of the propylene copolymer composition (P) is preferably at least 125.0 ° C, more preferably at least 128 ° C. Thus, it is particularly appreciated that the melting temperature (Tm) measured according to ISO 11357-3 of the propylene copolymer composition (P) is in the range of 125 to 145 ° C, more preferably in the range of 128 to 140 ° C.
[0032] Additionally, it is appreciated that the propylene copolymer (P) composition of the present invention has a crystallization temperature (Tc) measured according to ISO 11357-3 of at least 88 ° C, more preferably at least 90 ° C. Therefore, the polypropylene preferably has a crystallization temperature (Tc) measured in accordance with ISO 11357-3 in the range of 88 to 110 ° C, more preferably in the range of 90 to 105 ° C.
[0033] In addition, the propylene copolymer can be defined by the content soluble in ice cold xylene (XCS) measured according to ISO 6427. Therefore, the composition of the propylene copolymer (P) is preferably characterized by a soluble content in xylene ice cream (XCS) less than 20.0% by weight, more preferably less than 15.0% by weight, even more preferably less than or equal to 10.0% by weight, even more preferably below 5.0% by weight, as below 4.0% by weight. In this way, it is particularly appreciated that the propylene (P) copolymer composition of the present invention has a soluble content in chilled xylene (XCS) in the range of 0.3 to 20.0% by weight, more preferably in the range of 0 , 5 to 10.0% by weight, even more preferably in the range of 0.5 to 5.0% by weight.
[0034] Similar to soluble in cold xylene (XCS), the soluble in hot hexane (HHS) indicates that part of a polymer that has a low isotacticity and crystallinity and that is soluble in hexane at 50 ° C.
[0035] It is therefore preferred that the inventive propylene copolymer composition (P) has soluble in hot hexane (HHS) measured according to FDA 177.1520 not more than 2.5% by weight, more preferably not more than 2 , 0% by weight, such as not more than 1.5% by weight.
[0036] The propylene (P) copolymer composition of the present invention is also defined by its polymer fractions present. Accordingly, the propylene copolymer (P) composition of the present invention preferably comprises at least two fractions, i.e., the propylene copolymer (a) and the propylene copolymer (B).
[0037] Also, the propylene copolymer (a) is preferably the poor comonomer fraction since the propylene copolymer (B) is the rich comonomer fraction. Therefore, the comonomer content in the propylene copolymer (a) is lower compared to the comonomer content of the propylene copolymer (B). Thus, it is appreciated that the propylene copolymer composition (P) satisfies the correlation with (P) / with (a) being in the range of more than 1.0 to 10.0, more preferably being in the range of 1, 2 to 6.0, even more preferably in the range of 1.5 to 5.0, [0038] where [0039] with (a) is the comonomer content of the propylene copolymer (a) given as a percentage in weight [% by weight], [0040] with (P) is the comonomer content of the propylene copolymer composition (P) given as a percentage by weight [% by weight]. [0041] In this way, it is appreciated that the propylene copolymer (a) has a comonomer content of at least 1.0% by weight, more preferably the comonomer content is in the range of more than 1.0 to 4, 0% by weight, even more preferably in the range of 1.2 to 3.5% by weight.
[0042] The comonomers of the propylene copolymer (a) are C5 to C12 α-olefins, more preferably the comonomers of the propylene copolymer (a) are selected from the group C5 α-olefin, Ce α-olefin, C7 α-olefin, Cs α-olefin, C9 α-olefin, C10 α-olefin, C11 α-olefin, C12 α-olefin, even more preferably the comonomers of the propylene copolymer (a) are 1-hexene and / or 1-octene. The propylene copolymer (a) can contain more than one type of comonomer. In this way, the propylene copolymer (a) of the present invention can contain one, two or three different comonomers. However, it is preferred that the propylene copolymer (a) contains only one type of comonomer. Preferably, the propylene copolymer (A) comprises - in addition to propylene - only 1-hexene and / or 1-octene. In an especially preferred embodiment, the comonomer of the propylene copolymer (a) is only 1-hexene.
[0043] In this way, the propylene copolymer (a) is, in a preferred embodiment, a propylene copolymer of propylene and 1-hexene only, in which the 1-hexene content is in the range of more than 1.0 to 4.0% by weight, even more preferably in the range of 1.2 to 3.5% by weight.
[0044] As specified above, the propylene copolymer (B) has a higher comonomer content than the propylene copolymer (a). Therefore, the propylene copolymer (B) has a comonomer content of 2.5 to 20.0% by weight, preferably more than 3.0 to 18.0% by weight, more preferably 4, 0 to 15.0% by weight.
[0045] The comonomers of the propylene copolymer (B) C5 to C12 α-olefins, more preferably the comonomers of the propylene copolymer (B) are selected from the group of C5 α-olefin, Ce α-olefin, C7 α-olefin, C8 α-olefin, C9 α-olefin, C10 α-olefin, C11 α-olefin, and C12 α-olefin, even more preferably the comonomers of the propylene copolymer (B) are 1-hexene and / or 1-octene. The propylene copolymer (B) can contain more than one type of comonomer. In this way, the propylene copolymer (B) of the present invention can contain one, two or three different comonomers. However, it is preferred that the propylene copolymer (B) contains only one type of as-number. Preferably, the propylene copolymer (B) comprises - in addition to propylene - only 1-hexene and / or 1-octene. In an especially preferred embodiment, the comonomer of the propylene copolymer (B) is only 1-hexene.
[0046] Thus, the propylene copolymer (B) is, in a preferred embodiment, a propylene copolymer of propylene and 1-hexene only, in which the 1-hexene content is in the range of 2.5 to 20, 0 wt%, preferably more than 3.0 to 18.0 wt%, more preferably 4.0 to 15.0 wt%.
[0047] It is particularly preferred that the comonomers of the propylene copolymer (a) and the propylene copolymer (B) are the same. Therefore, in a preferred embodiment, the propylene copolymer (P) composition of the present invention preferably comprises only one propylene copolymer (a) and one propylene copolymer (B), in both polymers comonomer is just 1-hexene.
[0048] An important aspect of the present invention is that the propylene copolymer (a) and the propylene copolymer composition (P) differ in the comonomer content. In addition, the propylene copolymer (a) and the propylene copolymer composition (P) can also differ in the melt flow rate. Therefore, the MFR (A) / MFR (P) ratio is preferably in the range of 0.25 to 10.0, more preferably in the range of 0.5 to 5.0, even more preferably in the range of 0.7 to 2.5, [0049] where [0050] MFR (a) is the melting flow rate MFR2 (230 ° C) [g / 10min] measured according to ISO 1133 of the propylene copolymer (A), [ 0051] MFR (P) is the MFR2 melting flow rate (230 ° C) [g / 10min] measured according to ISO 1133 of the propylene (P) copolymer composition.
[0052] Also, it is appreciated that the propylene copolymer (a) has an MFR2 melting flow rate (230 ° C) measured according to ISO 1133 of at least 0.5 g / 10min, more preferably at least 2 , 0 g / 10min, even more preferably in the range of 0.5 to 70 g / 10min, even more preferably in the range of 2.0 to 50.0 g / 10min, such as 5.5 to 20.0 g / 10min.
