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    • 专利摘要:
    FIBER-REINFORCED COMPOSITION, PROCESS FOR PREPARATION OF A FIBER-REINFORCED COMPOSITION, AUTOMOTIVE ARTICLE, AND, FOAM ARTICLE. A fiber reinforced composition comprising (a) a random polypropylene copolymer comprising ethylene and/or a-olefin C4 to C8 (PP-RACO), (b) glass fibers (GF) and (c) a polar modified polypropylene such as adhesion promoter (AP), wherein (i) the polypropylene random copolymer comprising ethylene and/or a-olefin C4 to C8 (PP-RACO) raising an MFR2 melt flow (230°C) measured in accordance with ISO 1133 of at least 2.5 g/10 minutes, (ii) the glass fibers (GF) are cut glass fibers and (iii) the polymer contained in the reinforced composition forms a continuous phase with the matrix of the fiber reinforced composition .
    公开号:BR112016017887B1
    申请号:R112016017887-4
    申请日:2015-02-06
    公开日:2021-05-04
    发明作者:Luca Boragno；Cornelia Tranninger；Markus Gahleitner
    申请人:Borealis Ag；
    IPC主号:
    专利说明:

    [001] The present invention is directed to a fiber reinforced polypropylene composition with excellent impact/hardness balance at reduced emissions, as well as its preparation and use.
    [002] Polypropylene is a material used in a wide variety of technical fields and reinforced polypropylenes have, in particular, relevance in fields previously relying exclusively on non-polymeric materials, in particular metals. A particular example of reinforced polypropylenes are fiberglass reinforced polypropylenes. Such materials allow adjustment of composition properties by selecting the type of polypropylene, the amount of fiberglass, and sometimes by selecting the type of bonding agent used. Consequently, today, fiberglass-reinforced propylene is a well-established material for applications requiring high hardness, resistance to heat deflection, and resistance to both impact and dynamic fracture load (examples include automotive components in a supporting function load space in the engine compartment, the support parts for the polymeric body panels, washing machine and dishwasher components). However, one disadvantage of the available commercial fiber reinforcement material is its limited flow and process capability. The fact that there is a clear negative correlation between fiberglass content (usually ranging between 10 and 40% by weight) and flowability (MFR) makes the formation of thin wall or otherwise thin delicate parts or impossible.
    [003] There is a need in the art to have fiberglass (GF) reinforced polypropylene (PP) grades combining an excellent impact/hardness balance with increased toughness. A key parameter in this context is the force at break (or elongation at break, EB) which is typically at a very low level, ie < 3.0%) for grades of PP/GF.
    [004] This goal is generally considered to be difficult to achieve because the bond in PP/GF composites achieved by a chemical reaction between the GF sizing (surface coating) and the normally applied adhesion promoter is limiting the polymer deformation of matrix. The limit on deformation becomes even stronger with increasing fiberglass content, but bond quality on the other hand is decisive for the hardness and impact resistance (stiffness) of the material.
    [005] In addition, polymer processors today want material with low emissions to satisfy the consistently increasing demands of regulatory authorities as well as consumers.
    [006] Fujiyama M. and Kimura S. describe in "Effect of Molecular Parameters on the Shrinkage of Injection-Molded Polypropylene" (J. Appl. Polym. Sci. 22 (1978) 1225-1241) the compositions of PP homopolymers, random and impact copolymers with glass fibers that have been investigated in terms of shrinkage. Polymers are only very superficially characterized and glass fibers are not; mechanical data is missing.
    [007] WO 98/16359 A1 describes PP granules in the form of a stick containing glass and PP fibers, the fibers having the length of the granules. The core contains a blend of GF with PP fibers, the fibers being a PP homopolymer or a random copolymer with < 10% by weight C2 or C4-C10 as the comonomer, while the coating comprises a PP homopolymer and/or a random copolymer with <10% by weight C2 or C4-C10 as the comonomer and/or a PP impact copolymer with <27% by weight C2 or C4-C10 as the comonomer. Long glass fibers (LGF) as used in this case are generally more difficult to process and release parts with a very high degree of orientation and mechanical anisotropy.
    [008] EP 2062936 A1 describes PP glass fiber compositions with > 15% by weight of glass fibers and a heterophasic PP composition comprising a matrix phase and at least two dispersed elastomer components with a comonomer content total > 12% by weight and a comonomer content in the elastomer phase of > 20% by weight. While demonstrating good impact strength, the compositions described still show very limited breaking strength.
