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    • 专利摘要:
    POLYPROPYLENE WITH HIGH RESISTANCE OF IMPROVED QUALITY CAST. Use of an additive mixture containing a linear polypropylene and at least one additive in a polypropylene composition comprising said additive mixture and a branched polypropylene to reduce the gel index of said polypropylene composition.
    公开号:BR112014030791B1
    申请号:R112014030791-1
    申请日:2013-06-26
    公开日:2020-12-22
    发明作者:Katja Klimke；Hermann Braun
    申请人:Borealis Ag；
    IPC主号:
    专利说明:

    [001] The present invention relates to a method that provides a polypropylene composition having a high melt strength and a low OCS gel index. In addition, the present invention also relates to a corresponding high melt strength polypropylene (HMS) composition, as well as the use of a specific linear polypropylene to reduce the OCS gel index of a polypropylene composition.
    [002] Compositions of high strength polypropylene from the melt (HMS-OO) are generally known in the art. However, an existing challenge in HMS-PP is its variation in film quality. The quality of the film is expressed by means of the gel index, which is measured with the OCS gel inspection tool as described in WO 2008/022802.
    [003] As is known in the art, additives are usually added to plastic materials in order to improve their performance. Examples of typical additives are, for example, antioxidants or pigments, etc. These additives are often added to the plastic base material in the form of an additive mixture that has the additives incorporated in a small amount of polymer powder. The additive mixture is sometimes also referred to as the "masterbatch" (plastic granules that contain a high concentration of additives and color pigments). The small amount of polymer powder used for mixing additives is usually dosed at the end of the HMS process. However, the contribution to the final gel index of this additive mixture is often overlooked. And, until now, it was thought that the gel index and, therefore, the film quality of the resulting material depended only on the manufacture of polypropylene with high melt strength, instead of the properties of the masterbatch.
    [004] The document EP 0 879 830, deposited by Borealis in 1997, describes the basic concepts of the Borealis process of high-resistance melt post-reactor (HMS) where peroxide and butadiene are used to obtain long chain branched polypropylene materials (LCB-PP). This patent covers a wide range of melt flow rates (MFRs) and particle sizes. However, it does not specify the impact of the PP powder used for the preparation of the additive mixture on the HMS quality, in particular, on the quality of the OCS film expressed through the gel index.
    [005] There remains a need in the art for a method to produce HMS-PP of reliable and / or improved quality.
    [006] Therefore, the aim of the present invention is to provide a process that allows a qualified person to produce the polypropylene composition and a film made of polypropylene with said low gel content composition.
    [007] The present inventors have now discovered, surprisingly, that the final gel index actually does not depend on the particle size of the powder and PSD used for mixing additives. Instead, it has been found that the final gel index can be significantly reduced by simply increasing the MFR of the powder used for mixing additives.
    [008] Thus, the present invention relates to a process for providing a polypropylene composition with high melt strength, the process comprising the steps of: (a) providing a branched polypropylene (b-PP) with a melt strength F30 more than 5.5 cN and a v30 melt extensibility of more than 200 mm / s, where the F30 melt strength and the v30 melt extensibility are measured according to ISO 16790: 2005; (b) addition to the branched polypropylene (b-PP) of a polypropylene (PP '), preferably a linear polypropylene (l-PP), with a melt flow MFR2 (230 ° C) from 1 to 18 g / 10 min.
    [009] The present invention further provides a polypropylene composition comprising: (a) 95 to 99 parts by weight of a branched polypropylene (b-PP); and (b) 1 to 5 parts by weight of a linear polypropylene (1-PP), which has a melt flow rate MFR2 (230 ° C), measured according to ISO 1133, from 1 to 18 g / 10 min., preferably 3 to 15 g / 10 min .; wherein the polypropylene composition has: an MFR2 melt flow rate (230 ° C), measured according to ISO 1133, from 8 to 12 g / 10 min., and a gel index of less than 1,500; and wherein, in addition, the polypropylene and / or branched polypropylene (b-PP) composition has a melt strength of F30 of more than 5.5 cN, preferably 5.8-13.0 cN, and an extensibility of cast v30 greater than 200 mm / s, preferably 230-290 mm / s, where the strength of cast F30 and the extensibility v30 are measured in accordance with ISO 16790: 2005.
    [010] The present invention further provides a polypropylene composition comprising: (a) 95-99 parts by weight of a branched polypropylene (b-PP); and (b) 1 to 5 parts by weight of a linear polypropylene (1-PP), which has a melt flow rate MFR2 (230 ° C), measured according to ISO 1133, from 1 to 18 g / 10 min., preferably 3 to 15 g / 10 min .; where the polypropylene composition has: - a melt flow rate MFR2 (230 ° C), measured according to ISO 1133, from 4 to less than 8 g / 10 min., preferably from 5 to less than 7 g / 10 min . and - a gel index of less than 1,300, preferably less than 1,000; and wherein, in addition, the polypropylene and / or branched polypropylene (b-PP) composition has a melt strength F30 of more than 5.5 cN, preferably more than 6.0 to 13.0 cN, and a extensibility of the cast v30 greater than 200 mm / s, preferably 230-290 mm / s, where the strength of the cast F30 and the extensibility v30 are measured according to ISO 16790: 2005.
    [011] The present invention also features a film comprising a corresponding polypropylene composition, as described above.
    [012] In addition, the present invention relates to the use of an additive mixture (AM) containing a linear polypropylene (1-PP) and at least one additive (A) in a polypropylene composition comprising said mixture of additives ( AM) and a branched polypropylene (b - PP) to reduce the index of said polypropylene gel composition or films obtained from said polypropylene composition, wherein: (a) the branched polypropylene and / or polypropylene composition (b -PP) showing a melt strength of F30 of more than 5.5 cN and a melt extensibility of v30 of more than 200 mm / s, in which melt strength of F30 and melt extensibility of v30 are measured according to ISO 16790: 2005 standard; (b) linear polypropylene (l-PP) has a melt flow rate MFR2 (230 ° C) measured according to ISO 1133 from 1 to 18 g / 10 min .; and (c) the at least one additive (A) is selected from the group consisting of antioxidants, metal deactivators, UV stabilizers, antistatic agents, antifogging agents, acid cleaners, blowing agents, capture agents, lubricants , nucleating agents, gliding agents, anti-blocking agents and their mixtures.
    [013] The invention will be described in more detail below.
    [014] First the individual components used will be described, that is, the branched polypropylene (b-PP), the polypropylene (PP '), as well as the linear polypropylene (1-PP), and the additives (A), used in present invention, as well as the polypropylene composition. Thereafter, the process and use of the invention will be described in more detail. However, any information or any preferred embodiment provided for the individual components or the polypropylene composition is also applicable to the process of the invention and use, if reference is made to the individual components of the composition and polypropylene, respectively.
    [015] The main component for the polypropylene composition to be supplied according to the invention is a branched polypropylene (b-PP). A branched polypropylene differs from a linear polypropylene in that the backbone of the polypropylene comprises side chains, while an unbranched polypropylene, that is, a linear polypropylene, does not cover side chains. The side chains have a significant impact on the polypropylene rheology. Thus, linear and branched polypropylenes can be clearly distinguished by their flow behavior under stress.
    [016] Branching can be achieved using specific catalysts, that is, single site specific catalysts, or by chemical modification. With regard to the preparation of a branched polypropylene obtained by the use of a specific catalyst, specific reference is made to EP 1 892 264. With regard to a branched polypropylene obtained by chemical modification, it is referred to in EP 0 879 830 A1 . In such a case, branched polypropylene is also called high strength polypropylene from the melt. Preferably, the branched polypropylene (b-PP) of the present invention is obtained by chemical modification, as described in more detail below and, therefore, is a high melt strength polypropylene (HMS-PP).
    [017] Therefore, the branched polypropylene (b-PP), preferably the high-strength melt polypropylene (HMS-PP), as the main component of the polypropylene composition has a melt strength of F30 of more than 5.5 cN and a v30 melt extensibility greater than 200 mm / s, preferably it has a F30 melt strength of more than 5.5 to 20.0 cN and a v30 melt extensibility of more than 200 to 300 mm / s, at in order to provide a resulting polypropylene composition with good shear thinning properties. The strength of the F30 cast and the extensibility of the v30 cast are measured according to ISO 16790: 2005.
    [018] Typically, the instant polypropylene composition also has an F30 melt strength of more than 5.5 cN and a v30 melt extensibility greater than 200 mm / s, preferably has an F30 melt strength of more than 5, 5 to 20.0 cN and an extensibility of the v30 melt of more than 200 to 300 mm / s.