[0053] As a high melt flow rate indicates a low molecular weight, it is appreciated that the propylene copolymer (A) has a weight average molecular weight (Mw) of less than 450 kg / mol, even more preferably less than 400 kg / mol, even more preferably in the range of 150 to below 450 kg / mol, as in the range of 180 to 400 kg / mol.
[0054] Also, the propylene copolymer (a) preferably has a soluble content in chilled xylene (XCS) of less than 2.0% by weight, more preferably less than 1.5% by weight, even more preferably in the range of 0.3 to 2.0% by weight, even more preferably in the range of 0.5 to 1.5% by weight. It is particularly preferred that the propylene copolymer (a) has a lower soluble content in chilled xylene (XCS) than the propylene copolymer (B).
[0055] The propylene (P) copolymer composition may contain additives known in the art, such as antioxidants, nucleating agents, gliding agents and antistatic agents. The polymer fraction, preferably the sum of the fractions of the propylene copolymer (a) and the propylene copolymer (B), is at least 90% by weight, more preferably at least 95% by weight, even more preferably at least 98 % by weight, such as at least 99% by weight.
The propylene (P) copolymer composition is in particular obtainable, preferably obtained, by a process as defined in detail below.
[0057] Also, the invention is directed to the use of the present propylene copolymer (P) composition as a film, such as a molten film, an extruded blown film or a biaxially oriented polypropylene (BOPP) film. The propylene (P) copolymer composition of the present invention can also be used as a coating on an extrusion-coated substrate. [0058] Therefore, the invention is also directed to a film layer, preferably to a sealing layer of a molten film, an extruded blown film or a biaxially oriented polypropylene (BOPP) film, said layer film (sealing layer) comprises at least 70% by weight, more preferably at least 80% by weight, as at least 90% by weight, of the propylene (P) copolymer composition according to the present invention. In an especially preferred embodiment, the film layer (sealing layer) consists of the propylene (P) copolymer composition as defined herein.
[0059] Also, the present invention is directed to an extrusion-coated substrate comprising a coating, said coating comprising at least 70% by weight, more preferably at least 90% by weight, as at least 95% by weight, of the composition of propylene (P) copolymer according to the present invention. In an especially preferred embodiment, the extrusion-coated substrate coating consists of the propylene (P) copolymer composition as defined herein. The substrate can be, for example, paper, cardboard, fabrics and metal sheets.
[0060] Additionally, the present invention is directed to the preparation of the propylene (P) copolymer composition of the present invention. Therefore, the process for preparing a propylene (P) copolymer composition as defined above is a sequential polymerization process comprising at least two reactors connected in series, wherein said process comprises the steps of [0061] ( A) polymerization in a first reactor (R-1) being a suspension reactor (SR), preferably a loop reactor (LR), propylene and at least one C5 to C12 α-olefin, preferably 1-hexene, obtaining a propylene copolymer (a) as defined in the present invention, preferably as defined in any one of claims 1.8 to 10, [0062] (B) transferring said propylene copolymer (a) and unreacted comonomers from the first reactor in a second reactor (R-2) being a gas phase reactor (GPR-1), [0063] (C) supplying said second reactor (R-2) of propylene and at least one C5 to C12 a-olefin, [0064] (D) polymerization in said second reactor (R-2 ) and in the presence of said first propylene copolymer (A), propylene and at least one C5 to C12 α-olefin obtaining a propylene copolymer (B) as defined in the present invention, preferably as defined in any one of claims 1, 8, or 9, said propylene copolymer (a) and said propylene copolymer (B) form the propylene copolymer composition (P) as defined in the present invention, preferably as defined in any one of claims 1 to 7, [0065] in which also [0066] in the first reactor (R-1) and second reactor (R-2), the polymerization takes place in the presence of a solid catalyst system (SCS), said solid catalyst system (SCS) comprises (i) a transition metal compound of Formula (I) Rn (Cp ') 2MX2 (I) [0067] where [0068] "M" is zirconium (Zr) or hafnium ( Hf), [0069] each "X" is independently a mo-novalent σ-ligand, [0070] each "Cp '" is a ligand o organic cyclopentadienyl type independently selected from the group consisting of substituted cyclopenta-dienyl, substituted indenyl, substituted tetrahydroindenyl, and substituted or unsubstituted fluorenyl, said organic linkers coordinated to the transition metal (M), [0071] "R" is a group bivalent bridge bonding to said organic ligands (Cp '), [0072] "n" is 1 or 2, preferably 1, and [0073] (ii) optionally a co-catalyst (Co) comprising an element ( E) of group 13 of the periodic table (IUPAC), preferably a co-catalyst (Co) comprising an Al compound. [0074] Regarding the definition of the composition of propylene copolymer (P), of the copolymer propylene (a) and propylene copolymer (B), is referred to the definitions given above.
[0075] Due to the use of the catalyst system (SCS) in a sequential polymerization process, the production of the propylene copolymer composition (P) defined above is possible. In particular due to the preparation of a propylene copolymer, that is, the propylene copolymer (a), in the first reactor (R-1) and the conduction of said propylene copolymer and especially the conduction of unreacted comonomers in the second reactor ( R-2). it is possible to produce a propylene (P) copolymer composition with a high comonomer content in a sequential polymerization process. Typically, the preparation of a propylene copolymer with a high comonomer content in a sequential polymerization process results in obstruction or in severe cases blocking the transfer lines when comonomers normally unreacted condense on the transfer lines. However, with the new method, the conversion of the co-monomers is increased and from this a better incorporation into the polymer chain resulting in higher comonomer content and reduced adhesion problems.
[0076] The term "sequential polymerization process" indicates that the propylene (P) copolymer composition is produced in at least two reactors connected in series. More precisely, the "term sequential polymerization process" indicates in the present application that the polymer of the first reactor (R-1) is directly conducted with comonomers unreacted to the second reactor (R-2). Therefore, a decisive aspect of the present process is the preparation of the propylene copolymer composition (P) in two different reactors, in which the reaction material of the first reactor (R-1) is directly conveyed to the second reactor (R-2) . Thus, the present process comprises at least one first reactor (R-1) and a second reactor (R-2). In a specific modality, the present process consists of two polymerization reactors (R-1) and (R-2). The term "polymerization reactor" will indicate that the main polymerization occurs. Thus, in the case where the process consists of two polymerization reactors, this definition would not exclude the option in which the total process comprises, for example, a prepolymerization step in a prepolymerization reactor. The term "consists of is only a restricted formulation in view of the main polymerization reactors.
[0077] The first reactor (R-1) is preferably a suspension reactor (SR) and can be any continuous or simple agitated batch tank reactor or loop reactor operating under load or suspension. Loading means polymerization in a reaction medium comprising at least 60% (w / w), preferably 100% monomer. According to the present invention, the suspension reactor (SR) is preferably a loop reactor (LR) of (load).
[0078] The second reactor (R-2) and any subsequent reactor are preferably gas phase reactors (GPR). Such gas phase reactors (GPR) can be any mechanically mixed bed or fluid reactors. Preferably, gas phase reactors (GPR) comprise a mechanically agitated fluid bed reactor with gas velocities of at least 0.2 m / s. Thus, it is appreciated that the gas phase reactor is a fluidized bed type reactor, preferably with a mechanical stirrer.