    [009] EP 2308923 B1 describes a fiber reinforced composition comprising (a) a heterophasic copolymer of EP, (b) a homo or copolymer of PP with MFR > 500 and (c) fibers having good flowability. As in the case of EP 2062936 A1, the compositions described show very limited breaking strength.
    [0010] WO 2008/074713 discloses filled polyolefin compositions comprising: A) from 20% to 80% by weight of a polypropylene component; B) from 20% to 80% by weight of a charge; wherein the percentages of A) and B) are referred to the sum of A) and B), and A) is selected from the following compositions: a) a polypropylene composition containing from 20% to 80% by weight of a fraction of polypropylene AI) with a Melt Flow Rate value of 500 g /20 min. or more, and from 20% to 80% by weight of a fraction of polypropylene AII) with a Melt Flow Rate value of 0.1 to 30 g/10 min., said percentages of AI) and AII) being referred to the sum of AI) and AII); or b) a polypropylene composition containing from 15% to 72% by weight of polypropylene fraction AI) with a Melt Flow Rate value of 500 g/10 min. or more, from 15% to 70% by weight of a polypropylene AII fraction) with a Melt Flow Rate value of 0.1 to 30 g/10 min and from 0.5% to 15% by weight of a compatibilizer Q), the referred percentages of AI), AII) and Q) being referred to the sum of AI), AII) and Q).
    [0011] WO 2011/144703 refers to the composition comprising: (I) 30 to 85% by weight of a polypropylene component comprising a polypropylene copolymer; (II) 5 to 49% by weight of a second component comprising at least one ethylene alkyl (meth)acrylate polymer having a (meth)acrylate content of at least 15% by weight; and (III) 10 to 50% by weight of glass fibers.
    [0012] Consequently, although much development work has been carried out in the field of fiber reinforced polypropylene composition, there still remains a need for further improved PP/GF grades.
    [0013] In this way, the objective of the present invention is to provide the fiber reinforced composition with excellent elongation at break. It is still an object of the present invention to obtain an improved balance of mechanical properties such as flexural modulus, impact strength and elongation at break while at the same time reduced emissions.
    [0014] The discovery of the present invention is that a fibrous reinforcement material with excellent impact/hardness balance and reduced emissions can be obtained with fibers included in a monophasic alpha-olefin random copolymer, thus the alpha-random random copolymer. Propylene olefin is produced in the presence of a metallocene catalyst.
    [0015] In this manner, the present invention is directed to a fiber reinforced composition comprising (a) 50.0 to 84.5% by weight of a metallocene catalyzed polypropylene random copolymer comprising ethylene and/or α-olefin C4 to C8 (PP-RACO), (b) 15.0 to 45.0% by weight of glass fibers (GF) and (c) 0.5 to 5.0% by weight of a modified polypropylene as a promoter adhesion (AP), based on the total weight of the fiber reinforced composition, where (i) the polypropylene random copolymer comprising ethylene and/or α-olefin C4 to C8 (PP-RACO) has an MFR2 melt flow ( 230°C) measured in accordance with ISO 1133 from at least 2.5 g/10 minutes to 15.0 g/10 minutes, (ii) the glass fibers (GF) are cut glass fibers and (iii) the complete polymer contained in the reinforced composition forms a continuous phase with the matrix of the fiber reinforced composition being. Propylene random copolymer (PP-RACO)
    [0016] Polypropylene random copolymer comprising ethylene and/or α-olefin C4 to C8 (PPRACO) has a melt flow rate MFR2 (230°C) measured in accordance with ISO 1133 in the range of at least 2.5 g /10 minutes to 15.0 g/10 minutes, preferably in the range of 3.0 g/10 minutes to 12.0 g/10 minutes and more preferably in the range of 5.0 g/10 minutes to 10.0 g/ 10 minutes.
    [0017] It is also possible for one type of PP-RACO to be used, provided that all PPRACOs used form a single phase and provided that the complete monophase meets the physical and chemical requirements as described here for the random copolymer of polypropylene comprising ethylene and/or C4 to C8 α-olefin (PP-RACO). However, it is especially preferred that only one type of PP-RACO is used in the present fiber reinforced composition.