    [019] In a preferred embodiment, the branched polypropylene (b-PP), preferably the high-strength melt polypropylene (HMS-PP), has: (a) a F30 melt strength of more than 5, 6 cN , as of more than 5, 6-20.0 cN, more preferably greater than 5.7 cN, even more preferably from 5.7 to 18.0 cN, even more preferably from 5.7 to 15.0 cN, even more preferably from 5.8 to 13.0 cN; and (b) an extensibility of the v30 melt of more than 210 to 300 mm / s, as well as of more than 220 to 300 mm / s, more preferably of more than 225 mm / s, even more preferably of 225 to 300 mm / s , even more preferably from 230 to 290 mm / s.
    [020] In the especially preferred embodiment, the branched polypropylene (b-PP), preferably the high strength polypropylene of the melt (HMS-PP), has a melt strength of F30 of more than 5.6 cN and an extensibility of the melt v30 of more than 210 to 300 mm / s, as a resistance of the F30 melt of more than 5.6-20.0 cN and extensibility of the v30 melt of more than 220 to 300 mm / s, more preferably a resistance of the F30 melt more than 5.7 cN and extensibility of the v30 melt of more than 225 mm / s, even more preferably a strength of the F30 melt of 5.7 to 18.0 cN and extensibility of the v30 melt of 225 to 300 mm / s , even more preferably a resistance of the F30 melt of 5.7 to 15.0 cN and extensibility of the v30 melt of 230 to 290 mm / s, even more preferably a resistance of the F30 melt of 5.8-12.0 cN and extensibility of the v30 cast from 230 to 290 mm / s.
    [021] In addition or alternatively, the branching index of the branched polypropylene (b-PP), preferably the high strength polypropylene of the melt (HMS-PP), can be further defined by the strain-hardening factor (SHF). It is therefore preferable that the branched polypropylene (b-PP), preferably the high melt polypropylene (HMS-PP), has a strain-hardening factor (SHF) of at least 1.7, more preferably of at least 1.9, even more preferably in the range of 1.9 to 7.0, even more preferably in the range of 1.9-6.5 measured at a strain rate of 3.0 s-1 and a strain Hencky's 2.5.
    [022] Furthermore, it is preferable that the said branched polypropylene (b-PP), preferably the high strength polypropylene of the melt (HMS-PP), has a melt flow MFR2 (230 ° C), measured according to the ISO 1133 standard of at least 2.0 g / 10 min., more preferably in a range of 2.0 to 40.0 g / 10 min., even more preferably in a range of 4.0 to 30.0 g / 10 min., Even more preferably in a range of 5.0 to 20.0 g / 10 min., As in the range of 7.0 to 13.0 g / 10 min., As 8.0 to 12.0 g / 10 min.
    [023] Thus, in a specific modality, the branched polypropylene (b-PP), preferably the high strength polypropylene of the melt (HMS-PP), presents: (d) an MFR2 melt flow rate (230 ° C) of at least 2.0 g / 10 min., preferably in a range of 2.0 to 40.0 g / 10 min., more preferably in a range of 4.0 to 30.0 g / 10 min., still more preferably in the range of 5.0 to 20.0 g / 10 min., even more preferably in the range of 7.0 to 13.0 g / 10 min., such as 8.0 to 12.0 g / 10 min. .; (e) a resistance of the F30 melt of more than 5.6 cN, as well as more than 5.6 to 20.0 cN, more preferably more than 5.7 cN, even more preferably 5.7 to 18, 0 cN, still more preferably from 5.7 to 15.0 cN, even more preferably from 5.8 to 13.0 cN, and (c) an extensibility of the v30 melt of more than 210 to 300 mm / s, as from more than 220 to 300 mm / s, more preferably from more than 225 mm / s, even more preferably from 225 to 300 mm / s, even more preferably from 230 to 290 mm / s.
    [024] Preferably the branched polypropylene (b-PP), preferably the high melt polypropylene (HMS-PP), has a melting point of at least 130 ° C, more preferably 135 ° C and more preferably at least 140 ° C. The crystallization temperature is preferably at least 120 ° C.
    [025] In addition, the branched polypropylene (b-PP), preferably the high strength melt polypropylene (HMS-PP), can be a random branched propylene copolymer (bR-PP), preferably a random propylene copolymer high melt strength (R-HMS-PP), or a branched propylene homopolymer (bH-PP), preferably high strength melt propylene homopolymer (H-HMS-PP), the latter being preferred.
    [026] For the purpose of the present invention, the term "propylene homopolymer" refers to a polypropylene that consists substantially, that is, of at least 97 mol%, preferably of at least 98 mol%, more preferably of at least 99 mol%, more preferably at least 99.8 mol% of propylene units. In a preferred embodiment, only the propylene units in the propylene homopolymer are detectable.
    [027] In the case of branched polypropylene (b-PP), preferably high melt polypropylene (HMS-PP), is a random branched propylene copolymer (bR-PP), preferably a random propylene copolymer of high melt strength (R-HMS-PP), which comprises monomers copolymerizable with propylene, for example, comonomers such as ethylene and / or α-olefins C4 to C12, in particular ethylene and / or α-olefins C4 to C10, for example, 1-butene and / or 1-hexene. Preferably, the branched random propylene copolymer (bR-PP), preferably the melt high strength random propylene copolymer (R-HMS-PP), comprises, especially consists of copolymerizable monomers with propylene from the group consisting of ethylene, 1-butene and 1 hexene. More specifically, the branched random propylene copolymer (bR-PP), preferably the high strength random propylene copolymer of the melt of (R-HMS-PP) comprises in addition to propylene - units derived from ethylene units and / or 1-butene. In a preferred embodiment, the branched random propylene copolymer (b-R-PP), preferably the melt high strength random propylene copolymer (R-HMS-PP), comprises units derivable only from ethylene and propylene. The comonomer content in the branched random propylene copolymer (bR-PP), preferably in the melt high strength random propylene copolymer (R-HMS-PP), is preferably in the range of more than 0.2 to 10, 0 mol%, even more preferably in the range of more than 0.5 to 7.0 mol%.
    [028] In this regard it should be mentioned that the polypropylene with high melt strength (HMS-PP) being either a propylene homopolymer with high melt strength (H-HMS-PP) or a random propylene copolymer with high strength of the melt (R-HMS-PP) may additionally comprise different unsaturated monomers for the comonomers defined for the high-strength random propylene copolymer of the melt (R-HMS-PP). In other words, the high melt strength propylene homopolymer (H-HMS-PP) or the high melt random propylene copolymer (R-HMS-PP) can comprise unsaturated monomers, such as, monomer (s) bifunctional unsaturated (s) and / or low molecular weight polymer (s) multifunctional non-unsaturated (s), as defined in detail below, being different for propylene, ethylene and other C4 to C12 α-olefins. Consequently, the definition of homopolymer and copolymer by virtue of high melt strength polypropylene (HMS-PP) actually refers to the unmodified polypropylene used to obtain high melt strength polypropylene (HMS-PP) by chemical modification , as defined in detail below.
    [029] As mentioned, branched polypropylene (b-PP), when used in the form of a polypropylene with high melt strength (HMS-PP) is a modified polypropylene. In this way, a polypropylene with high melt strength (HMS-PP) can be further defined by the shape obtained. High melt strength polypropylene (HMS-PP) is preferably the result of treating unmodified polypropylene with thermal decomposition radical forming agents and / or with ionizing radiation. However, in such a case, there is a high risk that unmodified polypropylene will be degraded, which is harmful. Thus, it is preferred that the modification is obtained by using bifunctional unsaturated monomer (s) and / or low molecular weight multifunctional unsaturated polymer (s) in the form of chemically bridged unit (s). 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 Patents are included in this document for reference. Thus, the amount of peroxide is preferably in the range of 0.05-3.00% by weight based on the unmodified polypropylene.
    [030] Therefore, in a preferred embodiment, polypropylene with high melt strength (HMS-PP) comprises: (a) if it consists of propylene homopolymer units with high melt strength (H-HMS-PP) derived (i) propylene and (ii) bifunctional unsaturated monomer (s) and / or multifunctional unsaturated low molecular weight polymer (s), or (b) if it consists of random propylene copolymer units with high melt strength (R-HMS-PP) derived from: (i) propylene (ii) ethylene and / or α-olefins C4 to C10, for example, 1-butene and / or 1-hexene, preferably ethylene, and (iii) bifunctional unsaturated monomer (s) and / or low molecular weight, multifunctional unsaturated polymer (s).
    [031] "Bifunctional unsaturated or multifunctional unsaturated", as used above, preferably means in the presence of two or more double non-aromatic bonds such as, for example, divinylbenzene or cyclopentadiene or polybutadiene. Only such bi- or multifunctional unsaturated compounds are used, which can preferably be polymerized with the aid of free radicals. The unsaturated sites in the bi- or multifunctional unsaturated compounds are in their chemically linked state not really "unsaturated", because the double bonds are used for each covalent bond to the unmodified polypropylene polymer chains.
