composition of polypropylene (pp-c), fiber and network fused by blow, its preparation process, artic

专利摘要:
fused blown fibers of polypropylene compositions the present invention relates to a polypropylene composition comprising a polypropylene having a melt flow rate m-rf ~ 2 ~ (230 <198> c) of at least 450g / 10 min. and a molecular weight distribution (mwd) of no more than 3.5, a polypropylene with a melting flow rate mfr ~ 2 ~ (230 <198> c) equal to or below 20g / 10 min., the composition has a melt flow rate mrf ~ 2 ~ (230 <198> c) of at least 200g / 10 min.
公开号:BR112012011404B1
申请号:R112012011404
申请日:2010-11-11
公开日:2020-04-14
发明作者:Tynys Antii；Fiebig Joachim；Perrillat-Collomb Pascal
申请人:Borealis Ag；
IPC主号:

专利说明:

[0001] The present invention relates to a new composition of polypropylene, fibers melted by blowing comprising said polypropylene composition as well as its use to improve the elongation force in the processing of fibers melted by blow.
[0002] A blow-fused network, being a non-woven structure consisting of blow-fused fibers, is typically produced in a one-step process in which high-speed air blows a molten thermoplastic resin from one end of the die of the extruder on a conveyor or absorption screen to form the fine defibrated self-bonding network. In various end-use applications, nonwovens consisting of fibers with a small medium fiber diameter are required. Therefore, the focus has been on the development of new polymeric resins that can be used in the blown fusion process to produce finer fibers under industrially viable production conditions. In particular, ideal filtration media have an average fiber diameter of less than 1 pm. In the blown fusion process, the attenuation of the fiber is limited by the flywheel formation. In the flywheel formation, the polymer fiber is broken during elongation between the matrix and the mat, and the broken filaments are released from the mesh. In order to reach the finer fibers, the polymeric resin has to tolerate larger volumes of air without breaking the filament which should result in a thinner average fiber diameter. Especially in the case of the metallocene polypropylene resin produced by the reactor, the average diameter of the thinnest achievable fiber was relatively high, although these polymers offer significant advantages in terms of purity and absence of peroxide residues.
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2/50 [0003] In US 2005 / 0.182.198-A1 a polymeric composition is disclosed comprising 70 to 90% by weight of a polypropylene with melt flow rate MFR2 (230 ° C) from 30 to 400 g / 10 min. and from 30 to 10% by weight of a polypropylene with an MFR2 melt index (230 ° C) of 0.1 to 30 g / 10 min. However, no information is provided on how the nonwoven preparation can be economically improved.
[0004] In US 2005 / 0.165.173-A1 a polymeric composition is disclosed which comprises a first polypropylene with a melt index MFR2 (230 ° C) of 5 to 25 g / 10 min. and melting temperature of 110 to 135 ° C and a second polypropylene with an MFR2 melt index (230 ° C) of 25 to 50 g / 10 min. and melting temperature of 135 to 165 ° C. There is no indication as to how very fine fibers can be obtained without breaking the filament.
[0005] Thus, the aim of the present invention is to provide a polypropylene composition that allows to produce very fine blow-melted fibers with the risk of breaking the filament.
[0006] The finding of the present invention is that very thin fibers are obtainable, in the case of polypropylene resists the high elongation force. Another finding of the present invention is that the polypropylene composition must comprise a polypropylene with an MFR2 melt index (230 ° C) above 400 g / 10 min. and in addition another polypropylene with a very low melt index MFR2 (230 ° C), for example, less than 25 g / 10 min. Preferably, the low melt flow rate polypropylene MFR2 (230 ° C) has a hardening behavior under tension, such as 0 polypropylene with high melt strength.
[0007] Consequently, the present invention is directed to a polypropylene (PP-C) composition comprising (a) a polypropylene (A) having
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3/50 (i) an MFR2 melt index (230 ° C) measured according to ISO 1133 of at least 450 g / 10 min. and (ii) a molecular weight distribution (MWD) measured according to ISO 16014 not exceeding 3.5, (b) a polypropylene (B) showing an MFR2 fluidity index (230 ° C) measured according to ISO 1133 of 20 g / 10 min or less, and (c) optionally a polypropylene (C) having an MFR2 fluidity index (230 ° C) measured according to ISO 1133 of at least 2 times the rate melt flow rate MFR2 of polypropylene (B) and at least 2 times lower than the melt flow rate MFR2 of polypropylene (A).
[0008] where the composition (PP-C) has a flow rate MFR2 (230 ° C) measured according to ISO 1133 of at least 200 g / 10 min.
[0009] Preferably the polypropylene (PP-C) composition comprises polypropylene (A), 0 polypropylene (B) and optionally 0 polypropylene (C) as the only polymeric components. Consequently, in a preferred embodiment the composition may contain additives, but without other additional polymers such as those mentioned in this paragraph and with other details defined below.
[00010] It has surprisingly been found that such a polypropylene composition (PP-C) has superior properties over known polypropylene compositions, in particular those used for the processing of blow-melted fibers. The polypropylene (PP-C) composition of the present invention allows in particular to obtain a maximum applicable air volume during fiber processing compared to other polypropylenes, in particular to other metallocene-produced polypropylenes. So with the polypropylene composition of the invention (PP-C) fibers very
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4/50 fines are produced, which is not possible with the known polypropylenes.
[00011] In what follows the polypropylene composition of the invention (PP-C) and its individual components are described in more detail.
[00012] Especially good results are achievable in the case of the polypropylene composition which comprises a minimum amount of polypropylene (B). Previously small amounts of polypropylene (B) have been found to significantly improve the elongation strength of the polypropylene (PP-C) composition during the processing of melt blown fibers. Consequently, it is preferable that the polypropylene composition comprises at least 0.5% by weight of the polypropylene (B). Another finding is that at a certain level of polypropylene (B) the stretching performance can no longer be improved. Thus, it is observed that the amount of polypropylene within the polypropylene (PP-C) composition does not exceed 30.0% by weight. Consequently, it is particularly preferable that the polypropylene (PP-C) composition of the present invention comprises (a) 75.0 to 99.5% by weight, more preferably from 80.0 to 95.0% by weight, as of 82.0 to 93.0% by weight, of polypropylene (A), (b) 0.5 to 25.0% by weight, more preferably from 1.0 to 20.0% by weight, such as 1.5 to 12.0% by weight of polypropylene (B), and (c) 0 to 15% by weight, more preferably from 0.5 to 10.0% by weight, such as from 1.0 to 8.0% by weight weight, polypropylene (C), based on the total composition, preferably based on the polypropylenes present in the composition, more preferably based on polypropylene (A), polypropylene (B) and polypropylene
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5/50 (C) together.
[00013] Furthermore, it is preferable that polypropylene (A) and polypropylene (C) are unbranched, i.e., that the polymers have a g 'branching index of 1.0. The g 'branch index is described below in greater detail.
[00014] Thus, the polypropylene (PP-C) composition of the present invention can comprise other components. However, it is preferable that the polypropylene composition (PP-C) comprises as polymeric components only the polypropylenes (A), (B) and optionally (C) as defined in the present invention. Consequently, the amounts of the polypropylenes (A), (B) and optionally (C) cannot result in 100% by weight based on the total polypropylene composition (PP-C). Thus, the remainder up to 100.0% by weight can be made by other additives known in the art. However, this remaining part should not be more than 3.0% by weight, as well as not more than 1.0% by weight within the total composition. For example, the polypropylene composition of the invention (PP-C) can additionally comprise small amounts of antioxidants, stabilizers, fillers, dyes, nucleating agents and antistatic agents. In general, these are incorporated during the granulation of the powdery product obtained in the polymerization. Consequently, the polypropylenes (A), (B) and optionally (C) constitute at least 97% by weight, more preferably at least 99% by weight, of the total polypropylene composition (PP-C). Primary and secondary antioxidants include, for example, hindered phenols, hindered amines, and phosphates. Nucleating agents include, for example, sodium benzoate, sorbitol derivatives such as bis- (3,4dimethylbenzylidene) sorbitol and nonitol derivatives such as 1,2,3-trideoxy4,6: 5,7-bis-O [(4 -propylphenyl) methylene] -nonitol. Other additives such as dispersants and antistatic agents such as glycerol monostearate
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6/50 can also be included. Glidants include, for example, oleamide and erucamide. Catalyst deactivators are also commonly used, for example, calcium stearate, hydrotalcite, and calcium oxide, and / or other acid neutralizers known in the art.
[00015] Another mandatory requirement of the propylene composition (PP-C) is its very high melt flow rate, which differs from other polymers used, for example, in the nonwoven technique to produce fibers. The melt flow rate depends mainly on the average molecular weight. This is due to the fact that long molecules give the material a tendency to flow less than short molecules. An increase in molecular weight means a decrease in the MFR value. The melt flow rate (MFR) is measured in g / 10 min. of the polymer discharged through a mold defined under specific temperature and pressure conditions and the measure of the viscosity of the polymer which, in turn, for each type of polymer is influenced mainly by its molecular weight, but also by its degree of branching. The melt flow rate measured under a load of 2.16 kg at 230 ° C (ISO 1133) is indicated as MFR2 (230 ° C). Consequently, it is preferable that in the present invention the polypropylene (PP-C) composition has an MFR2 melt index (230 ° C) of at least 200 g / 10 min., More preferably at least 250 g / 10 min., even more preferably in the range of 200 to 3000 g / 10 min., even more preferably in the range of 250 to 1000 g / 10 min.
[00016] Furthermore, it is observed that the polypropylene (PP-C) composition according to this invention has a melting temperature Tm measured according to ISO 11357-3 of at least 149 ° C, more preferably at least 151 ° C, even more preferably at least 153 ° C. Consequently, the melting temperature Tm preferably ranges from 149 to 164 ° C, more preferably it varies from
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7/50
151 to 162 ° C.
[00017] In addition, the polypropylene (PP-C) composition can be further defined by the gel content. The gel content is a good indicator for the chemical modification of the polypropylene composition or its components. Consequently, the present invention is characterized by the relatively moderate gel content, that is, not more than 1.00% by weight, even more preferable not more than 0.80% by weight, even more preferable not more than 0.50% by weight, determined as the relative amount of boiling xylene-insoluble polymer (hot insoluble xylene fraction, XHI). On the other hand, the polypropylene (PP-C) composition achieves especially good results when it comprises a certain amount of polypropylene with high melt resistance (HMS-PP) as polypropylene (B). Consequently the amount of gel content in the polypropylene (PP-C) composition is preferably more than 0.10% by weight, more preferably at least 0.20% by weight. Thus, a preferred range for the gel content of the polypropylene composition is 0.05 to 0.80% by weight, as from 0.10 to 0.70% by weight, more preferable from 0.20 to 0.60 % by weight.
[00018] Furthermore, it is observed that the polypropylene (PP-C) composition is free of any elastomeric polymer component, such as an ethylene propylene rubber. In other words, the polypropylene (PP-C) composition should not be a heterophasic polypropylene composition, that is, a system consisting of a polypropylene matrix in which an elastomeric phase is dispersed. Such systems are characterized by a very high cold soluble xylene content (XCS). Consequently, the polypropylene composition present differs from such a heterophasic system in that it has a very low cold soluble xylene content (XCS). Therefore, the polypropylene composition preferably has a cold soluble xylene fraction (XCS) of no su
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8/50 greater than 12.0% by weight, more preferably not more than 10.0% by weight, even more preferably not more than 9.0% by weight, such as not more than 8.5% by weight .
[00019] The composition of polypropylene (PP-C) is in particular still defined by its individual components.
[00020] A mandatory requirement is the presence of a polypropylene with a very high fluidity index MFR2 (230 ° C). Consequently, the polypropylene (PP-C) composition will comprise a polypropylene (A) having an MFR2 melt index (230 ° C) measured according to ISO 1133 of at least 450 g / 10 min., More preferably at least 600 g / 10 min., Even more preferably at least 800 g / 10 min., Even more preferably in the range 600 to 3000 g / 10 min., Even more preferably in the range 750 to 2000 g / 10 min., even more preferably in the range of 850 to 1500 g / 10 min.
[00021] Polypropylene (A) is preferably produced in the presence of a single site catalyst, for example, a metallocene catalyst. Thus, in a preferred embodiment, polypropylene is characterized by a relatively limited molecular weight distribution (MWD). Consequently, polypropylene (A) has a molecular weight distribution (MWD) measured by size exclusion chromatography (SEC) according to ISO 16014 of not more than 3.5, more preferably not more than 3.0, yet more preferably not more than 2.8, even more preferably in the range of 1.3 to 3.5, even more preferably in the range of 1.5 to 2.8.