    [0018] Polypropylene random copolymer (PP-RACO) comprises, preferably consists of, propylene and a comonomer selected from ethylene and/or at least one α-olefin C4 to C8, preferably at least one comonomer selected from the group consisting of ethylene, 1-butene, 1-pentene, 1-hexene and 1-octene, more preferably ethylene and/or 1-butene and most preferably ethylene. Thus, in a preferred embodiment, the random propylene copolymer (PPRACO) according to this invention comprises derivable units of ethylene and propylene only.
    [0019] The comonomer content of polypropylene random copolymer (PP-RACO) is within the range of 1.0 to 10.0% by weight of ethylene and/or C4 to C8 α-olefin comonomer.
    [0020] Preferably, the comonomer content is in the range of 2.0 to 9.8% by weight, more preferably in the range of 2.2 to 9.5% by weight and even more preferably in the range of 2.5 to 9.0% by weight.
    [0021] In addition, polypropylene random copolymer (PP-RACO) has a cold soluble xylene content (XCS) in the range of 10.0 to 25.0% by weight, preferably in the range of 10.5 to 23, 0% by weight and more preferably in the range of 11.0 to 20.0% by weight.
    [0022] Furthermore, the random propylene copolymer (PP-RACO) has a melting temperature measured in accordance with ISO 11357-3 of at least 135°C, preferably at least 140°C and more preferably at least 142°C. The fusing temperature will normally not be higher than 160°C.
    [0023] Furthermore, the random propylene copolymer (PP-RACO) is preferably characterized by a relatively narrow molecular weight distribution as determined by size exclusion chromatography (SEC). The ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn) is commonly called polydispersity (Mw/Mn) and is preferably in the range of 1.5 to 6.5, more preferably in the range of 2. 0 to 6.0 and even more preferably in the range of 2.5 to 5.5.
    [0024] Additionally, the random propylene copolymer (PP-RACO) is preferably characterized by its monophasic nature, meaning the absence of an otherwise separated elastomer phase typical for high impact propylene compositions as described in EP 2062936 A1 and EP 2308923 B1 cited above. The presence or absence of such a separate elastomer phase can be, for example, detected in high resolution microscopy or atomic force microscopy or by dynamic thermal mechanical analysis (DMTA). Specifically in DMTA, the presence of a monophase structure can be identified by the presence of only a distinct glass transition temperature (Tg). For PP-RACO according to the present invention, the Tg will normally be in the range of -12 to +2°C. More preferably, the PP-RACO will not have a Tg below -20°C.
    [0025] A suitable propylene random copolymer (PP-RACO) according to this invention is preferably produced in a sequential polymerization process in the presence of a metallocene catalyst, more preferably in the presence of a catalyst (system) as defined below.
    [0026] The term "process and sequential polymerization" indicates that the random copolymer of propylene (PP-RACO) is produced in at least two reactors, preferably in two or three reactors, connected in series. Consequently, the present process comprises at least a first reactor (R1) and a second reactor (R2), as well as, optionally, a third reactor (R3). The term “polymerization reactor” should indicate that the main polymerization takes place. Thus, in case the process consists of two polymerization reactors, this definition does not exclude the option that the total process comprises, for example, a prepolymerization step in a prepolymerization reactor. The term “consists of” is only a final formulation in view of the main polymerization reactors.
    [0027] The first reactor (R1) is preferably a slurry reactor (SR) and can be any continuous or simple stirred batch tank reactor or loop reactor operating in bulk or slurry. Mass means a polymerization in a reaction medium comprising at least 60% (w/w) of monomer. According to the present invention, the slurry reactor (SR) is preferably a loop reactor (LR) (mass).
    [0028] The second reactor (R2) is preferably a gas phase reactor (GPR). Such a gas phase reactor (GPR) can be any mechanically mixed or fluid bed reactor. For example, the gas phase reactor (GPR) can be a mechanically stirred fluid bed reactor with a gas velocity of at least 0.2 m/sec. In this way, it is estimated that the gas-phase reactor is a fluidized-type bed reactor, optionally with a mechanical stirrer.
    [0029] In another embodiment, a third reactor (R3) being a second gas phase reactor (GPR2), connected in series with the first gas phase reactor (GPR), is used.
    [0030] In this way, in a preferred embodiment the first reactor (R1) is a slurry reactor (SR), as a loop reactor (LR), whereas the second reactor (R2) is a gas phase reactor ( GPR), optionally connected in series with a second gas-phase reactor (GPR2). Consequently for the present process at least two to three polymerization reactors, i.e. a slurry reactor (SR) such as a loop reactor (LR) and a gas phase reactor (GPR) and optionally a second phase reactor gas (GPR2) are connected in series. If necessary, before the slurry reactor (SR) a pre-polymerization reactor is placed.