    [032] The reaction of the multifunctional unsaturated bifunctional monomer (s) and / or multifunctional unsaturated low molecular weight polymer (s), preferably having a numerical average molecular weight (Mn) <10,000 g / mol, synthesized (s) from one and / or more monomers unsaturated with unmodified polypropylene can be carried out in the presence of a thermal free radical forming agent, for example, the decomposition of the free radical forming agent, such as a thermally decomposable peroxide and / or ionizing radiation or microwave radiation.
    [033] The bifunctional unsaturated monomers can be: divinyl compounds, such as divinylaniline, m-divinylbenzene, p-divinylbenzene, divinylpentane divinylpropane; (a) allyl compounds, such as allyl acrylate, allyl methacrylate, allyl maleate and methyl vinyl allyl ether; (b) dienes, such as 1,3-butadiene, chloroprene, cyclohexadiene, cyclopentadiene, 2,3-dimethylbutadiene, heptadiene, hexadiene, isoprene and 1,4-pentadiene; (c) aromatic and / or aliphatic bis (maleimide) bis (citradonimide) and / or mixtures of these unsaturated monomers. Especially preferred are the bifunctional unsaturated monomers 1,3-butadiene, isoprene, dimethyl butadiene and divinylbenzene.
    [034] The multifunctional unsaturated low molecular weight polymer, preferably having a numerical average molecular weight (Mn) ^ 10,000 g / mol can be synthesized from one or more unsaturated monomers.
    [035] Examples of such low molecular weight polymers are: (d) polybutadienes, especially where the microstructures differ from the polymer chain, that is, 1,4-cis, 1,4-trans and 1,2- (vinyl) they are predominantly in the 1,2- (vinyl) (e) butadiene and styrene copolymers having 1,2- (vinyl) in the polymer chain.
    [036] A preferred low molecular weight polymer is polybutadiene, in particular a polybutadiene having more than 50.0% by weight of butadiene in the 1,2- (vinyl) configuration.
    [037] Polypropylene with high melt strength (HMS-PP) may contain more than a bifunctional unsaturated monomer and / or a low molecular weight multifunctional unsaturated polymer. Even more preferred is the amount of bifunctional unsaturated monomer (s) and multifunctional unsaturated low molecular weight polymer (s) together in polypropylene with high melt strength (HMS-PP) 0.01 to 10, 0% by weight, based on said polypropylene with high melt strength (HMS-PP).
    [038] As noted above, it is preferable that the bifunctional unsaturated monomer (s) and / or multifunctional unsaturated low molecular weight polymer (s) be used in the presence of a free radical forming agent. thermal decomposition.
    [039] Peroxides are free radical forming agents of thermal decomposition. Most preferably, thermally decomposing free radical forming agents are selected from the group consisting of acyl peroxide, alkyl peroxide, hydroperoxide, perester and peroxycarbonate.
    [040] The peroxides listed below are specifically preferred: Acyl peroxides: benzoyl peroxide, 4-chlorobenzoyl peroxide, 3-methoxybenzoyl peroxide and / or methyl benzoyl peroxide. Alkyl peroxides: t-butyl allyl peroxide, 2,2-bis (t-butylperoxybutane), 1,1-bis (t-butylperoxy) -3,3,5-trimethylcyclohexane, n-butyl-4 valerate , 4-bis (t-butylperoxy), diisopropylaminomethyl-t-amyl peroxide, dimethylaminomethyl-t-amyl peroxide, diethylaminomethyl-t-butyl peroxide, dimethylaminomethyl-t-butyl peroxide, 1,1-di- (t- amylperoxy) cyclohexane, t-amyl peroxide, t-butylcumyl peroxide, t-butyl peroxide and / or 1-hydroxybutyl n-butyl peroxide. Peroxy peroxy and carbonates: butyl peracetate, cumila peracetate, cumila perpropionate, cyclohexyl peracetate, di-t-butyl peradipate, di-t-butyl perazelate, di-t-butyl perglutarate, di t-butyl, di-t-butyl persebacate, 4-nitrocumyl perpropionate, 1-phenylethyl perbenzoate, phenylethyl nitro-perbenzoate, t-butylbicyclo- (2,2,1) heptane, t-butyl perbutyrate percarboxylate 4-carbomethoxy, t-butylcyclobutane percarboxylate, t-butylcyclohexyl peroxycarboxylate, t-butylcyclopentyl percarboxylate, t-butylcyclopropane percarboxylate, t-butyldimethyl percinamate, t-butylvinyl 2- (2), butylvinyl perbenzoate t-butyl-4-methoxy perbenzoate, t-butyl perbenzoate, t-butylcarboxycyclohexane, t-butyl peptide, t-butyl peroxyisopropylcarbonate, t-butyl pertoluate, t-butyl-1-phenylcyclopropyl peroxycarboxylate, t butyl-2-propylperpentene-2-oate, t-butyl-1-methylcyclopropyl percarboxylate, peracetate t-butyl-4-nitrophenyl, t-butylnitrophenyl peroxycarbamate, t-butyl-N-succiimido peroxycarbamate, t-butyl percrotonate, t-butyl permaleic acid, t-butyl peretracrylate, t-butyl peracrylate and / or t-butyl perpropionate.
    [041] Mixtures of these free radical forming agents mentioned above are also contemplated.
    [042] Unmodified polypropylene for preparing such a high melt strength polypropylene (HMS-PP) preferably has an MFR2 melting flow rate (230 ° C) measured according to ISO 1133 in a range of 0.05 at 45.0 g / 10 min., more preferably in a range of 0.01 to 10.0 g / 10 min., even more preferably in a range of 0.01 to 1.0 g / 10 min., more preferably in a range of 0.01 to 0.5 g / 10 min.
    [043] Preferably, the unmodified polypropylene is a propylene homopolymer.
    [044] After preparation, polypropylene with high melt strength (HMS-PP) can be subjected to modification steps to further modify the polymer. Such modification steps include, for example, grafting, where one or more functional comonomers are grafted onto the polypropylene chain; and viscoreduction, in which the molecular weight of the polypropylene is reduced by combining polymer in the molten state in the extruder with a free radical generator, such as a peroxide. These steps are well known to those skilled in the art and references to them can be found in the literature.
    [045] The branched polypropylene (b-PP), preferably polypropylene with high melt strength (HMS-PP), is free of additives (A), as defined in more detail below.
    [046] The other important component of the present invention is polypropylene (PP '), preferably a linear polypropylene (l-PP), which must have an MFR2 melt flow rate (230 ° C), measured according to ISO 1133 from 1 to 18 g / 10 min., preferably from 3 to 15 g / 10 min., more preferably, from 4 to 15 g / 10 min., even more preferably from 5 to 13 g / 10 min.
    [047] As mentioned above, the term "linear" indicates that linear polypropylene (1-PP) does not have a structure without branches in the vicinity. Due to the absence of branches, linear polypropylene (1-PP) is preferably characterized by a low melt extensibility v30 and / or low melt strength F30. Thus, it is preferred that the linear polypropylene (1-PP) has: (f) a resistance of the F30 melt of more than 1.0 cN, preferably greater than 2.0 cN, more preferably in the range of 1.0- 65 cN, even more preferably in the range of 2.0-50 cN, such as in the range of 2.5 and 30 cN; and (g) a v30 melt extensibility of less than 200 mm / s, preferably below 190 mm / s, more preferably in the range of 100 to less than 200 mm / s, even more preferably in the range of 120-190 mm / s, even more preferably in the range of 120-175 mm / s, as in the range of 125-170 mm / s.
    [048] In other words, it is preferable that linear polypropylene (l-PP), has a melt strength of F30 of more than 1.0 cN and a melt extensibility of v30 below 200 mm / s, preferably a melt strength of F30 of more than 2.0 cN and melt extensibility of v30 below 190 mm / s, preferably melt strength of F30 in the range 1.0- 65 cN and melt extensibility of v30 in the range of 100 less than 200 mm / s, even more preferably a resistance of the F30 melt in the range of 2.0-50 cN and in the range of 120 to 190 mm / s, as well as a resistance of the F30 melt in the range 2.5 and 30 cN and an extensibility of the v30 melt in the range of 120 to 175 mm / s.