[00022] The weighted average molecular weight (Mw) is the first moment of a plane of the polymer weight in each molecular weight range against the molecular weight. The weighted average molecular weight (Mw) is very sensitive to changes in the number of large molecules in a given sample of a polymer. Thus, it is preferable that
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9/50 the weighted average molecular weight (Mw) measured by SEC according to ISO 16014 of polypropylene (A) is less than 85000 g / mol, more preferably less than 90000 g / mol, even more preferably less than 80000 g / mol mol. On the other hand, the weighted average molecular weight (Mw) of polypropylene (A) should not be too low. Thus, it is especially preferable that the weighted average molecular weight (Mw) measured according to ISO 16014 of polypropylene (A) is in the range of 20000 g / mol to 95000 g / mol, more preferably in the range of 30000 to 90000 g / mol mol, even more preferably in the range of 40000 to 85000 g / mol.
[00023] Another characteristic of polypropylene (A) is its low cold soluble xylene content (XCS). Low amounts of soluble xylene are also an indicator that polypropylene (A) was obtained from a polymerization process in which a single site catalyst was employed. Thus it is preferable that the cold soluble xylene content (XCS) measured in accordance with ISO 6427 (23 ° C) of polypropylene (A) is not more than 2.5% by weight, more preferably not more than 2.0 % by weight, even more preferably not more than 1.5% by weight, even more preferably not more than 1.0% by weight, even more preferably not more than 0.8% by weight, such as 0.3 to 1 , 5% by weight or 0.3 to 1.0% by weight.
[00024] Polypropylene (A) can be a propylene homopolymer (H-A) and / or a random propylene copolymer (R-A). Preferably, polypropylene (A) is a propylene homopolymer (H-PP).
[00025] The term propylene homopolymer as used throughout the present invention refers to a polypropylene that consists substantially, that is, of more than 99.5% by weight, even more preferably at least 99.7% by weight , as at least
99.8% by weight of propylene units. In a preferred embodiment only the propylene units in the homopolymer of
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10/50 propylene is detectable. The comonomer content can be determined with FT infrared spectroscopy, as described below in the examples.
[00026] The propylene homopolymer (H-A) is preferably an isotactic propylene homopolymer. In this way, it is observed that the polypropylene (HA) matrix has a quite high isotactic pentavalent concentration, that is, greater than 90 mol%, more preferably greater than 92 mol%, even more preferably greater than 93 mol% and even more preferably greater than 95 mol%, such as greater than 97 mol%.
[00027] Preferably the propylene homopolymer (H-A) has a melting temperature Tm measured according to ISO 11357-3 of at least 150 ° C, more preferably of at least 152 ° C, as of at least 153 ° C. Consequently, the melting temperature ranges preferably from 150 to 164 ° C, more preferably ranges from 151 to 158 ° C.
[00028] The random propylene (RA) copolymer preferably comprises, preferably consists of, units derived from (i) propylene and (ii) ethylene and / or at least one C4 to C20 α-olefin, preferably at least one α -olefin selected from the group consisting of ethylene, 1-butene, 1-pentene, 1-hexene and 1-octene, more preferably ethylene and / or 1-butene, even more preferably ethylene. [00029] Consequently, the random propylene (RA) copolymer can comprise units derived from propylene, ethylene and optionally at least another C4 to C10 α-olefin. In a specific aspect of the present invention the random propylene copolymer (RA) comprises units derived from propylene, ethylene and optionally at least one other α-olefin selected from the group consisting of α-olefin C4, α-olefin C5, α-olefin C6, α- olefin C7, α-olefin Cs, α
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11/50 C9 olefin and C10 α-olefin. More preferably, the random propylene (RA) copolymer comprises units derived from propylene, ethylene, and optionally at least one other α-olefin selected from the group consisting of 1-butene, 1-pentene, 1-hexene, 1-heptene, 1octene , 1-nonene and 1-decene, where 1-butene and 1-hexene, are preferred. It is particularly preferable that the random propylene copolymer (R-A) consists of units derived from propylene and ethylene. Preferably, the propylene derivative units constitute the main part of the random propylene copolymer (RA), i.e., at least 95.0% by weight, preferably at least 97.0% by weight, more preferably at least 98 .0% by weight, even more preferably from 95.0 to 99.5% by weight, even more preferably from 97.0 to 99.5% by weight, even more preferably from 98.0 to 99.2% by weight . The number of units derived from C2 to C20 α-olefins other than propylene in the random propylene (RA) copolymer is in the range of 0.5 to 5.0% by weight, more preferably from 0.5 to 3.0% by weight. weight, even more preferably from 0.8 to 2.0% by weight. It is noted in particular that the amount of ethylene in the random propylene (RA) copolymer, particularly in the case the random propylene (RA) copolymer comprises only the units derived from propylene and ethylene, is in the range of 0.5 to 5, 0% by weight, preferably from 0.8 to 2.0% by weight.
[00030] Preferably the random propylene copolymer (R-A) is isotactic. Thus, it is observed that the random propylene copolymer (R-A) has a very high pentavalent concentration, i.e., greater than 95 mol%, more preferably greater than 97 mol%, even more preferably greater than 98 mol%.
[00031] In addition, units derived from C2 to C20 α-olefins other than propylene within the random propylene (RA) copolymer are randomly distributed. Randomness indicates the amount
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12/50 of isolated comonomer units, that is, those that have no other comonomer units in proximity, compared to the total amount of comonomers in the polymer chain. In a preferred embodiment, the randomness of the random propylene copolymer (R-A) is at least 30%, more preferably at least 50%, even more preferably at least 60%, and even more preferably at least 65%.
[00032] Additionally, it is observed that the random propylene copolymer (RA) has a melting temperature Tm measured according to ISO 11357-3 of at least 140 ° C, preferably at least 145 ° C, more preferably at least 150 ° C. Consequently, the melting temperature preferably ranges from 140 to 164 ° C, more preferably it ranges from 150 to 160 ° C.
[00033] One possibility to obtain polypropylene having such high melt flow rates and a relatively limited molecular weight distribution (MWD) as indicated above is viscoreduction. However, in the present case it is preferable to produce polypropylene (A) without viscorreduction, that is, using a single site catalyst in the polymerization of polypropylene (A). An advantage of such a polymeric material is that no peroxide is required for degradation. The exact description of how polypropylene can be obtained is given below.
[00034] As another mandatory component within the polypropylene (PP-C) composition, polypropylene (B) must be present. Contrary to polypropylene (A), polypropylene (B) must have a very low fluidity index MFR2 (230 ° C). Consequently, it is observed that the polypropylene (B) has a melt index MFR2 (230 ° C) measured according to ISO 1133 equal to or less than 20 g / 0 min., More preferably equal to or less than 15 g / 10 min ., even more preferably equal to or less than 10 g / 10 min., even more preferably in the
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13/50 range of 1.0 to 20.0 g / 10 min., Even more preferably in the range of 2.0 to 15.0 g / 10 min., As in the range of 3.0 to 10.0 g / 10 min. 10 min ..
[00035] Especially good results are achievable in the case where the melt flow rate ratio of polypropylene (A) and polypropylene (B) [MFR2 (A) / MFR2 (B)] is in the range of 100 to 300, such as 110 to 280, where MFR2 melt flow rates (230 ° C) are measured according to ISO 1133.
[00036] Polypropylene (B) is preferably a propylene homopolymer (H-PP) or a polypropylene with high melt resistance (HMS-PP), the latter being especially preferred.
[00037] In the case the polypropylene is a propylene homopolymer (H-PP), said propylene homopolymer (H-PP) preferably has a cold soluble content of xylene (XCS) measured according to ISO 6427 (23 ° C ) equal to or greater than 0.5% by weight, even more preferably in the range of 0.5 to 3.5% by weight, such as 0.6 to 3.0% by weight.
[00038] So different from polypropylene (A), polypropylene (B) is, that is, the propylene homopolymer (H-PP) and the polypropylene with high melt resistance (HMS-PP), which can be produced, preferably produced in presence of a Ziegler-Natta catalyst.
[00039] Consequently, it is in particular observed that the propylene homopolymer (H-PP) has <1.2> royal defects of not more than 0.4 mol%, more preferably of not more than 0.2 mol%, not more than 0.1 mol%, determined by ¹³ C-NMR. [00040] The exact process for obtaining the propylene homopolymer (H-PP) is provided below.
[00041] As mentioned above, in a preferred embodiment, polypropylene (B) is a polypropylene with high melt resistance (HMS-PP).
[00042] Such types of polymer are characterized by a certain degree
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14/50 branching. Possible high-melt polypropylenes (HMS-PP) are so-called Y / H-polypropylenes and, for example, described in EP 0 787 750, that is, isolated branched polypropylene types (Y polypropylenes having a single-stranded main chain long side chain and a architecture that looks like a Y) and types of polypropylene in which the polymeric chains are coupled with a bridging group (an architecture that looks like an H). Such polypropylenes are characterized by very high melt resistance. A parameter of the degree of branching is the branching index g '. The g 'branch index correlates with the number of branches of a polymer. The branching index g 'is defined as g' = [IV] br / [IV] lin where g 'is the branching index, [IV] br is the intrinsic viscosity of the branched polypropylene and [IV] lin is the viscosity intrinsic linear polypropylene having the same weighted average molecular weight (within a range of ± 10%) as branched polypropylene. Thus, a low g 'value is an indicator for a high branched polymer. In other words, if the value of g 'decreases, the branching of the polypropylene increases. Reference is made in this context to B.H. Zimm and W.H. Stockmeyer, J. Chem. Phys. 17, 1301 (1949). This document is included here by reference. Thus it is preferable that the g 'branching index of high melt-resistant polypropylene (HMS-PP) is less than 1.0, more preferably less than or equal to 0.9, such as less than 0.8. In another preferred embodiment, the g 'branching index of the high melt resistance polypropylene (HMS-PP) should preferably be less than 0.75.
[00043] The high degree of branching of polypropylene with high melt resistance (HMS-PP) also contributes to its melt resistance. Consequently, it is preferable that the polypropylene with high melt resistance (HMS-PP) is further characterized by
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15/50 stress-hardening behavior with a drawing force Fmax of at least 7.0 cN and a drawing speed Vmax of at least 200 mm / s, more preferably due to a tensioning behavior with a drawing force Fmax of at least 20.0 cN and a drawing speed Vmax of at least 250 mm / s, even more preferably by a tensile hardening behavior with a drawing force Fmax of at least 10.0 cN and a drawing speed Vmax at least 245 mm / s.
[00044] Such a high melt resistance polypropylene (HMS-PP) is preferably obtained by modifying, i.e., chemical modifying, a polypropylene. Such a modification is necessary to achieve the branching structure and / or the tension-hardening phenomena of polypropylene with high melt resistance (HMS-PP). Such a modification also has an influence on the gel content of polypropylene with high melt resistance (HMS-PP). Consequently, it is justified to define polypropylene with high melt resistance (HMS-PP) later and / or alternatively by its gel content. Thus, it is observed that polypropylene with high melt resistance (HMS-PP) is characterized by a relatively moderate gel content, that is, less than 1.0% by weight, even more preferable not more than 0.80% in even more preferable weight not exceeding 0.50% by weight, determined as the relative amount of boiling xylene insoluble polymer (xylene hot insoluble fraction, XHI). On the other hand, polypropylene with high melt resistance (HMS-PP) can have a certain degree of branching and, therefore, a certain amount of gel content, that is, at least 0.15% by weight, more preferably of at least 0.27% by weight. Thus, a preferred range for the gel content of polypropylene with high melt resistance (HMS-PP) is 0.05 to 0.90% by weight, more preferable from 0.26 to 0.8% by weight.
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16/50 [00045] Additionally, it is preferable that the polypropylene with high melt resistance (HMS-PP) has a flow rate MFR2 (230 ° C) measured according to ISO 1133 in a range of 1.0 to 20, 0 g / 10 min., More preferably in a range of 2.0 to 15.0 g / 10 min., Even more preferably in a range of 3.0 to 10.0 g / 10 min. [00046] preferably, high melt-resistant polypropylene (HMS-PP) has a density measured according to ISO 1183-187 of at least 850 kg / m ³ , more preferably of at least 875 kg / m ³ and most preferably of at least 900 kg / m ³ .
[00047] Furthermore, preferably, polypropylene with high melt resistance (HMS-PP) has a density measured according to ISO 1183-187 of not more than 950 kg / m ³ , more preferably not more than 925 kg / m ³ and the most preferable of not more than 910 kg / m ³ .
[00048] Preferably, the high melt resistance polypropylene (HMS-PP) has a melting point of at least 140 ° C, more preferably at least 150 ° C and most preferably at least 160 ° C.