    [0031] A preferred multistage process is a “gas loop phase” process as developed by Borealis NS, Denmark (known as BORSTAR® technology) described, for example, in the patent literature such as in EP 0 887 379, WO 92/12182, WO 2004/000899, WO 2004/111095, WO 99/24478, WO 99/24479 or in WO 00/68315.
    A further suitable gas slurry phase process is the Basell Spheripol® process described, for example, in figure 20 of the paper by Galli and Vecello, Prog. Polymer Sci. 26 (2001) 1287-1336.
    [0033] Preferably, in the present process for the production of the propylene copolymer (R-PP) as defined above, the conditions for the first reactor (R1), that is, the slurry reactor (SR), as a reactor of circuit (LR) of step (a) can be as follows: - the temperature is within the range of 40°C to 110°C, preferably between 60°C and 100°C, such as 68 to 95°C, - a pressure is within the range of 2 mPa (20 bar) to 8 mPa (80 bar), preferably between 4 mPa (40 bar) to 7 mPa (70 bar), - hydrogen can be added to control the molar mass in a known manner for you.
    [0034] Subsequently, the reaction mixture from step (a) is transferred to the second reactor (R2), i.e. the gas phase reactor (GPR) and optionally subsequently to the second gas phase reactor (GPR2), of that Thus, 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 0.5 mPa (5 bar ) to 5 mPa (50 bar), preferably between 1.5 mPa (15 bar) and 3.5 mPa (35 bar), - hydrogen can be added to control the molar mass in a manner known per se.
    [0035] Resistance time may vary in the reaction zones identified above.
    [0036] In one embodiment of the process for producing the random propylene copolymer (PPRACO) the residence time of the first reactor (R1), that is, the slurry reactor (SR), as a loop reactor (LR), it is in the range of 0.2 to 4 hours, for example 0.3 to 1.5 hours and the residence time in gas phase reactors (optional GPR and GPR2) will generally be 0.2 to 6.0 hours , such as 0.5 to 4.0 hours.
    [0037] If desired, polymerization can be carried out in a known manner under supercritical conditions in the first reactor (R1), that is, in the slurry reactor (SR), as in the loop reactor (LR) and/or as a condensed mode in gas phase reactors (optional GPR and GPR2).
    [0038] Preferably, the process also comprises a pre-polymerization with the chosen catalyst system, as described in detail below.
    [0039] In a preferred embodiment, the prepolymerization is conducted as the slurry polymerization of dough in liquid propylene, i.e., the liquid phase mainly comprises propylene, with lesser amount of other reactants and optionally inert components dissolved therein.
    [0040] The prepolymerization reaction is typically conducted at a temperature from 0 to 50°C, preferably from 10 to 40°C, and more preferably from 10 to 23°C.
    [0041] The pressure in the prepolymerization reactor is not critical, but it should be high enough to keep the reaction mixture in the liquid phase. In this way the pressure can be from 2 to 10 mPa (20 to 100 bar), for example from 3 to 7 mPa (30 to 70 bar).
    [0042] The catalyst components are preferably all introduced to the prepolymerization step. However, when the solid catalyst component (i) and the cocatalyst (ii) can be fed separately, it is possible that only a part of the cocatalyst is introduced in the pre-polymerization stage and the remaining part in the subsequent polymerization stages. Also in such cases, it is necessary to introduce so much cocatalyst at the prepolymerization stage that sufficient polymerization is obtained there.
    [0043] It is possible to add other components also to the pre-polymerization stage. In this way, hydrogen can be added at the prepolymerization stage to control the molecular weight of the prepolymer as is known in the art. In addition, the antistatic additive can be used to prevent the particles from sticking to each other or to the reactor walls.
    [0044] Precise control of prepolymerization conditions and reaction parameters are within the skill of the art.