    [049] Therefore, in a specific modality of linear polypropylene (l-PP), it presents: (h) a flow rate of the melted MFR2 (230 ° C) from 1 to 18 g / 10 min., Preferably from 3 to 15 g / 10 min., More preferably, from 4 to 15 g / 10 min., Even more preferably from 5 to 13 g / 10 min .; (i) a resistance of the F30 melt of more than 1.0 cN, preferably greater than 2.0 cN, more preferably in the range of 1.0 to 65 cN, even more preferably in the range of 2.0 to 50 cN, such as in the range of 2.5 and 30 cN; and (j) a melt extensibility v30 of less than 200 mm / s, preferably below 190 mm / s, more preferably in the range of 100 to less than 200 mm / s, even more preferably in the range of 120 to 190 mm / s, more preferably in the range of 120 to 175 mm / s, as in the range of 125 to 170 mm / s.
    [050] Linear polypropylene (1-PP) can be produced in a known manner, using a single site catalyst or a Ziegler Natta catalyst. Linear polypropylene (1-PP) can be a linear propylene homopolymer (1-H-PP) or a linear propylene copolymer (1-R-PP). Regarding the comonomer content and type of comonomer see the information previously provided for branched polypropylene (b-PP). Preferably, linear polypropylene (1-PP) is a linear propylene homopolymer (1-H-PP).
    [051] As mentioned above, the main component of the polypropylene composition is branched polypropylene (b-PP), considering that linear polypropylene is present in lower quantities. It is therefore preferable that the polypropylene composition comprises: (k) 80 to 99 parts by weight, preferably 90 to 99 parts by weight, more preferably 95 to 99 parts by weight of the branched polypropylene (b-PP), preferably high-melt polypropylene (HMS-PP); and (l) 1 to 20 parts by weight, preferably 1 to 10 parts by weight, more preferably 1 to 5 parts by weight, of polypropylene (PP ') preferably of linear polypropylene (1-PP).
    [052] In a preferred embodiment, branched polypropylene (b-PP), that is, polypropylene with high melt strength (HMS-PP) and polypropylene (PP '), that is, linear polypropylene (l-PP) ), are the only components of the polymer in the polypropylene composition. In other words, the polypropylene composition may further comprise at least one additive (A), as defined in more detail below, but there are no other polymers in an amount greater than 5% by weight, more preferably greater than 2% by weight , even more preferably greater than 1% by weight, based on the total weight of the polypropylene composition. In a specific embodiment, the polypropylene composition consists of branched polypropylene (b-PP), preferably a polypropylene with high melt strength (HMS-PP), polypropylene (PP ') preferably linear polypropylene (l-PP) and at least one additive (A).
    [053] Illustrative additives (A) to be used in the polypropylene composition of the invention include, but are not limited to, stabilizers such as antioxidants (e.g., sterically hindered phenols, phosphites / phosphonites, sulfur-containing antioxidants, alkyl radical cleaners , aromatic amines, hindered amine stabilizers, or mixtures thereof, metal deactivators (for example, Irganox MD 1024), or UV stabilizers (for example, hindered amine light stabilizers). Other typical additives are modifiers, such as antistatic or anti-fog agents (for example, ethoxylated amines and amides or glycerol esters), acid cleaners (for example, Ca-esterarate), blowing agents, capture agents (for example, polyisobutene), lubricants and resins (ionomeric waxes, PE waxes and ethylene copolymer, Fischer-Tropsch waxes, Montana-based waxes, fluorine-based compounds or paraffin waxes), nucleating agents (eg talc, benzoates , phosphorus-based compounds, sorbitols, nonitol-based compounds or amide-based compounds), as well as glidants, anti-blocking agents (eg erucamide, oleamide, natural talc and synthetic silica or zeolites). Preferably additives (A) are selected from the group consisting of antioxidants (e.g., sterically hindered phenols, phosphites / phosphonites, sulfur-containing antioxidants, alkyl radical cleaners, aromatic amines, hindered amine stabilizers or combinations thereof), metal deactivators ( for example, Irganox MD 1024), or UV stabilizers (for example, hindered amine light stabilizers), antistatic or anti-fog agents (for example, ethoxylated amines and amides, or glycerol esters), acid cleaners (for example, Ca-stearate), blowing agents, capture agents (eg polyisobutene), lubricants and resins (ionomeric waxes, PE waxes and ethylene copolymer, Fischer-Tropsch waxes, Montana-based waxes, Montana-based compounds fluorine or paraffin waxes), nucleating agents (eg talc, benzoates, phosphorus-based compounds, sorbitols, nonitol-based compounds or amide-based compounds), as well as glide s, anti-blocking agents (eg, erucamide, oleamide, natural talc and synthetic silica or zeolites) and mixtures thereof.
    [054] Preferably the total amount of additives (A) in the polypropylene composition is not more than 5% by weight, more preferably not more than 1% by weight, such as in the range of 0.005 to 0.5% by weight, with based on the total weight of the polypropylene composition. Preferably, the additives (A) are introduced into the present polypropylene composition in the form of an additive mixture (AM). The additive mixture (AM) comprises and preferably consists of polypropylene (PP '), preferably linear polypropylene (1-PP) and additives (A). Typically, the total amount of additives in the additive mixture (AM) is not more than 25% by weight, more preferably not more than 20% by weight, such as, in the range of 5 to 20% by weight, based on weight total additive mixture (AM).
    [055] As mentioned above, branched polypropylene (b-PP), that is, preferably, high melt strength polypropylene (HMS-PP) is the dominant part in the present polypropylene composition. Therefore, it is preferable that the final polypropylene composition shows a rheological behavior similar to that of branched polypropylene (b-PP), that is, preferably, polypropylene with high melt strength (HMS-PP).
    [056] Thus, the present polypropylene composition has: (m) a resistance of the F30 melt of more than 5.6 cN, as well as of more than 5.6 to 20.0 cN, with more preference of more than 5.7 cN, even more preferably from 5.7 to 18.0 cN, even more preferably from 5.7 to 15.0 cN, even more preferably from 5.8 to 13.0 cN, and (n) a melt extensibility v30 of more than 210 to 300 mm / s, as well as of more than 220 to 300 mm / s, more preferably more than 225 mm / s, even more preferably from 225 to 300 mm / s, even more preferably from 230 to 290 mm / s.
    [057] In a preferred embodiment, the present polypropylene composition has a melt strength of F30 of more than 5.6 cN and an extensibility of melt v30 of more than 210 to 300 mm / s, such as a melt strength of F30 more than 5.6 to 20.0 cN and extensibility of the v30 melt of more than 220 to 300 mm / s, more preferably a strength of the F30 melt of more than 5.7 cN and extensibility of the v30 melt of more than 225 mm / s s, even more preferably a resistance of the F30 melt of 5.7 to 18.0 cN and extensibility of the v30 melt of 225 to 300 mm / s, even more preferably a resistance of the F30 melt of 5.7 to 15.0 cN and extensibility of the v30 melt from 230 to 290 mm / s, even more preferably a strength of the F30 melt of 5.8 to 12.0 cN and extensibility of the v30 melt from 230 to 290 mm / s.
    [058] In addition or alternatively to the branching index, the present polypropylene composition can be further defined by the strain hardening factor (SHF). Therefore, it is preferable that the present polypropylene composition has a strain-hardening factor (SHF) of at least 1.7, more preferably at least 1.9, even more preferably in the range of 1.9 to 7.0 , even more preferably in the range of 1.9 to 6.5 measured at a strain rate of 3.0 s-1 and a Hencky strain of 2.5. An essential finding of the present invention is that the present polypropylene composition and, therefore, the films obtained from said polypropylene composition (especially as defined below) show a reduced OCS gel index. It is therefore preferable that the present polypropylene composition has an OCS gel index of less than 1,500, preferably less than 1,000, more preferably in the range of 100 to 1,500, even more preferably in the range of 150 to 1,000, even more preferably in the range 200 to 800 range.