[00049] As mentioned above, the high melt resistance polypropylene (HMS-PP) is preferably a modified polypropylene. Consequently, polypropylene with high melt resistance (HMS-PP) can be further defined by the shape obtained. Thus, polypropylene with high melt resistance (HMS-PP) is preferably the result of treating an unmodified polypropylene (D) with thermal decomposition radical forming agents and / or with ionizing radiation. However, in such a case a high risk exists that polypropylene (D) is degraded, which is harmful. Thus, it is preferable that the modification be carried out by using a bifunctional unsaturated monomer and / or a low molecular weight multifunctional unsaturated polymer as the connecting units with ponPetition 870190135536, from 12/18/2019, p. 19/63
17/50 te chemically bonded. A suitable method for obtaining high melt strength polypropylene (HMS-PP) is, for example, disclosed in EP 0 787 750, EP 0 879 830 A1 and EP 0 890 612 A2. All documents are included here by reference. Thus, the amount of peroxide is preferably in the range of 0.05 to 3.00% by weight based on the unmodified polypropylene (D).
[00050] Consequently, in a preferred embodiment, the high melt resistance polypropylene (HMS-PP) comprises units derived from (i) propylene and (ii) bifunctional unsaturated monomer and / or multifunctional unsaturated low molecular weight polymer.
[00051] Bifunctional unsaturated or multifunctional unsaturated as used above means preferably in the presence of two or more non-aromatic double bonds, as in, for example, divinylbenzene or cyclopentadiene or polybutadiene. Only such bi- or multifunctional unsaturated compounds are used which can be preferably polymerized with the aid of free radicals. The unsaturated sites in the bi- or multifunctional unsaturated compounds are in their chemically bonded state not really unsaturated, because the double bonds are each used for a covalent bond to the polypropylene polymer chains (D).
[00052] The reaction of the bifunctional unsaturated monomer and / or multifunctional unsaturated low molecular weight polymer, preferably having a numerical average molecular weight (M _n ) 10,000 g / mol, synthesized from one and / or more unsaturated monomers with polymeric propylene composition can be carried out in the presence of a thermal free radical forming agent, for example, decomposition free radical forming agent, such as a thermally decomposable peroxide and / or ionizing radiation or
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18/50 microwave radiation.
[00053] Bifunctional unsaturated monomers can be
- divinyl compounds, such as divinylaniline, mdivinylbenzene, p-divinylbenzene, divinylpentane and divinylpropane;
- allyl compounds, such as allyl acrylate, allyl methacrylate, allyl methyl maleate and allyl vinyl ether;
- dienes, such as 1,3-butadiene, chloroprene, cyclohexadiene, cyclopentadiene, 2,3-dimethylbutadiene, heptadiene, hexadiene, isoprene and 1,4-pentadiene;
- aromatic and / or aliphatic bis (maleimide) bis (citraconimide) and mixtures of these unsaturated monomers.
[00054] Especially preferred bifunctional unsaturated monomers are 1,3-butadiene, isoprene, dimethyl butadiene and divinylbenzene.
[00055] The multifunctional unsaturated low molecular weight polymer, preferably having a numerical average molecular weight (M _n ) 10,000 g / mol, can be synthesized from one or more unsaturated monomers.
[00056] Examples of such low molecular weight polymers are
- polybutadienes, especially where the different microstructures in the polymer chain, that is, 1,4-cis, 1,4-trans and 1,2- (vinyl) are predominantly in the 1,2- (vinyl) configuration
- copolymers of butadiene and styrene with 1.2 (vinyl) in the polymer chain.
[00057] A preferred low molecular weight polymer is polybutadiene, in particular, a polybutadiene having more than 50.0% by weight of butadiene in the I, 2- (vinyl) configuration.
[00058] High melt resistance polypropylene (HMS-PP) may contain more than one bifunctional unsaturated monomer and / or low molecular weight multifunctional unsaturated polymer
Petition 870190135536, of 12/18/2019, p. 21/63
19/50 do. Even more preferable the amount of bifunctional unsaturated monomer and multifunctional unsaturated low molecular weight polymer together in high melt resistance polypropylene (HMS-PP) is 0.01 to 10.0% by weight based on said polypropylene with high fusion resistance (HMS-PP).
[00059] As mentioned above, it is preferable that the bifunctional unsaturated monomer and / or the multifunctional unsaturated low molecular weight polymer is used in the presence of a thermally decomposing free radical forming agent.
[00060] Peroxides are preferred thermal free decomposition agents. Most preferably the free radical-forming radicals of thermal decomposition are selected from the group consisting of acyl peroxide, alkyl peroxide, hydroperoxide, perester and peroxycarbonate.
[00061] The following peroxides listed are in particular preferred:
[00062] Acyl peroxides: benzoyl peroxide, 4-chlorobenzoyl peroxide, 3-methoxybenzoyl peroxide and / or methyl benzoyl peroxide.
[00063] Alkyl peroxides: t-butyl allyl peroxide, 2,2-bis (tbutylperoxybutane), 1,1-bis (t-butylperoxy) -3,3,5-trimethylcyclohexane, n-butyl4,4-bis ( t-butylperoxy) valerate, diisopropylaminomethyl-tamyl peroxide, dimethylaminomethyl-t-amyl peroxide, diethylaminomethyl-t-butyl peroxide, dimethylaminomethyl-t-butyl peroxide, 1,1-di- (tamylperoxy) cyclohexane, t-peroxide -amyl, t-butylcumil peroxide, t-butyl peroxide and / or 1-hydroxybutyl n-butyl peroxide.
[00064] Peresters and peroxy carbonates: butyl peracetate, cumila peracetate, cumila perpropionate, cyclohexyl peracetate, di-t-butyl peradipate, di-t-butyl perazelate, di-tbutyl perglutarate, di-tbutyl perglutarate t-butyl, di-t-butyl persebacate, perpropionate
Petition 870190135536, of 12/18/2019, p. 22/63
20/50 4-nitrocumyl, 1-phenylethyl perbenzoate, phenylethyl nitro-perbenzoate, t-butylbicyclo- (2,2,1 l) heptane, tbutyl-4-carbomethoxy perbutyrate, t-butylcyclobutane percarboxylate, peroxycarboxylate t-butylcyclohexyl, t-butylcyclopentyl percarboxylate, t-butylcyclopropane percarboxylate, t-butyldimethyl percinamate, t-butyl-2- (2,2-diphenylvinyl) perbenzoate, t-butyl-4-methoxy perbenzoate, tbutilbenzoate , t-butylcarboxyclohexane, t-butyl peptide, t-butyl peroxyisopropylcarbonate, t-butyl pertoluate, t-butyl-1-phenylcyclopropyl percarboxylate, t-butyl-2-propylperpentene-2-oate, t-butyl percarboxylate -1-methylcyclopropyl, t-butyl-4-nitrophenyl peracetate, t-butylnitrophenyl peroxycarbamate, t-butyl-Nsucciimido percarboxylate, t-butyl percrotonate, permalleic t-butyl acid, t-butyl permethacrylate, peroc -butyl, tbutyl peroxyisopropylcarbonate, t-butyl perisobutyrate, peracrylate d and t-butyl and / or t-butyl perpropionate.
[00065] Or mixtures of these free radical forming agents listed above.
[00066] The unmodified polypropylene (D) to prepare such a high melt resistance polypropylene (HMS-PP) preferably has an MFR2 melt index (230 ° C) measured according to ISO 1133 in a range of 0, 05 to 45.00 g / 10 min. Most preferably the melt flow rate MFR2 (230 ° C) measured according to ISO 1133 is in the range of 0.05 to 35.00 g / 10 min. in the case where the unmodified polypropylene (D) is a homopolymer. On the other hand the MFR2 melting flow rate (230 ° C) measured according to ISO 1133 is in a range of 0.05 to 45.00 g / 10 min., In case the unmodified polypropylene (D) it is a copolymer.
[00067] Preferably the unmodified polypropylene (D) is a homopolymer.
[00068] To further improve the properties of the composition
Petition 870190135536, of 12/18/2019, p. 23/63
21/50 of polypropylene (PP-C) according to this invention, it can additionally comprise a polypropylene (C), with a flow rate MFR2 (230 ° C) measured according to ISO 1133 in the range of 50 to 250 g / 10 min., more preferably in the range of 60 to 150 g / 10 min .. The melting temperature Tm is preferably at least 158 ° C, more preferably at least 160 ° C, even more preferably in the range of 158 to 168 ° C, even more preferably in the range of 160 to 166 ° C. Typically, the molecular weight distribution (MWD) of polypropylene (C) is higher compared to the molecular weight distribution (MWD) of polypropylene (A). Consequently, the molecular weight distribution (MWD) of the polypropylene (C) is preferably at least more than 3.5, more preferably at least 4.0, even more preferably in the range of more than 3.5 to 6, 5, such as 4.0 to 6.0.
[00069] Polypropylene (C) is preferably a random propylene copolymer or a propylene homopolymer, the latter being preferred. Typically, such polypropylene (C) is produced in the presence of a Ziegler-Natta catalyst.
[00070] In addition, the present invention is also directed to blow-melt fibers produced from the polypropylene (A) composition as defined above. Thus, the present invention is in particular directed to a blow-melted fiber having an average diameter of not more than 5.0 pm, said fiber preferably comprises at least 95% by weight, more preferably it consists of a composition polypropylene (PP-C) as defined above.
[00071] As mentioned above, an essential requirement of the fiber of the invention is that it is a blow-melted fiber. Blown melt fibers differ essentially from other fibers, in particular those produced by the nonwoven technique. In the blowing process
Petition 870190135536, of 12/18/2019, p. 24/63
22/50 melting a high speed gas stream collides with the melted polymer stream like the polymeric extrudates from the small capillary tube in the melt blowing matrix and quickly attenuates the polymer filament of about 500 pm in diameter at capillary tube up to diameters less than 5.0 pm, as well as up to diameters less than 3.0 pm. This corresponds to a reduction of 500 times in the fiber diameter and 2,500,000 times in the cross-sectional area. The process takes about 200 microseconds over a distance of a few centimeters. This is equivalent to 6 times more surface area and 36 times more fiber in a 1 to 3 pm blow-molded network compared to an equivalent fiber network produced by the carded or non-woven technique. So the main advantage of the melt blown process is that you can produce very fine fibers and very light melt blown nets with excellent uniformity. The result is a soft blow cast network with excellent barrier properties, which means effective filtration characteristics and resistance to penetration by aqueous liquids. In other words, the characteristics of the fused blown process are distinguished from such fibers produced from fibers produced by different technology. More precisely, the fibers melted by blow are very thin presenting diameters not executed with other fiber processes. Other networks comprised of such blow-fused fibers are softer and have less weight compared to networks of the same thickness, but produced by other technologies, such as the nonwoven process. [00072] Consequently, the blow-fused fiber according to the present invention preferably has a measured (average) diameter of not more than 5.0 pm, more preferably not more than 3.5 pm. In particular, it is observed that the (average) diameter of the blow-melted fiber is in the range of 0.1 to 5.0 pm, more preferably in the range of 0.5 to 5.0 pm, even more preferably in the range
Petition 870190135536, of 12/18/2019, p. 25/63
23/50 from 0.5 to 3.5 pm, as well as from 0.7 to 3.0 pm.
[00073] The present invention is not only directed to blow-blown fibers as such, but also to articles, such as nets, produced therefrom. Consequently, the present invention is directed to articles comprising the blow-melted fibers of the present invention, such as the filter medium (filter), diaper, sanitary towels, panty liner, adult incontinence product, protective clothing, surgical drapes , surgical robe, and surgical clothing. In particular, the present invention is directed to a blow-fused network comprising the blow-fused fibers of the present invention.
[00074] In addition, the present invention claims articles selected from the group consisting of filtration medium (filter), diaper, sanitary towels, panty liner, adult incontinence product, protective clothing, surgical drapes, surgical dressing gown, and surgical clothing, comprising a blow-melt network comprising the blow-melt fibers of the present invention. The articles of the present invention may comprise, in addition to the blow-fused network, a spun fabric known in the art.
[00075] The present invention is also directed to the use of a polypropylene (B) having a fluidity index MFR2 (230 ° C) measured according to ISO 1133 equal to or less than 20 g / 10 min. in a polypropylene composition (PP-C2) showing an MFR2 melt index (230 ° C) measured according to ISO 1133 of at least 200 g / 10 min. to improve the elongation force of said polypropylene composition (PP-C2), expressed by the maximum applicable air volume during the processing of the blown fiber, where the improvement is defined by formula (V), preferably defined by formula general (VI),
PP-2 / PP-1> 1.3 (V),
Petition 870190135536, of 12/18/2019, p. 26/63
24/50
PP-2 / PP-1> 1.4 (VI) where
PP-2 is the maximum applicable air volume [m ³ / h] of the composition (PP-C2) comprising polypropylene (B),
PP-1 is the maximum applicable air volume [m ³ / h] of the composition (PP-C2) without polypropylene (B).
[00076] Preferably, the maximum applicable air volume [m ³ / h] is determined by a distance from the die to the collector (DCD) of 180 mm, a base weight of 120 g / m ² and a melting temperature of 275 ° C.
[00077] Preferably the composition (PP-C2) comprises in addition to polypropylene (B) a polypropylene (A), where polypropylene (A) has (i) an MFR2 flow rate (230 ° C) measured according to ISO 1133 of at least 450 g / 10 min.
and / or (ii) a molecular weight distribution (MWD) measured according to ISO 16014 not exceeding 3.5.
[00078] It is especially preferable that the polypropylene (B) used in the polypropylene composition (PP-C2) be the polypropylene (B) as defined for the polypropylene composition (PP-C). In addition, it is preferable that the polypropylene (PP-C2) composition is the polypropylene (PP-C) composition as defined above. Finally, in an especially preferred embodiment, polypropylene (A) is that as defined for the polypropylene composition (PP-C).
[00079] The individual components used for the polypropylene composition of the invention can be easily produced by the information provided in what follows.