    [0045] The polymerization takes place in the presence of a metallocene catalyst system, the so-called metallocene catalyst system, comprises (i) an asymmetric complex of the formula (I)
    where M is zirconium or hafnium; each X is a sigma ligand; L is a bivalent bridge selected from -R'2C-, -R'2C-CR'2-, -R'2Si-, -R'2Si-SiR'2-, -R'2Ge-, where each R' is independently a hydrogen atom, C1-20 hydrocarbyl, tri(C1-20 alkyl)silyl, C6-20 aryl, C720 arylalkyl or C7-20 alkylaryl; R2 and R2' are each independently a C1-20 hydrocarbyl radical optionally containing one or more heteroatoms from groups 14 to 16; R5' is a C1-20 hydrocarbyl group optionally containing one or more heteroatoms from groups 14 to 16 is optionally substituted by one or more halo atoms; R6 and R6' are each independently hydrogen or a C1-20 hydrocarbyl group optionally containing one or more heteroatoms from groups 14 to 16; R7 and R7' are each independently hydrogen or C1-20 hydrocarbyl group optionally containing one or more heteroatoms from groups 14 to 16; Ar is an aryl or heteroaryl group having up to 20 carbon atoms optionally substituted by one or more R1 groups; Ar' is an aryl or heteroaryl group having up to 20 carbon atoms optionally substituted by one or more R1 groups; each R1 is a C1-20 hydrocarbyl group or two R1 groups on adjacent carbon atoms when together can form a non-aromatic 5- or 6-membered ring fused to the Ar group, said ring optionally being substituted by itself with one or more groups R4 and each R4 is a C1-20 hydrocarbyl group, and (ii) optionally a cocatalyst (Co) comprising an element (E) from group 13 of the periodic table (IUPAC), preferably a cocatalyst (Co) comprising a compound of Al. As mentioned above, the catalyst must comprise an asymmetric complex. Additionally, the catalyst may comprise a cocatalyst.
    [0046] Preferably, the molar ratio of cocatalyst (Co) to metal (M) of the complex, such as Zr, [Co/M] is below 500, more preferably in the range of more than 100 to below 500, still more preferably in the range 150 to 450, even more preferably in the range 200 to 450.
    [0047] In relation to the preparation of the cocatalyst composition as defined above reference is made to WO 2010/052260.
    [0048] The metallocene complex, especially the complexes defined by the formulas specified in the present invention, used for the manufacture of polypropylene random copolymer (PP-RACO) are asymmetric. Meaning that the two indenyl ligands forming the metallocene complex are different, that is, each indenyl ligand carries a series of substituents that are chemically different or located at different positions relative to the other indenyl ligand. More precisely, these are chiral racemic bridged bisindenyl metallocene complexes. While the complexes of the invention may be in their syn conformation, ideally they are in their anticonfiguration. For the purpose of this invention, racemic-anti means that the two indenyl ligands are oriented in opposite directions with respect to the cyclopentadienyl-metalcyclopentadienyl plane, while racemic-syn means that two indenyl ligands are oriented in the same direction with respect to the cyclopentadienyl-plane. metal-cyclopentadienyl, as shown in the Figure below.

    Formula (I) is intended to encompass both syn and anti configurations, preferably anti. It is further required that the R5' group is not hydrogen where the 5-position on the other ligand carries a hydrogen.
    [0050] In fact, the metallocene complexes used in the invention are C1-symmetric, but they maintain pseudo-C2-symmetry since they maintain C2-symmetry in proximity to the metal center, although not in the periphery of the ligand. The use of two different indenyl binders as described in this invention allows for much finer structural variation, and therefore a more accurate adjustment of catalyst performance, compared to typical C2-symmetric catalysts. By the nature of their chemistry, both anti and syn enantiomer pairs are formed during complex synthesis. However, using the linkers of this invention, the separation of the preferred anti-isomers from the syn-isomers is straightforward.
    This is preferred if the metallocene complexes of the invention are used as the anti rac isomer. Ideally, therefore, at least 95 mol%, such as at least 98 mol%, especially at least 99 mol% of the metallocene catalyst is in racemic antiisomeric form.
    [0052] In the complex of use in the invention: M is preferably Zr.
    [0053] Each X, which may be the same or different, is preferably a hydrogen atom, a halogen atom, a group R, OR, OSO2CF3, OCOR, SR, NR2 or PR2 where R is a radical, C1-alkyl 20, C2-20 alkenyl, C2-20 alkynyl, C6-20 aryl, C7-20 alkylaryl or linear or branched, cyclic or acyclic C7-20 arylalkyl; optionally containing heteroatoms belonging to groups 14-16. R is preferably a C1-6 alkyl, phenyl or benzyl group.
    More preferably, each X is independently a hydrogen atom, a halogen atom, a C1-6 alkoxy group or an R group, for example, preferably a C1-6 alkyl, phenyl or benzyl group. More preferably X is chlorine or methyl radical. Preferably both X groups are the same.