    [059] Preferably, the present polypropylene composition has a melt flow rate MFR2 (230 ° C), measured according to ISO 1133, of at least 2.0 g / 10 min., Preferably in a range of 2 , 0 to 40.0 g / 10 min., More preferably in a range of 4.0 to 30.0 g / 10 min., Even more preferably in a range of 5.0 to 20.0 g / 10 min. , even more preferably in the range of 7.0 to 13.0 g / 10 min., such as 8.0 to 12.0 g / 10 min. Thus, in a specific embodiment, the present polypropylene composition presents: (a) a flow rate of the melted MFR2 (230 ° C) of at least 2.0 g / 10 min., Preferably in a range of 2.0 to 40, 0 g / 10 min., More preferably in a range of 4.0 to 30.0 g / 10 min., Even more preferably in a range of 5.0 to 20.0 g / 10 min., Even more preferably in the range from 7.0 to 13.0 g / 10 min., such as 8.0 to 12.0 g / 10 min .; (b) a melt strength of F30 of more than 5.6 cN, such as more than 5.6 to 20.0 cN, more preferably more than 5.7 cN, even more preferably 5.7 to 18, 0 cN, even more preferably from 5.7 to 15.0 cN, even more preferably from 5.8 to 13.0 cN; and (c) an extensibility of the melt v30 of more than 210 to 300 mm / s, such as more than 220 to 300 mm / s, more preferably more than 225 mm / s, even more preferably 225 to 300 mm / s s, even more preferably from 230 to 290 mm / s. (d) 0] With the above information in mind, the present invention encompasses, for example, a polypropylene composition comprising: (a) 80 to 99 parts by weight, preferably 90 to 99 parts by weight, more preferably 95 to 99 parts by weight of the branched polypropylene (b-PP), preferably of the polypropylene with high melt strength (HMS-PP); (b) 1 to 20 parts by weight, preferably 1 to 10 parts by weight, more preferably 1 to 5 parts by weight of polypropylene (PP ') preferably of linear polypropylene (1-PP), having a melt flow rate MFR2 (230 ° C), measured according to ISO 1133 from 1 to 18 g / 10 min., Preferably from 3 to 15 g / 10 min., More preferably, from 4 to 15 g / 10 min., Even more preferably 5 to 13 g / 10 min .; and (c) optionally from 0.005 to 5, preferably from 0.005 to 2, more preferably from 0.05 to 1, such as 0.05 to 0.5, parts by weight of additives (A), wherein said additives (A) are selected from the group consisting of antioxidants, metal deactivators, UV stabilizers, antistatic agents, anti-fog agents, acid cleaners, blowing agents, capture agents, lubricants, nucleating agents, slip agents, anti-blocking agents and mixtures thereof; wherein the polypropylene composition has: - an MFR2 melt flow rate (230 ° C) of at least 2.0 g / 10 min., preferably in a range of 2.0 to 40.0 g / 10 min., more preferably in a range of 4.0 to 30.0 g / 10 min., even more preferably in a range of 5.0 to 20.0 g / 10 min., even more preferably in the range of 7.0 to 13 , 0 g / 10 min., Such as 8.0 to 12.0 g / 10 min .; and - a gel index of less than 1,500, preferably less than 1,000, more preferably in the range of 100 to 1,500, even more preferably in the range of 150 to 1,000, even more preferably in the range of 200 to 800; and where the composition of polypropylene and / or branched polypropylene (b-PP) has / has: - a resistance of the F30 melt of more than 5.6 cN, such as of more than 5.6 to 20.0 cN, more preferably from more than 5.7 cN, even more preferably from 5.7 to 18.0 cN, even more preferably from 5.7 to 15.0 cN, even more preferably from 5.8 to 13.0 cN, and an extensibility of the cast v30 of more than 210 to 300 mm / s, such as of more than 220 to 300 mm / s, more preferably of more than 225 mm / s, still more preferably of 225-300 mm / s, still more preferably from 230 to 290 mm / s.
    [060] With the above information in mind, the present invention encompasses, for example, a polypropylene composition comprising: (a) 80 to 99 parts by weight, preferably 90 to 99 parts by weight, more preferably 95 to 99 parts by weight of branched polypropylene (b-PP), preferably polypropylene with high melt strength (HMS-PP); b) 1 to 20 parts by weight, preferably 1 to 10 parts by weight, more preferably 1 to 5 parts by weight of polypropylene (PP ') preferably of linear polypropylene (1-PP), having a melt flow rate MFR2 ( 230 ° C), measured according to ISO 1133 from 1 to 18 g / 10 min., Preferably from 3 to 15 g / 10 min., More preferably from 4 to 15 g / 10 min., Even more preferably from 5 to 13 g / 10 min .; and (c) optionally from 0.005 to 5, preferably from 0.005 to 2, more preferably from 0.05 to 1, such as 0.05 to 0.5, parts by weight of additives (A), wherein said additives (A) are selected from the group consisting of antioxidants, metal deactivators, UV stabilizers, antistatic agents, anti-fog agents, acid cleaners, blowing agents, capture agents, lubricants, nucleating agents, slip agents, anti-blocking agents and mixtures thereof; wherein the polypropylene composition has: - an MFR2 melt flow rate (230 ° C) of at least 2.0 g / 10 min., preferably in a range of 2.0 to 40.0 g / 10 min., more preferably in a range of 4.0 to 30.0 g / 10 min., even more preferably in a range of 5.0 to 20.0 g / 10 min., even more preferably in the range of 7.0 to 13 , 0 g / 10 min., Such as 8.0 to 12.0 g / 10 min .; and - a gel index of less than 1,500, preferably less than 1,000, more preferably in the range of 100 to 1,500, even more preferably in the range of 150 to 1,000, even more preferably in the range of 200 to 800; and where the composition of polypropylene and / or branched polypropylene (b-PP) has / has: - a resistance of the F30 melt of more than 5.6 cN, such as of more than 5.6 to 20.0 cN, more preferably from more than 5.7 cN, even more preferably from 5.7 to 18.0 cN, even more preferably from 5.7 to 15.0 cN, even more preferably from 5.8 to 13.0 cN, and an extensibility of the cast v30 of more than 210 to 300 mm / s, such as of more than 220 to 300 mm / s, more preferably of more than 225 mm / s, still more preferably of 225-300 mm / s, still more preferably from 230 to 290 mm / s.
    [061] As mentioned above, the present invention also features a polypropylene film comprising the present composition described in the present document. Preferably the film is a fused film or a blown film. The film can also be a bi-oriented blown film. The differences between these films are known to those skilled in the art. Reference is made to the "Polypropylene Handbook", 2nd Edition, Nello Pasquini (Ed.), Hanser. Preferably, the film comprises at least 70% by weight, more preferably at least 80% by weight, more preferably at least 90% by weight, even more preferably at least 95% by weight of the present invention. In a preferred embodiment, the film is comprised of the present polypropylene composition.
    [062] Preferably, the present film has an OCS gel index of less than 1,500, preferably less than 1,000, more preferably in the range of 100 to 1,500, even more preferably in the range of 150 to 1,000, even more preferably in the range of 200 to 800.
    [063] The present process for the manufacture of the polypropylene composition comprises the supply of branched polypropylene (b-PP) (step (a)), followed by the addition of polypropylene (PP '), preferably linear polypropylene (1-PP) ), optionally together with at least one additive (A) to the branched polypropylene (b-PP) (step (b)). Preferably, the polypropylene (PP ') preferably the linear polypropylene (1-PP), and the at least one additive are added to the branched polypropylene (b-PP), in the form of the additive mixture (AM).
    [064] Preferably step (b) is started when at least 70%, preferably at least 80%, even more preferably at least 90%, such as at least 95% or 99% of the reaction between polypropylene (PP) and the thermal decomposition free radical forming agent and, optionally, the bifunctional unsaturated monomer happened to obtain the branched polypropylene (b-PP), preferably the polypropylene with high melt strength (HMS-PP).
    [065] In a preferred embodiment, an extruder, such as a twin screw extruder, is used for the addition of polypropylene (PP '), preferably linear polypropylene (1-PP), to branched polypropylene (b-PP) .
    [066] The use of an extruder is particularly advantageous, as it can be used simultaneously for the preparation of branched propylene (b-PP), preferably polypropylene with high melt strength (HMS-PP). In a preferred embodiment, (unmodified) polypropylene is added to an extruder together with - as described in details above - a free radical-forming person of thermal decomposition, preferably a peroxide, and optionally a bifunctional, preferably unsaturated monomer , selected from divinyl compounds, allyl compounds or dienes, to obtain branched polypropylene (b-PP), preferably polypropylene with high melt strength (HMS-PP), in one step (a). It is also possible to use a combination of an extruder downstream of a premixing device, in which the bifunctional unsaturated monomer and thermal decomposition free radical forming agent are added to the polypropylene in the premixing device. Subsequently, in a step (b), the polypropylene (PP ') preferably the linear polypropylene (1-PP), or the mixture of additives (AM) based on said polypropylene (PP'), preferably on said linear polypropylene (1-PP), which comprises at least one additive (A) is preferably added to the downstream end of the extruder spindle, in order not to interfere with the modification reaction to provide branched polypropylene (b-PP), preferably the polypropylene with high melt strength (HMS-PP), as described above. In this regard, the term "extruder spindle end" is understood to be the last within 60% of the extruder spindle length, preferably within the last 60% of the extruder spindle length, more preferably at least 70 % of the extruder spindle length, such as at least 75% of the extruder spindle.