[0079] The condition (temperature, pressure, reaction time, monomer feed) in each reactor is dependent on the desired product that is known to a person skilled in the art. As already indicated above, the first reactor (R-1) is preferably a suspension reactor (SR), like a loop reactor (LR), since the second reactor (R-2) is preferably a phase reactor gas (GPR-1). Subsequent reactors - if present - are also preferably gas phase reactors (GPR).
[0080] A preferred multi-stage process is a "gas loop" process, as developed by Borealis A / S, Denmark (known as BORSTAR® technology) described, for example, in patent literature, as as in EP 0 887 379 or WO 92/12182.
[0081] Multimodal polymers can be produced according to various processes which are described, for example, in WO 92/12182, EP 0 887 379, and WO 98/58976. The contents of these documents are included here by reference.
[0082] Preferably, in the present process for producing the propylene copolymer composition (P) as defined above the conditions for the first reactor (R-1), that is, the suspension reactor (SR), as a reactor loop (LR), step (a) can be as follows: the temperature is within the range of 40 ° C to 110 ° C, preferably between 60 ° C and 100 ° C, 70 to 90 ° C, the pressure is within the range of 20 bar to 80 bar, preferably between 40 bar to 70 bar, hydrogen can be added to control molar mass in a manner known per se.
[0083] Subsequently, the reaction mixture from step (A) is transferred to the second reactor (R-2), that is, the gas phase reactor (GPR-1), that is, to step (D), by means of than the conditions in step (D) are preferably as follows: the temperature is within the range of 50 ° C to 130 ° C, preferably between 60 ° C and 100 ° C, the pressure is within the range of 5 bar at 50 bar, preferably between 15 bar to 40 bar, hydrogen can be added to control molar mass in a manner known per se.
[0084] The residence time may vary in both reactor zones.
[0085] In one embodiment, the process for producing the propylene copolymer (P) composition, the residence time in the load reactor, for example, loop is in the range of 0.2 to 4 hours, for example, 0.3 to 1.5 hours and the residence time in a gas phase reactor will generally be 0.2 to 6.0 hours, such as 0.5 to 4.0 hours.
[0086] If desired, polymerization can be carried out in a known manner under supercritical conditions in the first reactor (R-1), that is, in the suspension reactor (SR), as in the loop reactor (LR), and / or as a condensed mode in the gas phase reactor (GPR-1). [0087] The conditions in the other gas phase reactors (GPR), if present, are similar to the second reactor (R-2).
[0088] The present process can also cover prepolymerization before polymerization in the first reactor (R-1). Prepolymerization can be conducted in the first reactor (R-1), however it is preferred that prepolymerization takes place in a separate reactor, so-called prepolymerization reactor.
[0089] In a specific embodiment, the solid catalyst system (SCS) has a porosity measured according to ASTM 4641 of less than 1.40 mL / g and / or a surface area measured according to ASTM D 3663 of less than 25 m2 / g.
[0090] Preferably, the solid catalyst system (SCS) has a surface area of less than 15 m2 / g, still up to less than 10 m2 / g and more preferred less than 5 m2 / g, which is the lower measurement limit. The surface area according to this invention is measured according to ASTM D 3663 (N2).
[0091] Alternatively or additionally, it is appreciated that the solid catalyst system (SCS) has a porosity of less than 1.30 ml / g and more preferably less than 1.00 ml / g. Porosity was measured according to ASTM 4641 (N2). In another preferred embodiment, porosity is not detectable when determined with the method applied according to ASTM 4641 (N2).
[0092] Furthermore, the solid catalyst system (SCS) typically has an average particle size of not more than 500 pm, that is, preferably in the range of 2 to 500 pm, more preferably 5 to 200 pm. It is particularly preferred that the average particle size is below 80 pm, even more preferably below 70 pm. A preferred range for the average particle size is 5 to 70 pm, or up to 10 to 60 pm.
[0093] As specified above, the transition metal (M) is zirconium (Zr) or hafnium (Hf), preferably zirconium (Zr).
[0094] The term "σ-ligand" is understood in the complete description in a known manner, that is, a group attached to the metal by means of a sigma bond. In this way, the anionic ligands "X" can independently be halogen or be selected from the group consisting of group R ', OR', SiR'3, OSiR'3, OSO2CF3, OCOR ', SR', NR'2 or PR'2 where R 'is independently hydrogen, a linear or branched, cyclic or acyclic, C1 to C20 alkyl, C2 to C20 alkenyl, C2 to C20 alkynyl, C3 to C12 cycloalkyl, C6 to C20 aryl, C7 to C20 arylalkyl, C7 to C20 alkylaryl, C8 to C20 arylalkenyl, where the group R 'may optionally contain one or more heteroatoms belonging to groups 14 to 16. In a preferred embodiment, the anionic ligands "X" are identical and or halogen, such as CI, or methyl or benzyl. [0095] A preferred monovalent anionic binder is halogen, in particular chlorine (CI).
[0096] The substituted cyclopentadienyl ligand (s) may have one or more substituent (s) being selected from the group consisting of halogen, hydrocarbyl (for example, C1 to C20 alkyl, C2 to C20 alkenyl, C2 to C20 alkynyl, C3 to C20 cycloalkyl, such as C5 to C20 cycloalkyl replaced by C1 to C20 alkyl, C6 to C20 aryl, C1 to C20 alkyl replaced by C5 to C20 cycloalkyl in which the residue cycloalkyl is replaced by C1 to C20 alkyl, C7 to C20 arylalkyl, C3 to C12 cycloalkyl containing 1, 2, 3 or 4 heteroatom (s) in the ring portion, Ce to C20 heteroaryl, C1 to C20 haloalkyl, -SiR'3 , -SR ", -PR" 2 or -NR "2, each R" is independently a hydrogen or hydrocarbyl (for example, C1 to C20 alkyl, C1 to C20 alkenyl, C2 to C20 alkynyl, C3 to C20 cycloalkyl, or Ce to C20 aryl) or, for example, in the case of -NR "2, the two substituents R" can form a ring, for example, a five or six membered ring, together with the nitrogen atom in which they are linked.
[0097] Also, "R" of Formula (I) is preferably a bridge of 1 to 4 atoms, such atoms being independently carbon (C) atom (s), silicon (Si), germanium (Ge) or oxygen ( O), whereby each of the bridge atoms can independently carry substituents, such as C1 to C20 hydrocarbyl, tri (Ci to C2o-alkyl) silyl, tri (Ci to C2o-alkyl) siloxy and more preferably "R" is a one-atom bridge, for example, -SiR "2-, where each R is independently C1 to C2o-alkyl, C2 to C2o-alkenyl, C2 to C2o-alkynyl, C3 to C12 cycloalkyl, Ce to C2- aryl, alkylaryl or arylalkyl, or tri (C1 to C20 al-kil) silyl residue, such as trimethylsilyl, or the two R's may be part of a ring system including the Si bridge atom.