    [0055] L is preferably an alkylene linker or a bridge comprising a heteroatom such as silicon or germanium, e.g. -SiR82-, wherein each R8 is independently C1-20 alkyl, C3-10 cycloalkyl, C6 aryl- 20 or tri(C 1-20 alkyl)silyl, such as trimethylsilyl. More preferably, R8 is C1-6 alkyl, especially methyl or C3-7 cycloalkyl, such as cyclohexyl. More preferably, L is a dimethylsilyl or methylcyclohexylsilyl (i.e., Me-Si-cyclohexyl) bridge. It could also be an ethylene bridge.
    [0056] R2 and R2' may be different, but these are preferably the same. R2 and R2' are preferably a C1-10 hydrocarbyl group, such as the C1-6 hydrocarbyl group. More preferably this is a linear or branched C 1-10 alkyl group. More preferably this is a C1-6 alkyl group, especially linear C1-6 alkyl group such as methyl or ethyl.
    [0057] The groups R2 and R2' can be interrupted by one or more heteroatoms, such as 1 or 2 heteroatoms, for example, a heteroatom selected from groups 14 to 16 of the periodic table. Such a heteroatom is preferably O, N or S, especially O. More preferably, however, the groups R2 and R2' are free from heteroatoms. More especially, R2 and R2' are methyl, especially both methyl.
    [0058] The two groups Ar and Ar' can be the same or different. The Ar' group can be unsubstituted. Ar' is preferably a phenyl-based group optionally substituted by R1 groups, especially an unsubstituted phenyl group.
    [0059] The Ar group is preferably a C6-20 aryl group, such as a phenyl group or naphthyl group. While the Ar group may be a heteroaryl group, such as carbazolyl, it is preferable that Ar is not a heteroaryl group. The Ar group may be unsubstituted or substituted by one or more R1 groups, more preferably by one or two R1 groups, especially at the 4-position of the aryl ring attached to the indenyl linker or at the 3.5-positions.
    [0060] In one modality, both Ar and Ar' are unsubstituted. In another embodiment Ar' is unsubstituted and Ar is replaced by one or two R1 groups.
    [0061] R1 is preferably a C1-20 hydrocarbyl group, such as a C1-20 alkyl group. The R1 groups can be the same or different, preferably the same. More preferably, R1 is a C210 alkyl group, such as the C3-8 alkyl group. Highly preferred groups are tert-butyl or isopropyl groups. It is preferred if the R1 group is bulky, that is, it is branched. The branch must be alpha or beta to the ring. Branched C3-8 alkyl groups are therefore also preferred.
    [0062] In another embodiment, the two R1 groups on adjacent carbon atoms when together can form a non-aromatic 5- or 6-membered ring fused to the Ar group, said ring being optionally substituted by itself with one or more groups A4. Such a ring must form a tetrahydroindenyl group with the Ar ring or a tetrahydronaphthyl group.
    [0063] If an R4 group is present, there is preferably only such a group. This is preferably a C1-10 alkyl group.
    [0064] It is preferred if there are one or two R1 groups present in the Ar group. Where there is an R1 group present, the group will preferably be for the indenyl ring (position 4). When two R1 groups are present, they are preferably in positions 3 and 5.
    [0065] R5' is preferably a C1-20 hydrocarbyl group containing one or more heteroatoms from groups 14 to 16 and optionally substituted by one or more halo atoms or R5' is a C1-10 alkyl group, such as methyl, but more preferably this is a Z'R3' group.
    [0066] R6 and R6' can be the same or different. In a preferred embodiment, one of R6 and R6' is hydrogen, especially R6. That is, preferred if R6 and R6' are not both hydrogen. If not hydrogen, it is preferred if each R6 and R6' is preferably a C1-20 hydrocarbyl group, such as a C1-20 alkyl group or C6-10 aryl group. More preferably, R6 and R6' are a C2-10 alkyl group, such as a C3-6 alkyl group. Highly preferred groups are tert-butyl groups. It is preferred if R6 and R6' are bulky, i.e. they are branched. Branched must be alpha or beta to the ring. Branched C3-8 alkyl groups are therefore also favored.
    [0067] The groups R7 and R7' can be the same or different. Each group R7 and R7' is preferably hydrogen, a C1-6 alkyl group or is a ZR3 group. It is preferred if R7 is hydrogen. It is preferred if R7 is hydrogen, C1-6 alkyl or ZR3. The combination of both R7 and R7' being hydrogen is more preferred. It is also preferred if ZR3 represents C1-6 alkyl, such as methoxy. Also preferred is R7 represents C1-6 alkyl such as methyl.