    [067] Therefore, the extruder (E) used for the present process preferably comprises, in the direction of operation, a feed throat (FT), a first mixing zone (MZ1), a second mixing zone (MZ2) and a matrix (D), in which a side feed throat (SFT) is located between the first mixing zone (MZ1) and the second mixing zone (MZ2). Preferably, the extruder is a screw extruder, like a double screw extruder. Therefore, the unmodified polypropylene, the free radical forming agent of thermal decomposition, preferably a peroxide, and optionally the bifunctional unsaturated monomer and / or the monomer of the multifunctional unsaturated low molecular weight polymer, preferably selected from from divinyl compounds, allyl compounds or dienes, but not polypropylene (PP '), that is, not linear polypropylene (1-PP), and not additives (A), are fed through the feed throat (FT) , therefore preferably using a feeder, in the extruder and is / are subsequently passed downstream through the first mixing zone (MZ1). Preferably, the shear stress in said first mixing zone (MZ1) is such that the unmodified polypropylene is melted and the chemical reaction with the radical forming agent and the optional bifunctional unsaturated monomer and / or the polymer of lower molecular weight multifunctional unsaturated. After the first mixing zone (MZ1), that is, between the first mixing zone (MZ1) and the second mixing zone (MZ2), polypropylene (PP '), preferably linear polypropylene (l-PP) or the additive mixture (AM) is added, that is, fed into the extruder. Preferably, polypropylene (PP '), preferably linear polypropylene (1-PP), or the mixture of additives (AM) is added through the side feed throat (SFT), thereby preferably using a side feeder. Subsequently, all components of the polypropylene composition, including polypropylene (PP '), preferably linear polypropylene (1-PP), or the additive mixture (AM) are passed downstream through the second mixing zone (MZ2) . Finally, the polypropylene composition is discharged through the matrix (D).
    [068] Preferably, the first mixing zone (MZ1) is longer than the second mixing zone (MZ2). Preferably, the length ratio between the first mixing zone (MZ1) to the second mixing zone of the mixing zone (MZ2) [mm (MZ1) / mm (MZ2)] is at least 2/1, more preferably 3/1, even more preferably in the range of 2/1 to 15/1, even more preferably from 3/1 to 10/1.
    [069] Film preparation is a procedure known in the art. For example, the film can be produced by molded film or blown film technology. In molded film technology the molten polypropylene composition is extruded through a slit extrusion die on the cooling roll to cool the polymer to a solid film. Typically, the polypropylene composition is first compressed and liquefied in an extruder, and it is possible that any additives are already added to the polymer or introduced at this stage through a masterbatch. The melt is then forced through a flat die matrix (slot die), and the extruded film is removed on one or more take-off rolls, during which it cools and solidifies. It has proved to be particularly favorable to keep the peel roll or rollers, whereby the extruded film is cooled and solidified, at a temperature of 10 to 50 ° C, preferably from 10 to 40 ° C, more preferably between 12 and 35 ° C. The product obtained is an unstretched film that can be desirably stretched biaxially.
    [070] In the blowing process of polypropylene film the composition is extruded through an annular matrix and blown into a tubular film by the formation of a bubble, which is collected between the tightening rollers after solidification. Blow extrusion can be carried out preferably at a temperature in the range 160-240 ° C, and cooled by water or preferably by blowing gas (usually air) at a temperature of 10 to 50 ° C to provide a line height freezing 0.5 to 8 times the diameter of the matrix. The blowing ratio would generally be in the range of 1.5 to 4, such as 2 to 4, preferably 2.5 to 3.5.
    [071] Finally, the present invention is also directed to the use of the additive mixture (AM) containing a polypropylene (PP '), preferably a linear polypropylene (1-PP), and at least one additive (A) in a polypropylene comprising said additive mixture (AM) composition and a branched polypropylene (b-PP) to reduce the index of said polypropylene gel composition or films obtained from said polypropylene composition, wherein: (a) the composition polypropylene and / or branched polypropylene (b-PP) (such as polypropylene with high melt strength (PP)) has / have (a1) a F30 melt strength of more than 5.6 cN, as well as more than 5 , 6 to 20.0 cN, more preferably more than 5.7 cN, even more preferably from 5.7 to 18.0 cN, even more preferably from 5.7 to 15.0 cN, even more preferably from 5.8 to 13.0 cN, and (a2) an extensibility of the v30 melt of more than 210 to 300 mm / s, as well as of more than 220 to 300 mm / s, more preferably more than 225 mm / s, even more preferably 225 to 300 mm / s, even more preferably 230 to 290 mm / s; (b) polypropylene (PP '), preferably linear polypropylene (1-PP), has a melt flow rate MFR2 (230 ° C) of 1 to 18 g / 10 min., preferably 3 to 15 g / 10 min., More preferably, from 4 to 15 g / 10 min., Even more preferably from 5 to 13 g / 10 min .; and (c) the at least one additive (A) is selected from the group consisting of antioxidants, metal deactivators, UV stabilizers, antistatic agents, anti-fog agents, acid cleaners, blowing agents, capture agents, lubricants, nucleating agents, gliding agents, anti-blocking agents and mixtures thereof.
    [072] Preferably, the reduction of the gel index is obtained in the case of the polypropylene composition or film manufactured from the polypropylene composition having an OCS gel index less than 1,500, preferably less than 1,000, more preferably in the range of 100 to 1,500, even more preferably in the range of 150 to 1,000, even more preferably in the range of 200 to 800.
    [073] With regard to the individual components and the final polypropylene composition, reference is made to the information provided above.
    [074] In the following, the present invention is described in more detail by way of examples. EXAMPLES A. Measurement Methods
    [075] The following definitions of the terms and methods of determination apply to the general description of the invention above, as well as to the examples below, unless otherwise defined. Polypropylene comonomer content
    [076] The comonomer content is determined by Fourier Transform Infrared Spectroscopy (FTIR) analysis after the basic assignment calibrated via 13C nuclear magnetic resonance (NMR) spectroscopy, in a manner well known in the art. Thin films are pressed to a thickness of 250 μm and spectra recorded in transmission mode.
    [077] Specifically, the ethylene content of a polypropylene-ketylene copolymer is determined using the baseline corrected peak area of the quantitative bands found at 720-722 and 730-733 cm-1. Propylene-1-butene copolymers were evaluated at 767 cm-1. Quantitative results are obtained based on the reference to the film thickness. Melting temperature (Tm) and heat of fusion (Hf), temperature of crystallization (Tc) and heat of crystallization (Hc)
    [078] Those cited immediately above were measured with Mettler TA820 differential scanning calorimetry (DSC) in samples of 5 to 10 mg. DSC is performed according to ISO 3146 / part 3 / method C2 in a heat / cold / heat cycle with a scanning speed of 10 ° C / min. in the temperature range from +23 to 210 ° C. Crystallization temperature and crystallization heat (Hc) are determined from the cooling step, while the melting temperature and melting heat (Hf) are determined from the second heating step.
    [079] MFR2 (230 ° C) is measured according to ISO 1133 (230 ° C, 2.16 kg load). Strain hardening factor (SHF)
    [080] The deformation hardening factor is defined as:
    where: é ^ is the uniaxial extensional viscosity; and ^ LVE ^ is three times the time-dependent shear viscosity '! (/) in the linear deformation range.
    [081] The determination of the linear viscoelastic envelope in the ^ ZKE ^ extension using IRIS Rheo Hub 2008, required the calculation of the separate relaxation time spectrum from the storage data and loss module (G ', G "(w). Linear viscoelastic data (G ', G "(w) are obtained by scanning frequency measurements carried out at 180 ° C for polypropylene or 140 ° C for polyethylene, on an Anton Paar MCR 300, coupled to the parallel plates of 25 The basic calculation principles used to determine the separate relaxation spectrum are described in Baumgartel M, Winter HH, "Determination of the discrete relaxation and retardation time spectra from dynamic mechanical data", Rheol. Acta 28: 511519 (1989 ) which is incorporated as a reference in its entirety. IRIS RheoHub 2008 expresses the relaxation time spectrum as a sum of the N Maxwell modes:
    where gi and Ài are material parameters and Ge is the equilibrium module. The choice for the maximum number of modes, N used to determine the separate relaxation spectrum, is made using the "optimal" option of the 2008 IRIS RheoHub. The equilibrium module Ge has been set to zero. The non-linear adjustment used to obtain 'L;1'1 is performed on the IRIS Rheo Hub 2008, using the Doi-Edwards model. The uniaxial extensional viscosity, 'l / e'-1 is obtained from uniaxial extensional flow measurements, conducted on an Anton Paar MCR 501 coupled with the Sentmanat extensional device (SER-1). The temperature for uniaxial extension flow measurements was fixed at 180 ° C, applying extension rates (deformation) (, i-'rt ranging from 0.3 s-1 to 10 s-1 and covering a Hencky deformation range :
    with I0 being the original and I the actual fixing length of the sample from 0.3 to 3.0. Special care was taken with the preparation of the samples for the extensional flow. The samples were prepared by compression molding at 230 ° C followed by slow cooling to room temperature (forced water or air cooling was not used). This procedure allowed to obtain well-formed samples free from residual stresses. The sample was left for a few minutes at the test temperature to ensure thermal stability (set temperature ± 0.1 ° C), before performing uniaxial extensional flow measurements. F30 cast strength and v30 cast extensibility
    [082] The test described in this document follows the ISO 16790: 2005 standard.