[00080] Preferably, polypropylene (A) is produced in the presence of a single site catalyst, in particular in the presence of a ca
Petition 870190135536, of 12/18/2019, p. 27/63
25/50 metallocene talisator, such as a metallocene catalyst of formula (I) (Cp) 2RzMX2 (I) where z is 0 or 1, preferably 1,
M is a transition metal group 4, 5 or 6 of the Periodic Table, for example, titanium (Ti), zirconium (Zr), hafnium (Hf), vanadium (V), niobium (Nb), tantalum (Ta), chromium (Cr), molybdenum (Mo) and tungsten (W), especially zirconium (Zr),
X is independently a monovalent anionic ligand, such as σ-ligand,
Cp is an organic ligand selected from the group consisting of unsubstituted cyclopentadienyl, unsubstituted indenyl, unsubstituted tetrahydroindenyl, unsubstituted fluorenyl, substituted indenyl, substituted tetrahydroindenyl, and substituted fluorenil, preferably with the proviso that both Cp ligands selected from the group mentioned above and both Cp ligands are chemically the same, that is, they are identical
R is a bridging group that connects the two Cp ligands, where R has the formula (II)
-Y (R ') ^2- (II) where
Y is C, Si or Ge, preferably Si,
R 'is C1 to C20 alkyl, C6-C12 aryl, C7-C12 arylalkyl, or trimethylsilyl, preferably with the proviso that both R' residues are selected from the aforementioned group and both R 'residues are chemically different.
[00081] Even more preferable polypropylene (A) is in particular ob
Petition 870190135536, of 12/18/2019, p. 28/63
26/50 tenable, more preferably obtained by a catalyst system comprising the metallocene of formula (I), said catalyst system has a surface area measured according to ISO 9277 below 20 m ² / g.
[00082] Due to the use of the catalyst system with a very low surface area comprising the specific metallocene of formula (I), the manufacture of the polypropylene defined above (A) is possible.
[00083] In addition, it is preferable that the catalyst system has a surface area lower than 15 m2 / g, and even lower than 10 m ² / g, and most preferably lower than 5 m ² / g. The surface area according to this invention is measured according to ISO 9277 (N2).
[00084] Additionally, it is observed that the catalyst system has a porosity of less than 1.40 ml / g, more preferably less than 1.30 ml / g, and most preferably less than 1.00 ml / g. Porosity was measured according to DIN 66135 (N2). In another preferred embodiment, porosity is not detectable when determined with the method applied in accordance with DIN 66135 (N2).
[00085] It is particularly preferable that porosity is not detectable when applying the method according to DIN 66135 (N2) and the catalyst system has a surface area measured according to ISO 9277 (N2) less than 5 m ² / g.
[00086] The term σ-ligand is understood throughout the description in a known way, that is, a group attached to the metal in one or more locations through a sigma bond. A preferred monovalent anionic ligand is halogen, in particular chlorine (Cl).
[00087] Preferably, in the metallocene of general formula (I) each X is chlorine (Cl) and / or in both Cp ligands, especially both identical Cp ligands, are substituted.
[00088] The one or more optional substituents attached to cyclopenta
Petition 870190135536, of 12/18/2019, p. 29/63
27/50 dienyl, indenyl, tetrahydroindenyl or fluorenyl can be selected from a group including halogen, hydrocarbyl (for example, C1-C20 alkyl, C2-C20 alkenyl, C2-C20 alkynyl, C3-C12 cycloalkyl, C6C20 aryl, or C7 arylalkyl -C20), C3-C12 cycloalkyl containing 1, 2, 3 or 4 heteroatoms in the ring component, C6-C20 heteroaryl, C1-C20 haloalkyl, -SiR3, -OSIR3, -SR, -PR2 and -NR2, where each R is independently a hydrogen or hydrocarbyl, for example C1C20 alkyl, C2-C20 alkenyl, C2-C20 alkynyl, C3-C12 cycloalkyl, or C6C20 aryl.
[00089] More preferably both Cp ligands, preferably both identical Cp ligands, are indenyl components in which each indenyl component carries one or two substituents as defined above. More preferably, each of the Cp (identical) ligands is an indenyl component that carries two substituents as defined above, preferably with the proviso that the substituents are selected in such a way that both Cp ligands are of the same chemical structure, i.e. , both Cp ligands have the same substituents chemically linked to the same indenyl component.
[00090] Even more preferably both Cp ligands, preferably both identical Cp ligands, are indenyl components in which the indenyl components comprise at least the five-membered ring of the indenyl component, more preferably in position 2, a substituent selected from the group consisting of alkyl, such as C1-C6 alkyl, for example, methyl, ethyl, isopropyl, and trialkyloxysiloxy, wherein each alkyl is independently selected from C1-C6 alkyl, such as methyl or ethyl, preferably with provided that the indenyl components of both Cp ligands are of the same chemical structure, that is, both Cp ligands have the same chemically bonded substituents
Petition 870190135536, of 12/18/2019, p. 30/63
28/50 to the same indenyl component.
[00091] Even more preferable both Cp ligands, preferably both identical Co ligands, are indenyl components in which the indenyl components comprise at least the six-membered ring of the indenyl component, more preferably in the 4 position, a substituent selected from the group consisting of a component of the C6-C20 aromatic ring, such as phenyl or naphthyl, preferably phenyl, which is optionally substituted with one or more substituents, such as C1-C6 alkyl, and a component of the heteroaromatic ring, of preferably with the proviso that the indenyl components of both Cp ligands are of the same chemical structure, i.e., both Cp ligands have the same substituents chemically linked to the same indenyl component.
[00092] Even more preferably both Cp ligands, preferably both identical Cp ligands, are indenyl components in which the indenyl components comprise in the five-membered ring of the indenyl component, more preferably in position 2, a substituent and in the six-membered ring of the indenyl component, more preferably in position 4, another substituent, wherein the substituent on the five-membered ring is selected from the group consisting of alkyl, such as C1-C6 alkyl, for example, methyl, ethyl, isopropyl and trialkyloxysiloxy, preferably methyl, and the other six-membered ring substituent is selected from the group consisting of a component of the C6-C20 aromatic ring, such as phenyl or naphthyl, preferably phenyl, which is optionally substituted with a or more substituents, such as C1-C6 alkyl, such as tert-butyl, and a heteroaromatic ring component, preferably with the proviso that the components of indent ila of both Cp ligands are of the same chemical structure, that is, both Cp ligands have the same substituents chemically bonded to the same component 870190135536, of 18/12/2019, pg. 31/63
29/50 te of indenila.
[00093] It is noted in particular that both Cp ligands, preferably both identical Cp ligands, are indenyl components in which the indenyl components comprise in the five-membered ring of the indenyl component in position 2 a substituent and the ring of six members of the indenyl component at position 4 an additional substituent, wherein the five-membered ring substituent is selected from the group consisting of methyl, ethyl and isopropyl, and the additional six-membered ring substituent is selected from the group consisting of phenyl , phenyl substituted by C1-C6 alkyl, such as 4-tert-butyl-phenyl, naphthyl, and naphthyl substituted by C1-C6 alkyl, preferably with the proviso that the indenyl components of both Cp ligands are of the same structure that is, both Cp ligands have the same substituents chemically linked to the same indenyl component.
With respect to the linking group R of the formula (II) -Y (R ') 2- (II) it is preferable that
Y be Si
R 'is C 1 to C 10 alkyl or C 6-C 12 aryl, preferably with the proviso that both R' residues are selected from the aforementioned group and both R 'residues are chemically different.
[00094] Consequently in a specific embodiment the catalyst is of formula (III) (Cp) 2RZrCl2 (III) in which
Cp is an indenyl substituted with a substituent in position 2 of the five-membered ring and a substituent in position 4 of the six-membered ring, where the substituent of the five-membered ring
Petition 870190135536, of 12/18/2019, p. 32/63
30/50 bros is methyl or ethyl and the six-membered ring substituent is phenyl substituted by C1-C6 alkyl, such as 4-methyl-phenyl or 4-tert-butyl-phenyl (the latter especially preferred), with the proviso that that both Cp ligands are chemically the same, that is, they are identical,
R is a bridging group that connects the two Cp ligands, where R has the formula (IV)
-Si (R ') 2- (IV) where
R 'is selected from the group consisting of methyl, ethyl, isopropyl, cyclohexyl, 4-C 1 to C 10 cyclohexyl, such as 4-methyl-cyclohexyl.
[00095] Preferably, with the proviso that both R 'residues are selected from the group mentioned above and both R' residues are chemically different.
[00096] In an especially preferred embodiment the catalyst is methylcyclohexylsilanediilbis dichloride (2-methyl-4-tert-butylphenyl-indenyl) zirconium.
[00097] Furthermore, it is preferable that the catalyst systems used are self-supporting, that is, they are solid, but do not comprise catalytically inert external carrier material, such as organic and inorganic support materials such as silica, MgCl2 or carrier material polymeric (porous).
[00098] The catalyst system described above is prepared according to the methods described in WO 01/48034.
[00099] It is particularly preferred that the catalyst system is obtained by emulsion solidification technology as described in WO 03/051934. This document is included here in its entirety by reference. Therefore, the catalyst system is preferably in the form of solid catalyst particles, obtainable by a process
Petition 870190135536, of 12/18/2019, p. 33/63
31/50 comprising the steps of
a) preparing a solution of one or more catalyst components;
b) dispersing said solution in a solvent immiscible with it, to form an emulsion in which said one or more catalyst components are present in the droplets of the dispersed phase,
c) solidifying said dispersed phase to convert said droplets into solid particles and optionally recovering said particles to obtain said catalyst.
[000100] Preferably a solvent, more preferably an 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, linear alkene, cyclic alkane, aromatic hydrocarbon and halogen-containing hydrocarbon.
[000101] Furthermore, the immiscible solvent that forms the continuous phase is an inert solvent, more preferably the immiscible solvent comprises a fluorinated organic solvent and / or a functionalized derivative thereof, even more preferably the immiscible solvent comprises a semi-hydrocarbon, highly or perfluorinated and / or a functionalized derivative thereof. It is preferable, in particular, that said immiscible solvent comprises a perfluorohydrocarbon or a functionalized derivative thereof, preferably perfluoroalkane, C3-C30 -alkanes or cycloalkanes, more preferable perfluoro-alkanes, -alkylene or cycloalkanes C4-C10, particularly preferable perfluoroexane, perfluoroeptane , perfluorooctane or perfluoro (methylcyclohexane) or a mixture thereof.
[000102] Furthermore, it is preferable that the emulsion comprising said continuous phase and said dispersed phase is a multiphase biou system as known in the art. An emulsifier can be used to form the emulsion. After the formation of the emul system
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32/50, said catalyst is formed in situ from catalyst components in said solution.
[000103] 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) heteroatoms, preferably halogenated hydrocarbons optionally having a functional group, preferably semi-, highly or perfluorinated hydrocarbons as known in the art. Alternatively, the emulsifying agent can be prepared during the preparation of the emulsion, for example, by reacting a surfactant precursor with a compound in the catalyst solution. Said surfactant precursor can be a halogenated hydrocarbon with at least one functional group, for example, a highly fluorinated C1 to C30 alcohol, which reacts, for example, with a cocatalyst component, such as aluminoxane.
[000104] In principle, any solidification method can be used to form the solid particles from the dispersed droplets. According to a preferred embodiment, solidification is effected by a temperature change treatment. Therefore, the emulsion is subjected to a gradual temperature change of up to 10 ° C / min., Preferably from 0.5 to 6 ° C / min. and more preferably from 1 to 5 ° C / min. Even more preferably, 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.
[000105] The recovered particles preferably have an average size range of 5 to 200 pm, more preferably 10 to 100 pm. [000106] Furthermore, the form of solidified particles has to
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33/50 preferably a spherical shape, a predetermined particle size distribution and a surface area as mentioned above preferably less than 25 m ² / g, even more preferably less than 20 m ² / g, even more preferably less than than 15 m ² / g, even more preferably less than 10 m ² / g, and most preferably less than 5 m ² / g, wherein said particles are obtained by the process as described above.
[000107] For further details, the modalities and examples of the continuous and dispersed phase system, emulsion formation method, emulsifying agent and reference solidification methods are prepared, for example, in the aforementioned international patent application WO 03/051934.
[000108] The catalyst components described above are prepared according to the methods described in WO 01/48034.
[000109] As mentioned above, the catalyst system may further comprise an activator such as a cocatalyst, as described in WO 03/051934, which is included herein by reference.
[000110] Preferred as metallocene cocatalysts, if desired, are aluminoxanes, in particular C1C10 alkylaluminoxanes, more particularly methylaluminoxane (MAO). Such aluminoxanes can be used as the sole cocatalyst or in conjunction with other cocatalysts. Thus, in addition, or in addition to aluminoxanes, other catalysts activators of complex capture formation can be used. Said activators are commercially available or can be prepared according to the prior art literature.