    [0068] Z and Z' are O or S, preferably O.
    [0069] R3 is preferably a C1-10 hydrocarbyl group, especially a C1-10 alkyl group, or aryl group optionally substituted by one or more halo groups. More especially R3 is a C1-6 alkyl group, such as a linear C1-6 alkyl group, for example methyl or ethyl.
    [0070] R3 is preferably a C1-10 hydrocarbyl group, especially a C1-10 alkyl group, or aryl group optionally substituted by one or more halo groups. More especially R3 is a C1-6 alkyl group, such as a linear C1-6 alkyl group, for example methyl or ethyl or this is a phenyl-based radical optionally substituted with one or more halo groups such as Ph or C6F5.
    Thus, preferred complexes of the invention are of the formula
    where M is zirconium or hafnium; independently a hydrogen atom, a halogen atom, C1-6 alkoxy group, C1-6 alkyl, phenyl or benzyl group; L is a bivalent bridge selected from -R'2C-, -R'2C-CR'2-, -R'2Si-, -R'2Si-SiR'2-, -R'2Ge-, where each R' is independently a hydrogen atom, C1-20 alkyl, C3-10 cycloalkyl, tri(C1-20 alkyl)silyl, C6-20 aryl, C7-20 arylalkyl or C7-20 alkylaryl; each R2 or R2 is a C1-10 alkyl group; R5, is a C1-10 alkyl group or Z'R3 group; R6 is hydrogen or a C1-10 alkyl group; R6' is a C1-10 alkyl group or C6-10 aryl group; R7 is hydrogen, a C1-6 alkyl group or ZR3 group; R7 is hydrogen or a C1-10 alkyl group; Z and Z' are independently O or S; R3' is a C1-10 alkyl group, or a C6-10 aryl group optionally substituted by one or more halo groups; R3 is a C1-10 alkyl group; each n is independently 0 to 4, for example 0, 1 or 2; and each R1 is independently a C1-20 hydrocarbyl group, for example C1-10 alkyl group.
    [0072] Further preferred complexes of the invention are those of formula (III) or (III'):
    where M is zirconium or hafnium; each X is a sigma linker, preferably each X is independently a hydrogen atom, a halogen atom, a C1-6 alkoxy group, C1-6 alkyl, phenyl or benzyl group; L is a bivalent bridge selected from -R'2C- or -R'2Si- where each R' is independently a hydrogen atom, C1-20 alkyl or C3-10 cycloalkyl; R6 is hydrogen or a C1-10 alkyl group; R6' is a C1-10 alkyl group or C6-10 aryl group; R7 is hydrogen, C1-6 alkyl or OC1-6 alkyl; Z' is O or S; R3' is a C1-10 alkyl group, or C6-10 aryl group optionally substituted by one or more halo groups; n is independently 0 to 4, for example 0, 1 or 2; and each R1 is independently a C1-10 alkyl group.
    [0073] Still the preferred complexes for use in the invention are those of formula (IV) or (IV'):
    where M is zirconium or hafnium; each X is a sigma linker, preferably each X is independently a hydrogen atom, a halogen atom, a C1-6 alkoxy group, C1-6 alkyl, phenyl or benzyl group; each R' is independently a hydrogen atom, C1-20 alkyl or C3-7 cycloalkyl; R6 is hydrogen or a C1-10 alkyl group; R6' is a C1-10 alkyl group or C6-10 aryl group; R7 is hydrogen, C1-6 alkyl or OC1-6 alkyl; Z' is O or S; R3' is a C1-10 alkyl group, or C6-10 aryl group optionally substituted by one or more halo groups; n is independently 0, 1 to 2; and each R' is independently a C3-8 alkyl group.
    [0074] More especially, the complex for use in the invention is of the formula (V) or (V'):
    wherein each X is a sigma linker, preferably each X is independently a hydrogen atom, a halogen atom, a C1-6 alkoxy group, C1-6 alkyl, phenyl or benzyl group; R' is independently C1-6 alkyl or C3-10 cycloalkyl; R' is independently C3-8 alkyl; R6 is hydrogen or a C3-6 alkyl group; R6' is a C1-6 alkyl group or C6-10 aryl group; R3' is a C1-6 alkyl group, or C6-10 aryl group optionally substituted by one or more halo groups and n is independently 0, 1 or 2.