[0098] In a preferred embodiment, the transition metal compound has Formula (II) [0099] M is zirconium (Zr) or hafnium (Hf), preferably zirconium (Zr), [00100] X are ligands with a σ-bond to the metal "M", preferably those as defined above for Formula (I), [00101] R1 preferably chlorine (CI) or methyl (CH3), the first especially preferred, are equal to or different one on the other, preferably equal to, and are selected from the group consisting of C1 to C20 linear saturated alkyl, C1 to C20 linear unsaturated alkyl, C1 to C20 branched saturated alkyl, C1 to C20 branched unsaturated alkyl, C3 to C20 cycloalkyl, Ce a C20 aryl, C7 to C20 alkylaryl, and C7 to C20 arylalkyl, optionally containing one or more hetero atoms from groups 14 to 16 of the periodic table (IUPAC), are preferably equal to or different from each other, preferably equal to, and are C1 to C10 straight or branched hydrocarbyl, more preferably i equal to or different from each other, preferably equal to, and are C1 to C straight or branched alkyl, [00102] R2 to R6 are equal to or different from each other and are selected from the group consisting of hydrogen, C1 to C20 alkyl linear saturated, C1 to C20 linear unsaturated alkyl, C1 to C20 branched saturated alkyl, C1 to C20 branched unsaturated alkyl, C3 to C20 cycloalkyl, Ce to C20 aryl, C7 to C20 alkylaryl, and C7 to C20 arylalkyl, optionally containing one or more hetero atoms of groups 14 to 16 of the Periodic Table (IUPAC), [00103] are preferably equal to or different from each other and are C1 to C10 linear or branched hydrocarbyl, more preferably they are equal to or different from each other and are C1 to C6 linear or branched alkyl, [00104] R7 and R8 are the same or different from each other and selected from the group consisting of hydrogen, C1 to C20 linear saturated alkyl, C1 to C20 linear unsaturated alkyl, C1 to C20 branched saturated alkyl, C1 the C20 here branched unsaturated la, C3 to C20 cycloalkyl, C6 to C20 aryl, C7 to C20 alkylaryl, C7 to C20 arylalkyl, optionally containing one or more heteroatoms from groups 14 to 16 of the periodic table (IUPAC), SiR103, GeR103, OR10, SR10 and NR102, where [00105] R10 is selected from the group consisting of C1 to C20 linear saturated alkyl, C1 to C20 linear unsaturated alkyl, C1 to C20 branched saturated alkyl, C1 to C20 branched unsaturated alkyl, C3 to C20 cycloalkyl, C6 to C20 aryl, C7 to C20 alkylaryl, and C7 to C20 arylalkyl, optionally containing one or more hetero atoms from groups 14 to 16 of the periodic table (IUPAC), [00106] and / or [00107] R7 and R8 being optionally part of a system of ring from C4 to C20 carbon together with the indenyl carbons to which they are attached, preferably a C5 ring, optionally a carbon atom can be replaced by a nitrogen, sulfur or oxygen atom, [00108] R9 is equal to or different from each other and are selected from the upo consisting of hydrogen, C1 to C20 linear saturated alkyl, C1 to C20 linear unsaturated alkyl, C1 to C20 branched saturated alkyl, C1 to C20 branched unsaturated alkyl, C3 to C20 cycloalkyl, C6 to C20 aryl, C7 to C20 alkylaryl, C7 a C20 arylalkyl, OR10, and SR10, [00109] preferably R9 are equal to or different from each other and are H or CH3, where [00110] R10 is defined as before, [00111] L is a bivalent group bridging with the two indenyl ligands, preferably being a [00112] unit of C2R114 or a SiR112 or GeR112, wherein, [00113] R11 is selected from the group consisting of H, C1 to C20 linear saturated alkyl, C1 to C20 alkyl linear unsaturated, C1 to C20 branched saturated alkyl, C1 to C20 branched unsaturated alkyl, C3 to C20 cycloalkyl, C6 to C20 aryl, C7 to C20 alkylaryl or C7 to C20 arylalkyl, optionally containing one or more hetero atoms from groups 14 to 16 in the table (TUPAC), [00114] preferably Si (CH3) 2, SiCH3C 6Hn, or SiPh2, [00115] where C6H11 is cyclohexyl.
[00116] Preferably, the transition metal compound of Formula (II) is C2-symmetric or pseudo-C2-symmetric. As regards the definition of symmetry, reference is made to Resconi and other Chemical Reviews, 2000, Vol. 100, No. 4 1263 and references cited herein.
[00117] Preferably, residues R1 are the same or different from each other, more preferably the same, and are selected from the group consisting of C1 to C10 linear saturated alkyl, C1 to C10 linear unsaturated alkyl, C1 to C10 branched saturated alkyl, C1 to C10 branched unsaturated alkyl and C7 to C12 arylalkyl. Even more preferably, the R1 residues are the same as or different from each other, more preferably the same, and are selected from the group consisting of C1 to C6 linear saturated alkyl, C1 to C6 linear unsaturated alkyl, C1 to C6 branched saturated alkyl, C1 to C6 branched unsaturated alkyl and C7 to C10 arylalkyl. Even more preferably, the R1 residues are the same or different from each other, more preferably the same, and are selected from the group consisting of C1 to C4 linear or branched hydrocarbyl, such as, for example, methyl or ethyl.
Preferably, residues R2 to R6 are the same as or different from one another and C1 to C4 linear saturated alkyl or C1 to C4 branched saturated alkyl. Even more preferably, residues R2 to R6 are the same as or different from each other, more preferably the same, and are selected from the group consisting of methyl, ethyl, iso-propyl and tert-butyl.
[00119] Preferably, R7 and R8 are the same or different from each other and are selected from hydrogen and methyl, or they are part of a 5-methylene ring including the two indenyl ring carbons to which they are attached. In another preferred embodiment, R7 is selected from OCH3 and OC2H5, and R8 is tert-butyl.
[00120] In a preferred embodiment, the transition metal compound is rac-methyl (cyclohexyl) silanediyl bis (2-methyl-4- (4-tert-butylphenyl) indenyl) zirconium.
[00121] In a second preferred embodiment, the transition metal compound is rac-bis (2-methyl-4-phenyl-1,5,6,7-tetrahydro-s-indacen-1-yl) zirconium dichloride dimethylsilanediyl.
[00122] In a third preferred embodiment, the transition metal compound is rac-dimethylsilanediyl bis (2-methyl-4-phenyl-5-methoxy-6-tert-butylindenyl) zirconium.
[00123] As an additional requirement, the solid catalyst system (SCS) according to this invention must comprise a cocata-lysador (Co) comprising an element (E) of group 13 of the periodic table (IUPAC), for example, the co-catalyst (Co) comprises an Al compound.
[00124] Examples of such a cocatalyst (Co) are aluminum organ compounds, such as aluminoxane compounds.
[00125] Such Al compounds, preferably aluminoxanes, can be used as the compound only in the cocatalyst (Co) or in conjunction with other co-catalyst compound (s). In this way, in addition to or in addition to the Al compounds, i.e., the aluminoxanes, other cation complex formation co-catalyst compounds, such as boron compounds can be used. Said cocatalysts are either commercially available or can be prepared according to the prior art literature. Preferably, however, in the production of the solid catalyst system only compounds of Al such as coca-talisator (Co) are employed.
[00126] In particular, the preferred (Co) cocatalysts are aluminoxanes, in particular C1 to C10 alkylaluminoxanes, more particularly methylaluminoxane (MAO).
[00127] Preferably, the organo-zirconium compound of Formula (I) and the cocatalyst (Co) of the solid catalyst system (SCS) represent at least 70% by weight, more preferably at least 80% by weight, even more preferably at least 90% by weight, even more preferably at least 95% by weight of the solid catalyst system. In this way, it is appreciated that the solid catalyst system is characterized by the fact that it is self-supporting, that is, it does not comprise any catalytically inert support material, such as, for example, silica, alumina or MgCb or porous polymeric material, which is otherwise commonly used in heterogeneous catalyst systems, that is, the catalyst is not supported on support material or external carrier. As a consequence of this. the solid catalyst system (SCS) is self-supporting and has a very low surface area.