    [083] The deformation hardening behavior is determined by the method described in the article "Rheotens-Mastercurves and Drawability of Polymer Melts", M.H. Wagner, Polymer Engineering and Sience, Vol. 36, pages 925-935. The content of the document was included as a reference. The behavior of polymer deformation hardening is analyzed by Rheotens apparatus (product of Gottfert, Siemensstr.2, 74711 Buchen, Germany) in which a molten filament is elongated by dragging downwards with a defined acceleration.
    [084] The Rheotens experiment simulates industrial rotation and extrusion processes. In principle, a melt is pressed or extruded through a round die and the resulting filament is removed. The stress on the extrudate is recorded as a function of the melting properties and measurement parameters (especially the relationship between production and withdrawal speed, which is practically a measure of the extension rate). For the results presented below, the materials were extruded with a laboratory extruder system HAAKE Polylab and a gear pump with cylindrical matrix (L / D = 6.0 / 2.0 mm). The gear pump was preset to a filament extrusion rate of 5 mm / s, and the melting temperature was set to 200 ° C. The length of the spinning line between the die and the Rheotens wheels was 80 mm. At the beginning of the experiment, the speed of removal of the Rheotens wheels was adjusted to the speed of the extruded polymer filament (zero tension force): Then, the experiment was started with the slow increase of the speed of removal of the Rheotens wheels until the polymer filament breaks. The acceleration of the wheels was sufficiently small, so that the tractive force was measured under quasi-stationary conditions. The drag acceleration of the molten filament is 120 mm / s2. 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 traction force and drag speed. The end points of the Rheotens curve (force versus speed of rotation of the pulley) are taken as the resistance of the F30 cast and values of drag capacity. OCS gel index 1. Apparatus
    [085] The device consists of a laboratory extruder ME 25/5200 VI with three heating zones, an adapter and a 150 mm wide die. The monitoring unit comprises a 140mm diameter CR-8 chillroll, including a Haake C40P heating and cooling device (15 to 90 ° C), an FS -5/4096 Pixel inline scanning camera (dynamic digital image conversion) grayscale) and a fan unit with automatic voltage control up to 10 N. 3. Specific material configurations for film making
    [086] The temperature adjustment for the heating zones in the cylinder and matrix is classified for polypropylene according to the MFR ranges in three groups: Group 1: MFR-range of 0.3-2.0 g / 10 min . (230 ° C / 2.16 kg), temperatures of 220/260/270/280/290 ° C Group 2: MFR-range of 2.0-10 g / 10 min. (230 ° C / 2.16 kg), temperatures 220/230/240/250/260 ° C Group 3: MFR-range 10-33 g / 10 min. (230 ° C / 2.16 kg), temperatures of 200/220/230/240/240 ° C
    [087] Predefined parameters: Rotation speed (spindle): 30 rpm Withdrawal speed: 3 m / min .; The film thickness is 50 μm. 4. Measurement
    [088] After compliance with the following parameters: In the case of similar materials, an operating period of about 60 min., In the case of highly divergent materials, approximately 120 minutes.
    [089] Objective: Adjust a homogeneous film at constant melting pressure and melt temperature. The measurement area is standardized at 5 m2. The measurement itself is automatically terminated when the area is completed. The report will be printed simultaneously. 5. Analysis
    [090] The number of defects found is, with reference to 1 / m2, divided into classes according to size and multiplied with the mass factor adding up to the gel index. Size class 1 100-300 μm mass factor x 0.1 Size class 2 301-600 μm mass factor x 1.0 Size class 3 601-1,000 μm mass factor x 5.0 Size class 4> 1,000 μm factor mass x 10 Example: 17 defects size class 1 x 0.1 = 1.7 5 defects size class 2 x 1.0 = 5.0 2 defects size class 3 x 5.0 = 10.0 0 defect class size 4 x 10.0 = 0 Gel index = 16.7 B. Examples Linear polypropylene (l-PP)
    [091] 1-PP1 is a linear propylene homopolymer with an MFR2 (230 ° C) of 0.37 g / 10 min., At a melting temperature Tm of 164 ° C, a melt strength of F30 of 68 cN and 146 mm / s cast v30 extensibility.
    [092] 1-PP2 is a linear propylene homopolymer with an MFR2 (230 ° C) of 3.48 g / 10 min., At a melting temperature Tm of 160 ° C, a melt strength of F30 of 6.5 cN and extensibility of the 160 mm / s v30 cast.
    [093] l-PP3 is a linear propylene homopolymer with an MFR2 (230 ° C) of 9.18 g / 10 min., A melting temperature Tm of 162 ° C, a melt strength of F30 of 3.0 cN and extensibility of the 160 mm / s v30 cast. Mixtures of additives
    [094] Linear polypropylenes 1-PPL, 1-PP2 and 1-PP3 were used to provide mixtures of additives containing other additives, such as masterbatch, for incorporation into a branched polypropylene based polymer. The additive mixtures each contain 87.50% by weight of the respective linear polypropylene, 10.00% by weight of Irganox B 225 FF (antioxidant), and 2.50% by weight of hydrotalcite. A summary of the properties of the resulting additive mixtures 1 to 3 is given in Table 1 which follows Table 1: Properties of the additive mixtures
    Examples IE1 to IE4 of the Invention and Comparative Examples CE1 and CE2:
    [095] l-PP1 was subjected to reactive extrusion in the presence of butadiene and peroxide as described below. Both butadiene and peroxide (the values are shown in Table 3) were pre-mixed with 1-PP1 powder before the melt mixing step in a horizontal mixer with paddle shaker at a temperature of 65 ° C, maintaining an average residence time of 15 to 20 minutes. The premix was transferred under an inert atmosphere to a corotative double screw extruder of the type Theyson TSK60 having a drum diameter of 60 mm and an L / D ratio sw 48 equipped with a high intensity mixing spindle with 3 kneading zones. and a two-step degassing configuration. The melting temperature profile is given in table 2. The spindle speed and yield are shown in table 3. In the first 3/4 of the length of the extruder, branched polypropylene is produced (b-PP). Subsequently, by means of a side feeder, that is, in the last 1/4 of the length of the extruder, an additive mixture, as defined in Table 1, is fed to the extruder to the branched polypropylene produced (b-PP). The extruded polypropylene composition was discharged and micronized. From these microspheres, films were produced as described above (OCS gel index). The final properties are shown in table 4. Table 2: Adjusting the temperature profile in the extruder
    Table 3: Process conditions
    Table 4: Properties of the polypropylene composition

    [096] A suitable polypropylene composition having a high melt strength can be prepared by incorporating an additive mixture like a masterbatch into a branched polypropylene. When using a masterbatch (additive mixture) having a higher melt flow rate, the resulting polypropylene composition has a low OCS gel index and, therefore, the favorable optical appearance. Additional experiments have shown that additive mixtures do not affect the values of MFR2, F30 and v30, however much of the OCS gel index negatively. All examples in which the branched polypropylene was not combined with additive mixtures 1 to 3 show the same values for MFR2, F30 and v30.
    权利要求:
    Claims (18)
    [0001]
    1. Process for obtaining a polypropylene composition with a high melt strength, the process characterized by the fact that it comprises the steps of: (a) providing 95 to 99 parts by weight of a branched polypropylene (b-PP) with a F30 melt strength of more than 5.5 cN and a v30 melt extensibility of more than 200 mm / s, where the F30 melt strength and the v30 melt extensibility are measured according to ISO 16790: 2005 , wherein the branched polypropylene (b-PP) is supplied by the reaction of polypropylene with a free radical-forming agent of thermal decomposition; (b) addition to the branched polypropylene (b-PP) of 1 to 5 parts by weight of a linear polypropylene (1-PP), with a melt flow MFR2 (230 ° C) of 1 to 18 g / 10 min.
    [0002]
    2. Process according to claim 1, characterized by the fact that the branched polypropylene (b-PP) is provided by reaction of a polypropylene (PP) with a peroxide, and / or, optionally, the preferably selected bifunctional unsaturated monomer divinyl compounds, allyl compounds or dienes, thereby obtaining branched polypropylene (b-PP).