[000111] Other aluminoxane cocatalysts are described in WO 94/28034 which is incorporated herein by reference. These are linear or cyclic oligomers with up to 40, preferably 3 to 20, - (Al (R ') O) - repeating units (where R' is hydrogen, C1-Petition alkyl 870190135536, from 12/18/2019, pg. 36/63
34/50
Cio (preferably methyl) or C6-C18 aryl or mixtures thereof.
[000112] The use and quantities of such activators are within the skills of an expert in the field. As an example, with boron activators, from 5: 1 to 1: 5, preferably from 2: 1 to 1: 2, such as 1: 1, ratio of transition metal to boron activator can be used. In the case of preferred aluminoxanes, such as methylaluminoxane (MAO), the amount of Al, provided by aluminoxane, can be selected to provide a molar ratio of Al: transition metal, for example, in the range of 1 to 10,000, suitably 5 to 8000, preferably from 10 to 7000, for example, from 100 to 4000, such as from 1000 to 3000. Typically, in the case of solid (heterogeneous) catalyst, the ratio is preferably less than 500.
[000113] The amount of cocatalyst to be used in the catalyst of the invention is, therefore, variable, and depends on the conditions and the particular transition metal compound selected in a manner well known to a person skilled in the art.
[000114] Any additional components to be contained in the solution comprising the organotransition compound can be added to said solution before or, alternatively, after the dispersion step.
[000115] Polypropylene polymerization (A) can be a mass polymerization, preferably carried out in a so-called closed loop reactor. Alternatively, the polymerization of polypropylene (A) is a two-stage polymerization carried out in a combination of a closed loop reactor that operates in the slurry phase and a gas phase reactor as, for example, applied in the Borstar polypropylene process.
[000116] Preferably, in the process for the production of polypropylene (A) as defined above the conditions for the mass reactor of the step can be as follows:
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35/50
- 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 2 x 10 ³ kPa at 8 x 10 ³ kPa (20 bar at 80 bar), preferably between 3 x 10 ³ kPa at 6 x 10 ³ kPa (30 bar at 60 bar) - hydrogen can be added to control molar mass in a manner known per se.
[000117] Subsequently, the mass (volume) reactor reaction mixture is transferred to the gas phase reactor, whereby the conditions are preferably as follows:
- the temperature is within the range of 50 ° C to 130 ° C, preferably between 60 ° C and 100 ° C,
- the pressure is within the range of 5 x 10 ² kPa to 5 x 10 ³ kPa (5 bar to 50 bar), preferably from 1.5x to 3.5x 10 ³ kPa ³ 10 kPa (15 bar to 35 bar)
- hydrogen can be added to control molar mass in a manner known per se.
[000118] The residence time may vary in both reactor zones. In an embodiment of the process for the production of the propylene polymer the residence time in the mass reactor, for example, closed circuit, is in the range of 0.5 to 5 hours, for example, from 0.5 to 2 hours and the residence time in the gas phase reactor will generally be 1 to 8 hours.
[000119] If desired, the polymerization can be carried out in a known manner under supercritical conditions in the mass reactor, preferably closed loop, and / or as a condensed mode in the gas phase reactor.
[000120] Propylene homopolymer (H-PP), as one of the two options for polypropylene (B), as well as polypropylene (C), are obtained with a process using a Ziegler-Natta system. Propylene homopolymer (H-PP) or polypropylene (C) can be prepared
Petition 870190135536, of 12/18/2019, p. 38/63
36/50 by polymerization, in a slurry reactor, for example, a closed loop reactor, propylene in the presence of a polymerization catalyst to produce at least a part of the propylene homopolymer (H-PP) or polypropylene ( Ç). In case only part of the propylene homopolymer (H-PP) or part of the polypropylene (C) is produced, this part is subsequently transferred to a gas phase reactor, in which in the gas phase reactor the propylene is reacted so as to produce an additional part in the presence of the reaction product of the first stage. This reaction sequence provides a reactor mixture of parts (i) and (ii) that makes up the propylene homopolymer (H-PP) or polypropylene (C). It is naturally possible by the present invention that the first reaction is carried out in a gas phase reactor while the second polymerization reaction is carried out in a slurry reactor, for example, a closed loop reactor. In addition, it is also possible to invert the production order of parts (i) and (ii), which was described above in the order of the first production part (i) and then the production part (ii). The process discussed above, comprising at least two polymerization steps, is advantageous in view of the fact that it provides easily controllable reaction steps which allows the preparation of a desired reactor mixture. The polymerization steps can be adjusted, for example, by the appropriate selection monomer feed, hydrogen feed, temperature and pressure, in order to properly adjust the properties of the obtained polymerization products. In particular, it is possible to obtain a multimodality, preferably bimodality, of the propylene homopolymer (H-PP) in relation to the molecular weights and MFR2 values (230 ° C) during said multi-stage polymerization procedures. However, propylene homopolymer (H-PP) or polypropylene (C) can also be produced in a reactor, such coPetition 870190135536, of 12/18/2019, p. 39/63
37/50 mo to a closed circuit reactor, a method that is preferred.
[000121] Such a process (one reactor or more reactors in sequence) can be carried out using any catalyst suitable for the preparation of propylene homopolymer (H-PP) or polypropylene (C). Preferably, the process as discussed above is carried out using a Ziegler-Natta catalyst, in particular a high-performance Ziegler-Natta catalyst (so-called fourth and fifth generation type to differentiate from low-yield, so-called second Ziegler-Natta catalysts generation). A suitable ZieglerNatta catalyst to be employed in accordance with the present invention comprises a catalyst component, a cocatalyst component and at least one electron donor (internal and / or external electron donor, preferably at least one external donor). Preferably, the catalyst component is a Ti-Mg based catalyst component and typically the cocatalyst is an Al-alkyl based compound. Suitable catalysts are, in particular, disclosed in US 5,234,879, WO 92/19653, WO 92/19658 and WO 99/33843.
[000122] Preferred external donors are known donors based on silane, such as dicyclopentyl dimethoxy silane or cyclohexyl methyldimethoxy silane.
[000123] One embodiment of a process for the propylene homopolymer (H-PP) or polypropylene (C), as discussed above, is a recirculation phase process or a gas-recirculation phase process, as developed by Borealis, known as the Borstar ^® technology, described, for example, in EP 0 887 379 A1 and WO 92/12182.
[000124] With respect to the preferred recirculation phase process mentioned above (slurry), the following general information can be provided regarding the conditions of the process.
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38/50 [000125] The temperature from 40 to 110 ° C, preferably between 60 and 100 ° C, in particular between 80 and 90 ° C, with a pressure in the range of 20 to 80 bar, preferably from 30 to 60 bar, with the option of adding hydrogen in order to control the molecular weight. The slurry polymerization reaction product, which is preferably carried out in a closed loop reactor, is then transferred to the subsequent gas phase reactor (in the case of a sludge phase process), at which temperature is preferred. is within the range of 50 to 130 ° C, more preferably 80 to 100 ° C, at a pressure in the range of 5 to 50 bar, preferably 15 to 35 bar, again with the option of adding hydrogen in order to control the molecular weight.
[000126] The residence time may vary in the reactor zones identified above. In the embodiments, the residence time in the slurry reaction, for example, the closed loop reactor, is in the range of 0.5 to 5 hours, for example, from 0.5 to 2 hours, while the time of permanence in the gas phase reactor will generally be from 1 to 8 hours.
[000127] The properties of the propylene homopolymer (H-PP) or polypropylene (C) produced with the process outlined above can be adjusted and controlled with the conditions of the process as known to the skilled person, for example, by one or more of the following process parameters: temperature, hydrogen supply, propylene supply, catalyst, type and quantity of external donor, division between two or more components of a multimodal polymer.
[000128] Polypropylene with high melt resistance (HMS-PP), as one of the two options for polypropylene (B), is preferably obtained by a process as described in EP 0 879 830 A1 and EP 0 890 612 A2. Both documents are included here by reference. Con
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39/50 consequently, high melt resistance polypropylene (HMS-PP) is produced by (a) mixing (i) an unmodified propylene homopolymer and / or copolymer (D) as defined above, preferably a propylene homopolymer unmodified (D) with a weighted average molecular weight (Mw) of 500,000 to 1,500,000 g / mol, (ii) from 0.05 to 3% by weight based on the components of (i) and (ii), a peroxide selected from the group consisting of acyl peroxide, alkyl peroxide, hydroperoxide, perester and peroxycarbonate, and (iii) optionally diluted with inert solvents, (b) heat from 30 to 100 ° C, preferably from 60 to 90 ° C , (c) sorption of volatile bifunctional monomers, preferably ethylenically unsaturated multifunctional monomers, such as C4 to C10 dienes and / or divinyl compounds C7 to C10, by the homopolymer and / or unmodified propylene (D) copolymer, preferably homopolymer of unmodified propylene (D) from the gas phase at a temperature of 20 to 120 ° C, preferably 60 to 100 ° C, where the amount of the bifunctional unsaturated monomers is from 0.01 to 10.00% by weight, preferably from 0.05 to 2.00 % by weight, based on the propylene homopolymer (D), (d) heat and melt the polypropylene composition in an atmosphere comprising an inert gas and / or volatile bifunctional monomers, from the sorption temperature up to 210 ° C , after which free radical generators are decomposed, and then (e) heat the melt to 280 ° C in order to remove unreacted monomers and decomposition products, and (f) agglomerate the melt.
[000129] The process for the production of polypropylene with high re
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40/50 fusion resistance (HMS-PP) is preferably a continuous method, performed in continuous reactors, mixers, kneaders and extruders. Batch production of polypropylene with high melt resistance (HMS-PP), however, is also possible.
[000130] The practical sorption times τ of the bifunctional volatile monomers vary from 10 to 1000 s, where sorption times τ 60 to 600 are preferred.
[000131] The process of the invention or any of its modalities above allows highly viable means for the production and further cutting of the polymeric propylene composition within the invention, for example, the properties of the polymeric composition can be adjusted or controlled in a way known, for example, with one or more of the following process parameters: temperature, hydrogen feed, comonomer feed, propylene feed, for example, in the gas phase reactor, catalyst, the type and quantity of an external donor (if used), division between components.
[000132] The above process allows very viable means for obtaining the polypropylene produced in the reactor as defined above.
[000133] In addition, the polypropylene (PP-C) composition according to the present invention can be prepared by the composition of the components within melt mixing devices suitable for the preparation of polymeric compounds, including in the particular extruders, extruders of single screw as well as double screw extruders. Other suitable fusion mixing devices include planetary extruders and single screw mixers. Especially preferable are twin screw extruders including high intensity mixing and kneading sections. The melting temperatures suitable for the preparation of the compositions are in the range of 170 to 300 ° C, preferably in the range of 200 to 260 ° C and a screw speed of 50 to 300 rpm.
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41/50 [000134] The polypropylene composition thus obtained (PP-C) is used in the form of a globule or granule for the process of blowing molten fiber. In the process, measuring pumps are used to pump the melted polypropylene (PP-C) composition to a distribution system featuring a series of matrix tips, the polypropylene (PP-C) composition being in the molten state at some processing temperature. . The die tip is designed in such a way that the orifices are in a straight line with high speed air impinging on each side. A typical matrix will be 0.3 to 0.5 mm in diameter, preferably 0.4 mm in diameter, holes spaced 10 to 16 per cm (25 to 40 per inch). The high-speed hot air colliding attenuates the filaments and forms the desired fibers. Immediately below or adjacent to the matrix, a large amount of ambient air is attracted to the hot air stream containing the fibers which cools the hot gas and solidifies the fibers on a forming belt or other solid surface that is typically moved in such a way as to create a continuously renewed surface for the fibers to contact and form a network. The processing temperature is a factor in the final properties of the network. The ideal processing temperature is one in which the ideal properties of the network are achieved such as low granulation with good handling and high barrier properties, or good filtration properties.
[000135] The present invention will now be described in more detail by the examples provided below.
EXAMPLES
1. Definitions / Measurement Methods [000136] The following definitions of terms and methods of determination apply to the general description above of the invention, as well as the examples below, unless otherwise defined.