[00128] In one embodiment, the solid metallocene catalyst (SCS) system is obtained by emulsion solidification technology, the basic principles of which are described in WO 03/051934. This document is hereby included in its entirety by reference.
Consequently, the solid catalyst system (SCS) is preferably in the form of solid catalyst particles, obtainable by a process comprising the steps of a) preparing a solution of one or more catalyst components; b) dispersing said solution in a second solvent to form an emulsion in which said one or more catalyst components are present in the drops of the dispersed phase, c) solidifying said dispersed phase to convert said drops to the solid particles and optionally coating said particles to obtain said catalyst.
[00130] Preferably, a first solvent, more preferably a first organic solvent, is used to form said solution. Even more preferably, the organic solvent is selected from the group consisting of a linear alkane, cyclic alkane, aromatic hydrocarbon and halogen-containing hydrocarbon.
[00131] Furthermore, the second solvent forming the continuous phase is a solvent inert to the catalyst components. The second solvent could be immiscible in the solution of the catalyst components at least under conditions (such as temperature) during the dispersion step. The term "immiscible with the catalyst solution" means that the second solvent (continuous phase) is totally immiscible or partially immiscible, that is, not completely miscible with the dispersed phase solution.
[00132] Preferably, the immiscible solvent comprises a fluorinated organic solvent and / or a functionalized derivative thereof, even more preferably the immiscible solvent comprises a semi-, highly- or perfluorinated hydrocarbon and / or a functionalized derivative thereof. It is particularly preferred that said immiscible solvent comprises a perfluorohydrocarbon or a functionalized derivative thereof, preferably C3 to C30 perfluoroalkanes, -alkenes or -cycloalkanes, more preferred C4 to C10 perfluoroalkanes, -alkenes or -cycloalkanes, particularly preferred perfluorohexane , perfluoro-heptane, perfluorooctane or perfluoro (methylcyclohexane) or perfluoro (1,3-dimethylcyclohexane) or a mixture thereof.
[00133] Furthermore, it is preferred that the emulsion comprising said continuous phase and said dispersed phase is a bi-or multiphase system as known in the art. An emulsifier can be used to form and stabilize the emulsion. After formation of the emulsion system, said catalyst is formed in situ from catalyst components in said solution.
[00134] In principle, the emulsifying agent can be any suitable agent that contributes to the formation and / or stabilization of the emulsion and that has no adverse effect on the catalytic activity of the catalyst. The emulsifying agent may, for example, be a surfactant based on hydrocarbons optionally interrupted with (a) heteroatom (s), preferably halogenated hydrocarbons optionally having a functional group, preferably semi-, highly- or perfluorinated hydrocarbons as known in the art. technical. Alternatively, the emulsifying agent can be prepared during the preparation of the emulsion, for example, by reacting a surfactant precursor with a compound of the catalyst solution. Said surfactant precursor can be a halogenated hydrocarbon with at least one functional group, for example, a highly fluorinated C1-n (suitably C4-30 or C5-15) alcohol (for example, heptanol, octanol or highly fluorinated nonanol), oxide (eg propenoxide) or acrylate ester which reacts, for example, with a cocatalyst component, such as aluminoxane to form the "current" surfactant.
[00135] In principle, any solidification method can be used to form the solid particles of the dispersed droplets. According to a preferable modality, the solidification is effected by a temperature change treatment. As a result, the emulsion is subjected to a gradual temperature change of up to 10 ° C / min, preferably 0.5 to 6 ° C / min and more preferably 1 to 5 ° C / min. Even more preferred, the emulsion is subjected to a temperature change of more than 40 ° C, preferably more than 50 ° C within less than 10 seconds, preferably less than 6 seconds.
[00136] For additional details, modalities and examples of the continuous and dispersed phase system, emulsion formation method, emulsifying agent and solidification methods, reference is made, for example, to the above-mentioned international patent application WO 03 / 051934.
[00137] All or part of the preparation steps can be done in a continuous manner. Reference is made to WO 2006/069733 describing principles of such a method of continuous or se-micontinuous preparation of types of solid catalyst, prepared by means of emulsion / solidification method.
[00138] The catalyst components described above are prepared according to the methods described in WO 01/48034.
[00139] Furthermore, the present invention is related to the production of extruded coated substrates by conventional extrusion coating of the propylene (P) copolymer composition as defined herein.
[00140] The film according to this invention can be obtained in a conventional manner, for example, by fused film technology or extruded blown film technology. In this case, the film will be stretched, i.e., a biaxially oriented polypropylene film, it is preferably produced as follows: first, a molten film is prepared by extrusion of propylene copolymer (P) composition in the form of pellets. The prepared melt films can typically have a thickness of 50 to 100 µm as used for additional film stretching. Subsequently, a stack of fused films can be prepared from several sheets of fused film to obtain a specific stack thickness, for example, 700 to 1,000 µm. The drawing temperature is typically set at a temperature slightly below the melting point, for example, 2 to 4 ° C below the melting point, and the film is stretched in a specific established relationship in the machine and transverse direction.
[00141] The extrusion coating process can be performed using conventional extrusion coating techniques. Consequently, the propylene (P) copolymer composition obtained from the polymerization process defined above is fed, typically in the form of pellets, optionally containing additives, to an extrusion device. From the extruder, the polymer melt is preferably passed through a flat matrix to the substrate to be coated. Due to the distance between the matrix edge and the narrowing, the molten plastic is oxidized in the air for a short period, usually resulting in an improved adhesion between the coating and the substrate. The coated substrate is cooled in a cooling cylinder after it is passed through edge trimmers and rolled up. The line width can vary between, for example, 500 to 1,500 mm, for example, 800 to 1,100 mm, with a line speed of up to 1,000 m / min, for example, 300 to 800 m / min. The polymer melting temperature is typically between 275 and 330 ° C. The propylene (P) copolymer composition of the invention can be extruded into the substrate as a monolayer coating or as a coextruded layer. In any of these cases it is possible to use the propylene (P) copolymer composition as such or to combine the propylene (P) copolymer composition with other polymers. The combination can occur in a post-reactor treatment or just before extrusion in the coating process. However, it is preferred that only the propylene (P) copolymer composition as defined in the present invention is coated by extrusion. In a multi-layer extrusion coating, the other layers can comprise any polymer resin having the desired properties and processability. Examples of such polymers include: barrier layer PA (polyamide) and EVA; polar ethylene copolymers, such as ethylene and vinyl alcohol copolymers or ethylene copolymers and an acrylate monomer; adhesive layers, for example, ionomers, ethylene copolymers and ethyl acrylate, etc; HDPE for hardening; LDPE resins produced in a high pressure process; LLDPE resins produced by polymerization of ethylene and alpha-olefin comonomers in the presence of a Ziegler, chromium or metallocene catalyst; and MDPE resins.
[00142] Thus, the present invention is preferably related to extrusion-coated substrates comprising a substrate and at least one layer of the extrusion-coated propylene (P) copolymer composition on said substrate as defined in this invention.
[00143] In addition, the present invention is also directed to the use of the inventive article as packaging material, in particular as a packaging material for food and / or medical products.