    [0003]
    3. Process according to claim 1 or 2, characterized by the fact that step (b) is initiated when at least 80% of the reaction between the polypropylene (PP) and the free radical forming agent occurs thermal decomposition and optionally the bifunctional unsaturated monomer.
    [0004]
    4. Process according to any of claims 1 to 3, characterized by the fact that steps (a) and (b) are carried out in an extruder, said extruder comprises, in the direction of operation, a first mixing zone (MZ1) and a second mixing zone (MZ2), in which step (a) additionally is carried out in the first mixing zone (MZ1), while step (b) takes place in the second mixing zone (MZ2).
    [0005]
    5. Process according to claim 4, characterized by the fact that the extruder comprises in the direction of operation a feed throat (FT), the first mixing zone (MZ1), the second mixing zone (MZ2) and a matrix (D), in which between the first mixing zone (MZ1) and the second mixing zone (MZ2) is located a side feed throat (SFT), in which, in addition, polypropylene (PP), the free radical formation of thermal decomposition and, optionally, the bifunctional unsaturated monomer are fed through the feed throat (FT) and the linear polypropylene (l-PP) is fed through the side feed throat (SFT).
    [0006]
    6. Process according to claim 4 or 5, characterized by the fact that: (a) the reaction between the polypropylene (PP) and the thermal decomposition free radical forming agent and, optionally, the bifunctional unsaturated monomer is performed in the first mixing zone (MZ1); and / or (b) no more than 10% by weight of the total amount of the branched polypropylene (b-PP) of the polypropylene composition is produced in the second mixing zone (MZ2).
    [0007]
    Process according to any one of the preceding claims, characterized in that 1 to 3 parts by weight of linear polypropylene (1-PP) are added to 97 to 99 parts by weight of branched polypropylene (b-PP), more preferably, in which 2 parts by weight of linear polypropylene (1-PP) are added to 98 parts by weight of branched polypropylene (b-PP).
    [0008]
    8. Process according to any of the preceding claims, characterized by the fact that: (a) linear polypropylene (l-PP) comprises at least one additive (A) selected from the group consisting of antioxidants, metal deactivators , UV stabilizers, antistatic agents, anti-fog agents, acid cleaners, blowing agents, capture agents, lubricants, nucleating agents, slip agents, anti-blocking agents and mixtures thereof, and / or (b) branched polypropylene ( b-PP) is free of additives (A).
    [0009]
    Process according to any one of the preceding claims, characterized by the fact that the resulting propylene composition has: (a) melt strength of F30 of more than 5.5 cN and melt extensibility of v30 greater than 200 mm / s, where the strength of the F30 cast and the extensibility of the v30 cast are measured according to ISO 16790: 2005; and / or (b) a gel index of less than 1,500.
    [0010]
    10. Polypropylene composition, characterized by the fact that it comprises: (a) 95 to 99 parts by weight of a branched polypropylene (b-PP) obtainable by reaction of a polypropylene (PP) with a free radical-forming agent of thermal decomposition ; and (b) 1 to 5 parts by weight of a linear polypropylene (1-PP), which has a melt flow rate MFR2 (230 ° C), measured according to ISO 1133 from 1 to 18 g / 10 min., preferably 3 to 15 g / 10 min .; where the polypropylene composition has: - a flow rate of the melted MFR2 (230 ° C), measured according to ISO 1133, from 8 to 13 g / 10 min., and - a gel index of less than 1,500; and wherein in addition the composition of polypropylene and / or branched polypropylene (b-PP) has: a resistance of the F30 melt of more than 5.5 cN, preferably from 5.8 to 13.0 cN, and - an extensibility of the v30 melt of more than 210 to 300 mm / s, preferably from 230 to 290 mm / s, where the strength of the F30 melt and the extensibility of the v30 melt are measured according to ISO 16790: 2005.
    [0011]
    11. Polypropylene composition, characterized by the fact that it comprises: (a) 95 to 99 parts by weight of a branched polypropylene (b-PP) obtainable by reaction of a polypropylene (PP) with a free radical-forming agent of thermal decomposition ; and (b) from 1 to 5 parts by weight of a linear polypropylene (1-PP), which has a melt flow rate MFR2 (230 ° C), measured according to ISO 1133, from 1 to 18 g / 10 min. , preferably from 3 to 15 g / 10 min .; where the composition has polypropylene has: - an MFR2 melt flow rate (230 ° C), measured according to ISO 1133, from 4 to less than 8 g / 10 min., and a gel index of less than 1,300 ; and wherein in addition the composition of polypropylene and / or branched polypropylene (b-PP) has: - a melt strength of F30 of more than 5.5 cN, preferably more than 6.0-13.0 cN, and - a extensibility of the v30 melt greater than 200 mm / s, preferably from 230 to 290 mm / s, in which the strength of the F30 melt and the extensibility of the v30 melt are measured according to ISO 16790: 2005.
    [0012]
    12. Polypropylene composition according to claim 10 or 11, characterized in that the polypropylene composition comprises at least one additive (A) selected from the group consisting of antioxidants, metal deactivators, UV stabilizers , antistatic agents, anti-fog agents, acid cleaners, blowing agents, capture agents, lubricants, nucleating agents, gliding agents, anti-blocking agents and mixtures thereof.
    [0013]
    13. Process according to any one of claims 1 to 9, or polypropylene composition according to any one of claims 10 to 12, characterized in that the composition of propylene and / or branched polypropylene (b-PP ) have a strain-hardening factor (SHF) of at least 1.9, preferably in the range of 1.9 to 7.0, more preferably in the range of 1.9 to 6.5, measured at a strain rate 3.0 s-1 and a Hencky strain of 2.5.
    [0014]
    Process according to any one of claims 1 to 9, or propylene composition according to claim 10 or 11, characterized in that the linear polypropylene (l-PP) has a melt flow MFR2 (230 ° C) from 3 to 15 g / 10 min., Preferably 4 to 15 g / 10 min., More preferably from 5 to 13 g / 10 min.
    [0015]
    15. Film characterized by the fact that it comprises the polypropylene composition defined in any one of the preceding claims 10 to 12.
    [0016]
    16. Use of an additive mixture (AM) containing a linear polypropylene (1-PP) and at least one additive (A) in a polypropylene composition comprising said mixture of additives (AM) and a branched polypropylene (b-PP) ) characterized by the fact that it is to reduce the gel index of said polypropylene composition or films obtained from said polypropylene composition, in which: (a) the composition of polypropylene and / or branched polypropylene (b-PP) has a melt strength of F30 of more than 5.5 cN and a melt extensibility of v30 greater than 200 mm / s, where melt strength of F30 and melt extensibility of v30 are measured according to ISO 16790: 2005, (b) linear polypropylene (l-PP), has a melt flow MFR2 (230 ° C) measured according to ISO 1133, from 1 to 18 g / 10 min., and (c) at least one additive ( A) is selected from the group consisting of antioxidants, metal deactivators, UV stabilizers, anti-aging agents static agents, anti-fog agents, acid cleaners, blowing agents, capture agents, lubricants, nucleating agents, gliding agents, anti-blocking agents and mixtures thereof, and (d) the polypropylene composition comprises 95 to 99 parts of the branched polypropylene (b-PP) and 1 to 5 parts of linear polypropylene (1-PP).
    [0017]
    17. Use according to claim 16, characterized by the fact that the gel reduction index is obtained in the case of the polypropylene composition or film manufactured from the polypropylene composition having a gel index of less than 1,500.
    [0018]
    18. Use according to claim 16 or 17, characterized by the fact that: (a) the polypropylene composition, and / or (b) the branched polypropylene (b-PP) and / or (c) the linear polypropylene (1-PP) are further defined in any one of claims 1 to 12.
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    法律状态:
    2018-03-06| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|
    2018-03-13| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|
    2018-03-20| B06I| Publication of requirement cancelled [chapter 6.9 patent gazette]|Free format text: ANULADA A PUBLICACAO CODIGO 6.6.1 NA RPI NO 2462 DE 13/03/2018 POR TER SIDO INDEVIDA. |
    2020-03-03| B06U| Preliminary requirement: requests with searches performed by other patent offices: procedure suspended [chapter 6.21 patent gazette]|
    2020-11-10| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|
    2020-12-22| B16A| Patent or certificate of addition of invention granted [chapter 16.1 patent gazette]|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 26/06/2013, OBSERVADAS AS CONDICOES LEGAIS. |
    优先权:
    申请号 | 申请日 | 专利标题
    EP12174070.8|2012-06-28|
    EP12174070.8A|EP2679630B1|2012-06-28|2012-06-28|High melt strength polypropylene of improved quality|
    PCT/EP2013/063400|WO2014001394A1|2012-06-28|2013-06-26|High melt strength polypropylene of improved quality|
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