[000137] Quantification of the isotactic capacity in polypropylene by
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42/50 spectroscopy ¹³ C NMR [000138] Isotactic capacity is determined by quantitative nuclear magnetic resonance (MRI) ¹³ C spectroscopy after the basic designation, for example, in: V. Busico and R. Cipullo, Progress in Polymer Science , 2001, 26, 443-533. The experimental parameters are adjusted to ensure measurement of the quantitative spectra for this specific task, for example, in: S. Berger and S. Braun, 200 and More NMR Experiments: A Practical Course, 2004, Wiley-VCH, Weinheim. Quantities are calculated using the simple corrected ratios of the signal integrals of the representative sites in a manner known in the art. The isotactic capacity is determined at the pentavalent level, that is, mmmm fraction of the pentavalent distribution.
Propylene 2,1-inserts [000139] The relative amount of propylene monomer 2,1-inserts in the chain was determined by ¹³ C NMR spectroscopy and calculated as described in EP 0 629 632 B1.
Randomness [000140] In FTIR measurements, films of 250 mm thickness were molded by compression at 225 ° C and investigated in a Perkin-Elmer System 2000 FTIR instrument. The maximum ethylene area (760 to 700 cm ^-1 ) was used as a measure of the total ethylene content. The absorption range for the structure -PEP- (an ethylene unit between the propylene units), runs at 733 cm ^-1 . This range characterizes the random ethylene content. For longer ethylene sequences (more than two units), an absorption range occurs at 720 cm ^-1 . Generally, a protrusion corresponding to longer periods of ethylene is observed for random copolymers. Calibration for the total ethylene content based on the area and the random ethylene content (PEP) based on the maximum height at 733 cm ^-1 was performed by
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43/50 ¹³ C NMR. (Thermochimica Acta, 66 (1990) 53-68).
[000141] Randomness = random ethylene content (-P-E-P-) / the total ethylene content x 100%.
[000142] Numerical average molecular weight (Mn), weighted average molecular weight (Mw) and molecular weight distribution (MWD) are determined by size exclusion chromatography (SEC), using the Waters Alliance GPCV 2000 instrument with online viscometer . The oven temperature is 140 ° C. Trichlorobenzene is used as a solvent (ISO 16014).
[000143] Density is measured according to ISO 1183-187. Sample preparation is done by compression molding according to ISO 1872-2: 2007.
[000144] MFR2 (230 ° C) is measured according to ISO 1133 (230 ° C,
2.16 kg of load).
Quantification of the comonomer content by FTIR spectroscopy [000145] Quantitative infrared (IR) spectroscopy was used to quantify the amount of comonomer. The calibration was obtained through the correlation with the comonomer contents determined by the quantitative nuclear magnetic resonance (NMR) spectroscopy.
[000146] The calibration procedure based on the results obtained from the quantitative ¹³ C-NMR spectroscopy was undertaken in the conventional manner well documented in the literature. The amount of comonomer (N) was determined as a weight percent (% by weight) using:
N = k1 (A / R) + k2 [000147] where A is the maximum defined absorbance of the comonomer range, R the maximum absorbance defined as the maximum height of the reference peak and with k1 and k2 the linear constants obtained by
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44/50 calibration.
[000148] For poly (ethylene-co-propene-co-butene) (EPB) systems, quantification was achieved through two characteristic absorbance ranges:
• 1-butene content through 760 cnr ¹ (linear baseline correction between 750 to 810 cnr ¹ ) • ethylene content through 720 or 730 cnr ¹ (linear baseline correction between 710 to 750 cm ¹ ) [000149] The range used to quantify the ethane content is selected depending on whether the ethylene content is random (730 cm ¹ ) or similar to a block (720 cm ¹ ). The absorbance at 4324 cm ¹ was used as a reference range.
[000150] The amount of comonomer (N) as determined as molar percent (mol%) was obtained by converting units of percent by weight (% by weight) using the molecular weight (Mw) of the comonomer:
NA [molar%] = (NA [% by weight] / MwA) / ((NA [% by weight] / MwA) + (NB [% by weight] / MWB) + ((100 [% by weight] - NA [% by weight] - NB [% by weight]) / MwC)) [000151] Infrared spectra in solid state were recorded using an FTIR spectrometer on thin films molded by compression (100 to 800 pm) at a resolution of 4 cnr ¹ and analyzed in transmission mode.
Quantification of the comonomer content by ¹³ C NMR spectroscopy [000152] The comonomer content was determined using quantitative nuclear magnetic resonance (NMR) spectroscopy after the base assignment (eg NMR Spectra of Polymers and Polymer Additives, AJ Brandolini and DD Hills, 2000, Marcel Dekker, Inc. New York).
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45/50 [000153] The experimental parameters have been adjusted to ensure the measurement of the quantitative spectra for this specific task (eg 200 and More NMR Experiments: A Practical Course, S. Berger and S. Braun, 2004, Wiley-VCH, Weinheim). The quantities were calculated using the simple corrected ratios of the signal integrals of representative sites in a manner known in the art.
Melting temperature Tm [000154] The melting temperature (maximum temperature) Tm was measured by DSC according to ISO 11357-3 using the maximum temperature in the second heating in a heating cycle - cooling - heating at a rate of 10 K / min between room temperature e210 ° C.
[000155] Xylene soluble (XCS,% by weight): Xylene soluble content (XCS) is determined at 23 ° C according to ISO 6427.
[000156] The gel content is assumed to be identical to the fraction of hot insoluble xylene (XHI), which is determined by extracting 1 g of finely cut polymeric sample with 350 ml of xylene in a Soxhlet extractor for 48 hours at temperature boiling. The amount of solid remaining is dried at 90 ° C and weighed to determine the insoluble amount.
[000157] Hardening behavior under tension (melting resistance):
[000158] The curing behavior under tension is determined by the method as described in the article Rheotens-Mastercurves and Drawability of Polymer Melts, Μ. H. Wagner, Polymer Engineering and Sience, MID-APRIL ISW, Vol. 36, NO. 7, pages 925 to 935. The content of the document is included by reference.
[000159] The stress-hardening behavior of polymers is analyzed by the Rheotens mechanism (product of Gõttfert, Sie
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46/50 mensstr.2, 74711 Buchen, Germany) in which a melting filament is elongated by stretching with a defined acceleration. The drawing force F depending on the drawing speed v is recorded. [000160] The test procedure is performed in a standard air-conditioned room with a controlled ambient temperature of 23 ° C and 3 x 10 ³ kPa (30 bar). The Rheotens mechanism is combined with an extruder / fusion pump for continuous feeding of the fusion filament. The extrusion temperature is 200 ° C; a matrix of capillary tube with a diameter of 2 mm and a length of 6 mm is used. The resistance length between the capillary tube matrix and the Rheotens wheels is 80 mm. At the beginning of the experiment, the absorption speed of the Rheotens wheels was adjusted to the speed of the extruded polymer filament (zero tensile force): Then, the experiment was started by slowly increasing the absorption speed of the Rheotens wheels until the filament polymer breaks. The acceleration of the wheels was small enough so that the tractive force was measured under almost stable conditions. The acceleration of the stretched melting filament is 120 mm / s ² . Rheotens was operated in combination with the PC EXTENS program. This is a real-time data acquisition program that displays and stores the measured data of the pulling force and stretching speed.
Net weight [000161] The unit weight (grammage) of the net in g / m ² was determined in accordance with ISO 536: 1995.
Average fiber diameter in the grid [000162] The numerical average fiber diameter was determined using scanning electron microscopy (SEM). A representative part of the network was selected and an SEM micrograph of adequate magnification was recorded, then the diameter of 20 fibers was measured and the numerical average was calculated.
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47/50
2. Preparation of Examples
Preparation of PP A1 Catalyst [000163] A metallocene catalyst as described in example 1 of EP 1741725 A1 was used for the preparation of the propylene homopolymer PP 2.
Polymerization [000164] The propylene homopolymer PP A 'was produced in a Borstar PP pilot plant as follows: The catalyst was fed together with triethyl aluminum as a cocatalyst with an Al / Zr [mol / mol] ratio of 911 in a reactor of prepolymerization of agitated tank together with propylene and hydrogen in a ratio of 0.19 mol / kmol of propylene, the reactor being operated at 35 ° C with an average residence time of 0.4 hour. The main polymerization step was carried out in a closed loop reactor at a temperature of 70 ° C and a pressure of 6000 kPa that supplies the additional propylene at 150 kg / h with hydrogen in a ratio of 0.70 mol / kmol of propylene , maintaining an average residence time of 0.65 hours, reaching a catalyst productivity of 17.6 kg / g. After deactivating the catalyst with steam and drying the resulting polymer powder with hot nitrogen, the resulting polypropylene homopolymer was combined together with 0.07% by weight of Calcium Stearate and 0.60% Irganox B225 (antioxidant combination provided by Ciba Specialty Chemicals) in a twin screw extruder at 230 to 250 ° C.
[000165] The resulting propylene homopolymer has an MFR2 (2.16 kg, 230 ° C) of 900 g / 10 min., A density of 902 kg / m ³ , a melting point of 153 ° C and a content of XS of 1.4% by weight. The GPC determination resulted in a weighted average molecular weight (Mw) of 69 kg / mol, a numerical average molecular weight (Mn)
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48/50 of 30 kg / mol and a MWD (Mw / Mn) of 2.3.
Preparation of PP A2 [000166] The same catalyst and polymerization process as for PP A1 was applied, however using a hydrogen feed in a ratio of 0.75 mol / kmol of propylene, maintaining an average residence time of 0, 60 hours, reaching a catalyst productivity of 15.6 kg / g. The deactivation and additives were carried out again in the same way as for PP A1. The resulting propylene homopolymer has an MFR2 (2.16 kg,
230 ° C) of 980 g / 10 min., A density of 902 kg / m ³ , a melting point of 153 ° C and an XS content of 1.1% by weight. The determination
GPC resulted in a weighted average molecular weight (Mw) of 63 kg / mol, a numerical average molecular weight (Mn) of 27 kg / mol and a MWD (Mw / Mn) of 2.3.
[000167] Table 1: Properties of PP-A1 and PP-A2 polypropylene homopolymers
PP-A1 PP-A2 MFR2 (230 ° C) [g / 10 min] 900 980 Mw [kg / mol] 69 63 MWD [-] 2.3 2.3 Tm [° C] 153 153 AHf [J / g] 105.3 108.3 Tc [° C] 118 117 AHc [J / g] 103.5 98.3 XCS [% by weight] 1.4 1.1 g ' [-] 1.0 1.0
[000168] PP-A1 and PP-A2 were mixed with low MFR materials HMS-PP and PP-B summarized in Table 2. Powder material PP-C was added in some mixtures in order to improve the mixing of the low and high MFR components.
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49/50 [000169] Table 2: Properties of HMS-PP, the propylene homopolymer PP-B and the polypropylene homopolymer PP-C
HMS-PP PP-B PP-C MFR2 (230 ° C) [g / 10 min] 6.0 8.2 80 Density [kg / m ³ ] 905 905 905 Tm [° C] 165 164 164 XHI [% by weight] 0.35 0.0 0.0 XCS [% by weight] 2.5 1.2 1.8 g ' [-] 0.64 1.0 1.0
[000170] HMS-PP is the polypropylene with high resistance to commercial fusion Daploy ™
WB180HMS from Borealis AG based on a propylene homopolymer, in which the high melt resistance polypropylene Daploy ™ WB180HMS has a melting force of 11.5 cN at a maximum speed of 242 mm / s,
PP-B is the commercial HD601CF propylene homopolymer from Borealis AG in which no 2,1-insertion of propylene monomers in the chain is detectable by 13C-NMR spectroscopy. [000171] Table 3: Mixtures for fusion blowing experiments
IE 1 IE 2 IE 3 IE 4 IE 5 PP-A1 [% by weight] 90 90 98 - - PP-A2 [% by weight] - - - 85 85 HMS-PP [% by weight] 10 - 2 10 - PP-B [% by weight] - 10 - - 10 PP-C [% by weight] - - - 5 5 Tm [° C] 154 156 154 156 156 MFR2 (230 ° C) [g / 10 min] 300 340 445 500 545 XCS [% by weight] 1.5 1.4 1.4 1.3 1.2 XHI [% by weight] 0.04 0.0 0.01 0.04 0.0
[000172] The mixtures were tested on the pilot line blown in
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50/50 Reicofil fusion, using a matrix with 0.4 mm diameter holes and 35 holes per inch. The melting temperature was set at 275 ° C and the air temperature at 270 ° C. Additionally HL504FB from Borealis was tested as a viscorreduced reference material on the same pilot line. The effect of distance from the matrix to collector (DCD) and the melting temperature on the processability and network properties were investigated. The basic weight was 120 g / m ² . The reported air volumes are the highest applicable ones that can be used without the formation of steering wheels.
Maximum applicable air volumes:
[000173] The maximum applicable air volumes are shown in Figure 1 (DCD 180 mm, base weight 120 g / m ² , melting temperature 275 ° C). As shown in Figure 1, higher air volumes can be applied for all mixtures compared to the reference material PP-A2 and commercial grade HL504FB. The highest possible air volume (550 m ³ / h, pilot line limitation) can be applied for mixtures IE 4 and IE 5.
Average fiber diameters:
[000174] The measured average fiber diameters and standard deviations are illustrated in Figure 2. (DCD 180 mm, base weight 120 g / m ² , melting temperature 275 ° C).
[000175] Typically the fused blown nets produced from the mixtures show a lower average fiber diameter compared to the reference base materials PP-A1 and PP-A2.
[000176] Figures 1 and 2 clearly demonstrate that the elongation strength of the fibers produced from the polypropylene (PP-C) composition comprising a polypropylene (A) has been improved by mixing with a low MFR polypropylene (B). This was seen as higher applicable air volumes and resulting thinner average fiber diameters.