[00144] In the following, the present invention is described by way of examples. EXAMPLES Measurement methods [00145] The following definitions of terms and methods of determination apply by the above general description of the invention as well as the examples below unless otherwise defined. Microstructure quantification by NMR spectroscopy [00146] Quantitative nuclear magnetic resonance (NMR) spectroscopy was used to quantify the isotacticity, regularity and comonomer content of the polymers.
[00147] Quantitative 13C {1H} NMR spectra recorded in the molten state using a Broker Advance III 500 NMR spectrometer operating at 500.13 and 125.76 MHz for 1H and 13C respectively.
All spectra were recorded using a 7 mm magic angle rotating probe head (MAS) optimized by 13C at 180 ° C using nitrogen gas for all tires. Approximately 200 mg of material were stored in a 7 mm outer diameter MAS zirconia rotor and rotated at 4 kHz. Standard single pulse excitation was employed using NOE for short recycling delays (as described in Pollard, M., Klimke, K., Graf, R., Spiess, HW, Wilhelm, M., Sperber, O., Piel, C, Kaminsky, W., Macromolecules 2004,37,813, and in Klimke, K., Parkin-son, M., Piel, C, Kaminsky, W., Spiess, HW, Wilhelm, M., Macromol. Chem. Phys. 2006,207,382) and the RS-HEPT decoupling scheme (as described in Filip, X., Tripon, C, Filip, C, J. Mag. Resn. 2005,176,239, and in Griffin, JM, Tripon , C, Samoson, A., Filip, C, and Brown, SP, Mag. Res. In Chem. 2007.45, S1, S198). A total of 1,024 (lk) transients were acquired by spectra.
[00148] Quantitative 13C {1H} NMR spectra were processed, integrated and relevant quantitative properties determined from the integrals. All chemical shifts are internally referenced to the isotactic methyl pentad (mmmm) at 21.85 ppm.
[00149] The tacticality distribution was quantified by integrating the methyl region into the 13C {1H} spectra, correcting for any signal unrelated to the stereo inserted propylene sequences (1,2), as described in Busico, V ., Cipullo, R., Prog. Polim. Sci. 2001,26,443 and in Busico, V., Cipullo, R., Monaco, G., Vacatello, M., Segre, A.L., Macromolecules 1997,30,6251.
[00150] Characteristic signs corresponding to the defects were observed (Resconi, L., Cavallo, L., Fait, A., Piemontesi, F., Chem. Rev. 2000,100,1253). The influence of region defects in the quantification of tacticality distribution was corrected by subtracting region defect integrals representative of specific integrals of the stereo sequences.
[00151] Isotacticity was determined at the triad level and reported as the percentage of mm isotactic triad with respect to all triad sequences:% mm = (mm / (mm + mr + rr)) * 100 [00152] Signs characteristics corresponding to the incorporation of 1-hexene were observed, and the 1-hexene content was calculated as the percentage in mol of 1-hexene in the polymer, H (mol%), according to: [H] = Htot / (Ptot + Htot) [00153] where: Htot = I (oB4) / 2 + I (ααB4) x2 [00154] where Ι (α B4) is the integral of the sites of α B4 at 44.1 ppm, which identifies the 1- isolated hexene incorporated into PPHPP sequences, and Ι (ααΒ4) is the integral of the ααΒ4 sites at 41.6 ppm, which identifies the 1-hexene consecutively incorporated into PPHHPP sequences.
[00155] Ptot = Integral of all CH3 areas in the methyl region with correction applied to underestimate other propene units not being responsible in this region and over-estimation due to other sites found in this region. and H (mol%) = 100x [H] [00156] which is then converted to% by weight using the correlation H (% by weight) = (100xHmol% x84.16) / (Hmol% x84.16 + (100 -Hmol%) x42.08) [00157] A statistical distribution is suggested for the relationship between the hexene content present in isolated comonomer sequences (PPHPP) and consecutive (PPHHPP): [HH] <[H] 2 [00158] Calculation of the comonomer content of the propylene copolymer (B): [00159] where [00160] w (a) is the weight fraction of the propylene copolymer (A), [00161] w (B) is the weight fraction of the propylene copolymer (B), [00162] C (A) is the comonomer content [in% by weight] measured by 13C NMR spectroscopy of the propylene copolymer (A), that is, the product of the first reactor (R1 ), [00163] C (CPP) is the comonomer content [in% by weight] measured by 13C NMR spectroscopy of the product obtained in the second reactor (R2), that is, the mixture of the propylene copolymer (a) and the copolymer propylene (B) [of the prop copolymer composition ilene (P)], [00164] C (B) is the calculated comonomer content [in% by weight] of the propylene copolymer (B) Mw, Mn, MWD
[00165] Mw / Mn / MWD are measured by Gel Permeation Chromatography (GPC) according to the following method: [00166] The average weight molecular weight (Mw), the number average molecular weight ( Mn), and the molecular weight distribution (MWD = Mw / Mn) are measured by a method based on ISO 16014-1: 2003 and ISO 16014-4: 2003. A Waters Alliance Instrument GPCV 2000, equipped with refractive index detector and online viscometer are used with 3 x TSK-gel (GMHXL-HT) columns from TosoHa-as and 1,2,4-trichlorobenzene (TCB, stabilized with 200 mg / 2,6-Di tert butyl-4-methyl-phenol) as solvent at 145 ° C and at a constant flow rate of 1 mL / min. 216.5 μΙ_ of sample solution is injected by analysis. The column set is calibrated using relative calibration with 19 strict MWD polystyrene (PS) standards in the range of 0.5 kg / mol to 11 500 kg / mol and a group of well-characterized broad polypropylene standards. All samples are prepared by dissolving 5 to 10 mg of polymer in 10 mL (at 160 ° C) of stabilized TCB (even as a mobile phase) and maintaining for 3 hours with continuous agitation before sampling on the GPC instrument. Fusion Flow Rate (MFR) [00167] Fusion flow rates are measured with a load of 2.16 kg (MFR2) at 230 ° C. The melt flow rate is that amount of polymer in grams that the ISO 1133 standardized test apparatus extrudes within 10 minutes at a temperature of 230 ° C under a load of 2.16 kg.
[00168] Calculation of MFR2 fusion flow rate (230 ° C) of the propylene copolymer (B): [00169] where [00170] w (A) is the weight fraction of the polypropylene (A), [00171] w (B) is the weight fraction of the propylene copolymer (B), [00172] MFR (A) is the melting flow rate MFR2 (230 ° C) [in g / 10min] measured according to ISO 1133 of polypropylene (A), [00173] MFR (P) is the melt flow rate MFR2 (230 ° C) [in g / 10min] measured according to ISO 1133 of the propylene (P) copolymer composition, [00174] MFR (B) is the calculated melt flow rate MFR2 (230 ° C) [in g / 10min] of the propylene copolymer (B).
Fraction soluble in frozen xylene (XCS% by weight) [00175] The fraction soluble in frozen xylene (XCS) is determined at 23 ° C according to ISO 6427.
Soluble in hexane [00176] FDA section 177.1520 [00177] 1 g of a 100 pm thick polymer film is added to 400 ml of hexane at 50 ° C for 2 hours while stirring with a reflux cooler.
[00178] After 2 hours, the mixture is immediately filtered on filter paper No. 41.
[00179] The precipitate is collected in an aluminum container and the residual hexane is evaporated in a steam bath under N2 flow. [00180] The amount of soluble in hexane is determined by the Formula ((sample by weight + crucible by weight) - (crucible by weight)) / (by sample weight) · 100.
[00181] Melting temperature Tm, crystallization temperature T „is measured with Mettler TA820 differential scanning calorimetry (DSC) in samples of 5 to 10 mg. Both crystallization and melting curves were obtained during cooling and heating sweeps from 10 ° C / min between 30 ° C and 225 ° C. Melting and crystallization temperatures were taken as the peaks of endoutroms and exoutroms.
[00182] Also, the enthalpy of fusion and crystallization (Hm and He) were measured by the DSC method according to ISO 11357-3.
[00183] Porosity: BET with N2 gas, ASTM 4641, Mi-cromeritics Tristar 3000 apparatus; sample preparation: at a temperature of 50 ° C, 6 hours in a vacuum.
[00184] Surface area: BET with N2 gas ASTM D 3663, Micromeritics Tristar 3000 apparatus: sample preparation at a temperature of 50 ° C, 6 hours in a vacuum. Tension Module: [00185] Tension modules in machine and transverse direction have been determined acc. ISO 527-3 in films with a thickness of 100 pm at a crosshead speed of 1 mm / min. Subsequently, the elongation at break in machine and transverse direction was determined acc. ISO 527-3 on the same specimens using a crosshead speed of 50 mm / min. Test speed was changed after a 0.25% strain. Specimen type 2 acc. ISO 527-3 in the form of strips with a width of 15 mm and a length of 200 mm was used.
Sealing initiation temperature (SIT); sealing and temperature (SET), sealing range: [00186] The method determines the sealing temperature range (sealing range) of polypropylene films, in particular blown films or fused films. The sealing temperature range is the temperature range, in which the films can be sealed according to the conditions given below. The lower limit (heat sealing start temperature (SIT)) is the sealing temperature at which a sealing intensity of> 3 N is obtained. The upper limit (sealing and temperature (SET)) is reached, when the films stick to the sealing device.
[00187] The sealing range is determined on a Type 3000 J&B Universal Sealing Machine with a 100 pm thick film with the following additional parameters: Specimen width: 25.4 mm Seal pressure: 0.1 N / mm2 Sealing time: 0.1 s Cooling time: 99 s Peeling speed: 10 mm / s Start temperature: 80 ° C
Finishing temperature: 150 ° C
Increments: 10 ° C specimen is sealed A to A at each sealbar temperature and the seal strength (strength) is determined at each step.
[00188] The temperature is determined at which the seal intensity reaches 3 N.
Heat bond strength: [00189] The heat bond strength is determined on a J&B Heat Adhesion Analyzer with a 100 pm thick film with the following additional parameters: Specimen width: 25.4 mm Sealing pressure : 0.3 N / mm2 Sealing Time: 0.5 s Cooling Time: 99 s Peeling Speed: 200 mm / s Start temperature: 90 ° C End temperature: 140 ° C Increments: 10 ° C
[00190] The maximum heat bond strength, that is, the maximum of a force / temperature diagram is determined and reported. B. Examples [00191] The polymers in Table 1 were produced in a Borstar PP pilot plant in a two-stage polymerization process starting in a loop-phase reactor followed by polymerization in a gas-phase reactor, varying the molecular weight as well as the ethylene and hexene content by appropriate hydrogen and comonomer feeds. The catalyst used in the polymerization process was a metallocene catalyst as described in Example 1 of EP 1 741 725 Al.
Table 1: Preparation of examples Handle defines polypropylene (A) GPR defines propylene copolymer (B) Final defines composition of propylene copolymer (P) C6 is 1-hexene content C2 is ethylene content Table 2: Properties of the examples TM (MD) is the tension module in machine direction TM (TD) is the tension module in transverse direction SIT is the heat seal start temperature SET is the heat seal end temperature SET - SIT is the difference of SET and SIT ST is the sealing temperature HTF is the heat bond strength TPE is the total penetration energy

权利要求:
Claims (15)
[1]
1. Composition of propylene copolymer (P), characterized by the fact that it comprises: (a) a propylene copolymer (a) having a comonomer content of at least 1.0% by weight, the comonomers are C5 to C12 α -olefins, and (b) a propylene copolymer (B) with a comonomer content of 4.0 to 20.0% by weight, the comonomers are C5 to C12 α-olefins, with (i) the content of comonomer in the propylene copolymer (a) is lower compared to the comonomer content in the propylene-copolymer (B), (ii) the propylene copolymer composition (P) has a comonomer content of 3.5 to 6.5 % by weight, the comonomers are C5 to C12 α-olefins, (iii) the weight ratio of the propylene copolymer (a) to the propylene copolymer (B) is in the range 20/80 to 80/20, and (iv ) said propylene copolymer composition (P) has a crystallization temperature (Tc), measured according to ISO 11357-3, in the range of 88 to 110 ° C.
[2]
2. Propylene (P) copolymer composition, according to claim 1, characterized by the fact that with (P) / with (a) it is in the range of 1.0 to 10.0, with (A) is the comonomer content of the propylene copolymer (a) given in percentage by weight [% by weight], and with (P) is the comonomer content in the propylene cup-polymer composition (P) given in percentage by weight [ % by weight].
[3]
3. Propylene (P) copolymer composition, according to claim 1 or 2, characterized by the fact that it satisfies Equation (I) Tm - SIT> 22 ° C (I) in which Tm is the melting temperature given in centigrade [° C] of the propylene copolymer (P), SIT is the heat sealing start temperature (SIT) given in centigrade [° C] of the propylene copolymer (P).
[4]
Propylene (P) copolymer composition according to any one of claims 1 to 3, characterized by the fact that it has a heat sealing initiation temperature (SIT) of not more than 120 ° C.
[5]
5. Propylene (P) copolymer composition according to any one of claims 1 to 4, characterized by the fact that it presents: (a) an MFR2 melting flow rate (230 ° C), measured according to ISO 1133, in the range of 2.0 to 50.0 g / 10min, and / or (b) a melting temperature Tm of at least 125 ° C, and / or (c) a soluble xylene content (XCS), determined at 23 ° C according to ISO 6427, less than 20.0% by weight.
[6]
6. Propylene (P) copolymer composition according to any one of claims 1 to 5, characterized by the fact that the comonomers are selected from the group of C5 α-olefin, C6 α-olefin, C7 α-olefin, C8 α-olefin, C9 α-olefin, C10 α-olefin, C11 α-olefin and C12 α-olefin, preferably the propylene copolymer composition (P) is a propylene 1-hexene copolymer.
[7]
7. Propylene (P) copolymer composition according to any one of claims 1 to 6, characterized in that it has a molecular weight distribution (MWD) measured by gel permeation chromatography (GPC) not exceeding 4 , 0.
[8]
8. Propylene (P) copolymer composition according to any one of claims 1 to 7, characterized by the fact that the MFR (A) / MFR (P) ratio is in the range of 0.25 to 10.0 being that MFR (A) is the melting flow rate MFR2 (230 ° C) [g / 10min], measured according to ISO 1133, of the propyl-no copolymer (A), MFR (P) is the flow rate melting point MFR2 (230 ° C) [g / 10min], measured according to ISO 1133, of the propylene (P) glass-polymer composition.