权利要求:
Claims (17)
[1]
1. Polypropylene (PP-C) composition, characterized by the fact that it comprises:
(a) a polypropylene (A) having (i) an MFR2 melt index (230 ° C), measured according to ISO 1133, of at least 450 g / 10 min, and (ii) a molecular weight distribution ( MWD), measured in accordance with ISO 16014, not exceeding 3.5, (b) a polypropylene (B) having a fluidity index MFR2 (230 ° C), measured according to ISO 1133, equal to or less than 20 g / 10 min, with the composition (PP-C) having a fluidity index MFR2 (230 ° C), measured according to ISO 1133, of at least 200 g / 10 min.
[2]
2. Polypropylene (PP-C) composition, according to claim 1, characterized by the fact that polypropylene (A) has:
(a) a weighted average molecular weight (Mw), measured according to ISO 16014, in the range of 20,000 to 95,000 g / mol, and / or (b) a cold soluble xylene content (XCS), measured according to ISO 6427 (23 ° C), not exceeding 2.5% by weight, and / or (c) a melting temperature Tm, measured according to ISO 11357-3, of at least 150 ° C.
[3]
3. Polypropylene (PP-C) composition according to claim 1 or 2, characterized by the fact that polypropylene (B) is a propylene homopolymer (H-PP) or a polypropylene with high melt resistance (HMS -PP).
[4]
4. Polypropylene (PP-C) composition, according to claim 3, characterized by the fact that the propylene homopolymer (H-PP) has:
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2/4 (a) a cold soluble xylene content (XCS), measured according to ISO 6427 (23 ° C), in the range of 0.5 to 3.5% by weight, and / or (b) <1.2> regiodefects not exceeding 0.4 mol%, determined by ¹³ C spectroscopy.
[5]
5. Polypropylene composition (PP-C), according to claim 3, characterized by the fact that polypropylene with high melt resistance (HMS-PP) features:
(a) a hot insoluble fraction of xylene (XHI) less than 1.0% by weight, and / or (b) a branch index g 'of less than 1.0, and / or (c) a melting temperature Tm , measured in accordance with ISO 11357-3, of at least 140 ° C.
[6]
6. Polypropylene (PP-C) composition according to any one of claims 1 to 5, characterized by the fact that it also comprises a polypropylene (C) having a flow rate MFR2 (230 ° C), measured according to ISO 1133, in the range of 50 to 250 g / 10 min.
[7]
7. Polypropylene (PP-C) composition according to any one of claims 1 to 6, characterized by the fact that it comprises:
(a) 75.0 to 99.5% by weight of polypropylene (A), (b) 0.5 to 25.0% by weight of polypropylene (B), and (c) 0 to 15% by weight of polypropylene (C), based on the total composition.
[8]
8. Polypropylene (PP-C) composition, according to claim 7, characterized by the fact that it comprises:
(a) 75.0 to 99.5% by weight of polypropylene (A), (b) 0.5 to 25.0% by weight of polypropylene (B), and (c) 0 to 15% by weight of polypropylene (C), based on the polypropylenes present in the composition.
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3/4
[9]
9. Blow-melted fiber, characterized by the fact that it has an average diameter of not more than 5.0 pm, and that comprises at least 95% by weight of a polypropylene (PP-C) composition, as defined in any one of claims 1 to 8.
[10]
10. Blow-melted fiber according to claim 9, characterized by the fact that it has been cooled with air.
[11]
11. Blow-fused network, characterized by the fact that it comprises blow-fused fibers, as defined in claim 9 or 10, and / or a polypropylene (PP-C) composition, as defined in any of claims 1 to 8 .
[12]
12. Article, characterized by the fact that it comprises a blow-fused fiber, as defined in claim 9 or 10, and / or a blow-fused network, as defined in claim 11, and which is selected from the group consisting of filtration medium , diaper, sanitary towel, panty liner, adult incontinence product, protective clothing, surgical cloths, surgical dressing gown, and surgical clothing.
[13]
13. Article according to claim 12, characterized by the fact that it also comprises a spun fabric.
[14]
Process for preparing a melt-blown fiber, as defined in claim 9 or 10, characterized in that a polypropylene (PP-C) composition, as defined in any of claims 1 to 8, has been melt-blown through the use of a blow fusion installation with a matrix with holes from 0.3 to 0.5 mm in diameter and 10 to 16 holes per cm.
[15]
15. Use of a polypropylene (B) having a fluidity index MFR2 (230 ° C), measured according to ISO 1133, equal to or less than 20 g / 10 min, in a polypropylene composition (PP-C2) presenting an MFR2 fluidity index (230 ° C), measured according to
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4/4 with ISO 1133, of at least 200 g / 10 min, characterized by the fact that it is to improve the stretching force of said polypropylene composition (PP-C2) expressed by the maximum air volume applicable during the processing of blow-melted fibers, and the improvement is defined by Formula (V) PP-2 / PP-1> 1.3 (V), in which
PP-2 is the maximum applicable air volume [m ³ / h] of the composition (PP-C2), which comprises polypropylene (B), and
PP-1 is the maximum applicable air volume [m ³ / h] of the composition (PP-C2), without polypropylene (B).
[16]
16. Use, according to claim 15, characterized by the fact that the composition (PP-C2) further comprises a polypropylene (A) presenting (i) a fluidity index MFR2 (230 ° C), measured according to ISO 1133, of at least 450 g / 10 min, and / or (ii) a molecular weight distribution (MWD), measured according to ISO 16014, not exceeding 3.5.
[17]
17. Use according to claim 15 or 16, characterized by the fact that:
(i) the polypropylene (PP-C2) composition is the polypropylene (PP-C) composition, as defined in any one of claims 1 to 8, and / or (ii) polypropylene (A) is further defined by any one of claims 1 to 8, and / or (iii) polypropylene (B) is further defined by any one of claims 1 to 8.