[9]
9. Propylene (P) copolymer composition according to any one of claims 1 to 8, characterized by the fact that the propylene copolymer (a) has: (a) a comonomer content in the range of 1.0 to 4.0% by weight, and / or (b) an MFR2 melting flow rate (230 ° C), measured according to ISO 1133, of at least 0.5 g / 10min, and / or (c) a soluble xylene content (XCS) less than 2.0% by weight.
[10]
10. Propylene copolymer (P) composition according to any one of claims 1 to 9, characterized in that the propylene copolymer (a) and / or propylene copolymer (B) preferably comprises (m) comprises (m) only 1-hexene as a comonomer.
[11]
11. Process for the preparation of a propylene (P) copolymer composition, as defined in any one of claims 1 to 10, characterized by the fact that it is a sequential polymerization process comprising at least two reactors connected in series , and said process comprises the steps of: (A) polymerization in a first reactor (R-1) being a suspension reactor (SR), preferably a loop reactor (LR), propylene and at least one C5 a C12 α-olefin, preferably 1-hexene, obtaining a propylene copolymer (a) as defined in any one of claims 1,2 and 8 to 10, (B) transferring said propylene copolymer (A) and non-comonomers reacted from the first reactor in a second reactor (R-2) being a gas phase reactor (GPR-1), (C) feeding to said second reactor (R-2) of propylene and at least one C4 to C10 α- olefin, (D) polymerization in said second reactor (R-2) and in the presence of said of the first propylene copolymer (a) propylene and at least one C5 to C12 α-olefin obtaining a propylene copolymer (B) as defined in claim 1 or 10, said propylene copolymer (a) and said propylene copolymer (B) form the propylene copolymer composition (P), as defined in any one of claims 1 to 8, and even in the first reactor (R-1) and second reactor (R-2) the polymerization occurs at presence of a solid catalyst system (SCS), said solid catalyst system (SCS) comprises: (i) a transition metal compound of Formula (I) Rn (Cp ') 2MX2 (I) in which "M" is zirconium (Zr) or hafnium (Hf), each "X '" is independently a modern anionic σ-ligand, each "Cp" is an organic ligand of the cyclopentadienyl type independently selected from the group consisting of substituted cyclopentadienyl, substituted indenyl , substituted tetrahydroindenyl, and substituted fluorenyl and not -substituted, said organic linkers coordinate with the transition metal (M), "R" is a bivalent bridge group linking said organic linkers (Cp '), "n" is 1 or 2, preferably 1, and ( ii) optionally, a cocatalyst (Co) comprising an element (E) of group 13 of the periodic table (IUPAC), preferably a co-catalyst (Co) comprising an Al compound.
[12]
12. Process according to claim 11, characterized by the fact that the transition metal compound of Formula (I) is an organo-zirconium compound of Formula (II) in which M is zirconium (Zr) or hafnium ( Hf), preferably zirconium (Zr), X are binders with a σ-bond to the metal "M", R1 are equal to or different from each other, and are selected from the group consisting of C1 to C20 linear saturated alkyl, C1 to C20 linear unsaturated alkyl, C1-C20 branched saturated alkyl, C1 to C20 branched unsaturated alkyl, C3 to C20 cycloalkyl, C6 to C20 aryl, C7 to C20 alkylaryl, and C7 to C20 arylalkyl, optionally containing one or more hetero atoms from groups 14 to 16 of the periodic table (IUPAC), R2 to R6 are equal to or different from each other and are selected from the group consisting of hydrogen, C1-C20 linear saturated alkyl, C1-C20 linear unsaturated alkyl, C1-C20 branched saturated alkyl, C1 -C20 branched unsaturated alkyl, C3-C20 cycloalkyl, C6-C20 aryl, C7-C20 alkylaryl, and C7-C20 arylalkyl, optionally containing one or more heteroatoms from groups 14 to 16 of the periodic table (IUPAC), R7 and R8 are equal to or different from each other and selected from the group consisting of hydrogen, C1 to C20 linear saturated alkyl, C1 to C20 linear unsaturated alkyl, C1 to C20 branched saturated alkyl, C1 to C20 branched unsaturated alkyl, C3 to C20 cycloalkyl, C6 to C20 aryl, C7 to C20 alkylaryl, C7 to C20 arylalkyl, optionally containing one or more hetero atoms from groups 14 to 16 of the periodic table (IUPAC), SiR103, GeR103, OR10, SR10 and NR102, where R10 is selected from the group consisting of C1-C20 linear saturated alkyl, C1 to C20 linear unsaturated alkyl , C1 to C20 branched saturated alkyl, C1 to C20 unsaturated branched alkyl, C3 to C20 cycloalkyl, C6 to C20 aryl, C7 to C20 alkylaryl, and C7 to C20 arylalkyl, optionally containing one or more hetero atoms from groups 14 to 16 of the periodic table (IUPAC), and / or R7 and R8 being optionally part of a C4 to C20 carbon ring system together with the indenyl carbons to which they are attached, preferably a C5 ring, optionally a carbon atom can be replaced by a nitrogen, sulfur or oxygen atom , R9 are the same or different from each other and are selected from the group consisting of hydrogen, C1 to C20 linear saturated alkyl, C1 to C20 linear unsaturated alkyl, C1 to C20 branched saturated alkyl, C1 to C20 branched unsaturated alkyl, C3 to C20 cycloalkyl, C6 to C20 aryl, C7 to C20 alkylaryl, C7 to C20 arylalkyl, OR10, and SR10, where R10 is defined as before, L is a bivalent group bridging with the two indenyl ligands, preferably being a unit of C2R114 or a SiR112 or GeR112, wherein, R11 is selected from the group consisting of H, C1 to C20 linear saturated alkyl, C1 to C20 linear unsaturated alkyl, C1 to C20 branched saturated alkyl, C1 to C20 branched unsaturated alkyl , C3 to C20 cycloalkyl, C6 to C20 aryl, C7 to C20 alkylaryl or C7 to C20 arylalkyl, optionally containing one or more heteroatoms from groups 14 to 16 of the periodic table (IUPAC).
[13]
13. Propylene (P) copolymer composition according to any one of claims 1 to 10, characterized by the fact that it was obtained by a process, as defined in any of claims 11 or 12.
[14]
14. Film, preferably biaxially oriented film or fused film, characterized in that it comprises a propylene (P) copolymer composition, as defined in any of claims 1 to 10 and 13.
[15]
15. Extrusion-coated substrate, characterized in that it comprises a coating, said coating comprising a propylene (P) copolymer composition, as defined in any of claims 1 to 10 and 13.

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法律状态:
2018-04-10| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|

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2019-09-10| B06U| Preliminary requirement: requests with searches performed by other patent offices: procedure suspended [chapter 6.21 patent gazette]|

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2020-01-21| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|

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2020-03-10| B16A| Patent or certificate of addition of invention granted [chapter 16.1 patent gazette]|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 18/04/2011, OBSERVADAS AS CONDICOES LEGAIS. |

优先权:

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申请号 | 申请日 | 专利标题

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EP10160631|2010-04-21|

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EP10160631.7|2010-04-21|

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PCT/EP2011/056181|WO2011131639A1|2010-04-21|2011-04-18|Propylene/1-hexene copolymer composition with low sealing temperature|

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