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JP2010537036A|2010-12-02|Compatibilized polyolefin composition

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BR0306556B1|2012-11-27|yarn nonwoven fiber, cast spinning process for the manufacture thereof, as well as compositions and processes for preparing said compositions.

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JP2012512919A|2012-06-07|Polyolefin fiber

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EP2133389A1|2009-12-16|Polypropylene composition

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JP4741818B2|2011-08-10|Polypropylene nonwoven fabric molding

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BR112014000025B1|2020-03-10|COPOLYMER OF PROPYLENE AND 1-HEXEN, FIBER AND NON-WOVEN FABRIC

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JP2003138460A|2003-05-14|Nonwoven polypropylene fabric for food packaging

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JP2022508335A|2022-01-19|Polyolefin fiber

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KR20200051498A|2020-05-13|Resin composition for bi-component fiber

同族专利:

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公开号 | 公开日

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BR112012011404A2|2016-04-19|

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US9234303B2|2016-01-12|

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EP2325248B1|2012-05-16|

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EP2325248A1|2011-05-25|

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PL2325248T3|2012-11-30|

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CN102597096B|2015-11-25|

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US20120270039A1|2012-10-25|

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WO2011058118A1|2011-05-19|

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CN102597096A|2012-07-18|

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法律状态:
2018-04-10| B06F| Objections, documents and/or translations needed after an examination request according art. 34 industrial property law|

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2019-07-09| B06T| Formal requirements before examination|

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2019-09-17| B15K| Others concerning applications: alteration of classification|Free format text: AS CLASSIFICACOES ANTERIORES ERAM: C08L 23/10 , D01F 6/46 Ipc: D01F 6/46 (1974.07), C08L 23/10 (1974.07), D01D 5/ |

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2020-02-27| B09A| Decision: intention to grant|

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2020-04-14| B16A| Patent or certificate of addition of invention granted|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 11/11/2010, OBSERVADAS AS CONDICOES LEGAIS. |

优先权:

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申请号 | 申请日 | 专利标题

---

EP09176063A|EP2325248B1|2009-11-16|2009-11-16|Melt blown fibers of polypropylene compositions|

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PCT/EP2010/067324|WO2011058118A1|2009-11-16|2010-11-11|Melt blown fibers of polypropylene compositions|

---