    Particular compounds of the invention include: rac-anti-Me2Si(2-Me-4-Ph-6-tBu-Ind)(2-Me-4-Ph-5-OMe-6-tBu-Ind)ZrCl2 , rac-anti-Me2Si(2-Me-4-(p-tBuPh)-Ind)(2-Me-4-Ph-5-OMe-6-tBu-Ind)ZrCl2, rac-anti-Me2Si(2- Me-4-(3,5-di-tBuPh)-6-tBu-Ind)(2-Me-4-Ph-5-OMe-6-tBu-Ind)ZrCl2, rac-anti-Me2Si(2-Me -4-Ph-6-tBu-Ind)(2-Me-4,6-di-Ph-5-OMe-Ind)ZrCl2, rac-anti-Me2Si(2-Me-4-(p-tBuPh)- Ind)(2-Me-4-Ph-5-OC6F5)-6-iPr-Ind)ZrCl2, rac-anti-Me(CyHex)Si(2-Me-4-Ph-6-tBu-Ind)(2 -Me-4-Ph-5-OMe-6-tBu-Ind)ZrCl2, rac-anti-Me2Si(2-Me-4-(3,5-di-tBuPh)-7-Me-Ind)(2- Me-4-Ph-5-OMe-6-tBu-Ind)ZrCl2, rac-anti-Me2Si(2-Me-4-(3,5-di-tBuPh)-7-OMe-Ind)(2-Me -4-Ph-5-OMe-6-tBu-Ind)ZrCl2, rac-anti-Me2Si(2-Me-4-(p-tBuPh)-6-tBu-Ind)(2-Me-4-Ph- 5-OMe-6-tBu-Ind)ZrCl2, rac-anti-Me2Si(2-Me-4-(p-tBuPh)-Ind)(2-Me-4-(4-tBuPh)-5-OMe-6 -tBu-Ind)ZrCl2, rac-anti-Me2Si(2-Me-4-(p-tBuPh)-Ind)(2-Me-4-(3,5-tBu2Ph)-5-OMe-6-tBu- Ind)ZrCl2 and rac-anti-Me2Si(2-Me-4-(p-tBuPh)-Ind)(2-Me-4-Ph-5-OiBu-6-tBu-Ind)ZrCl2.
    [0076] For the avoidance of doubt, any more limited definition of a substituent offered above may be combined with any other broad or more limited definition of any other substituent.
    [0077] Everywhere in the above description, where a more limited definition of a substituent is presented, that more limited definition is considered to be described in conjunction with all broader and more limited definitions of other substituents in the application.
    In an especially preferred embodiment the complex is rac-anti-Me2Si(2-Me-4-(p-tBuPh)-Ind)(2-Me-4-Ph-5-OMe-6-tBu-Ind) ZrCl2.
    [0079] With regard to the synthesis of the complex according to the invention, WO 2013/007650 Al.
    [0080] To form an active catalytic species it is usually necessary to use a cocatalyst as is well known in the art. Cocatalysts comprising one or more compounds from metal groups 13, similar to organoaluminum compounds or borates used to activate metallocene catalysts are suitable for use in this invention.
    [0081] Thus the catalyst according to this invention comprises (i) a complex as defined above and (ii) a cocatalyst, similar to an alkyl aluminum compound (or other suitable cocatalyst), or the reaction product thereof. Thus the cocatalyst is preferably an alumoxane, similar to MAO or an alumoxane other than MAO.
    [0082] Borate cocatalysts can also be used. It will be evident to the skilled person that where boron based cocatalysts are used, it is normal to preactivate the complex by reacting it with an alkyl aluminum compound such as TIBA. This procedure is well known and any suitable aluminum alkyl, for example Al(C1-6 alkyl)3 can be used.
    [0083] Boron-based cocatalysts of interest include those of the formula BY3 where Y is the same or different and is a hydrogen atom, an alkyl group of 1 to about 20 carbon atoms, an aryl group of 6 to about 15 carbon atoms, alkylaryl, arylalkyl, haloalkyl or haloaryl each having from 1 to 10 carbon atoms in the alkyl radical and from 6-20 carbon atoms in the aryl radical or fluorine, chlorine, bromine or iodine. Preferred examples for Y are trifluoromethyl, p-fluorophenyl, 3,5-difluorophenyl, pentafluorophenyl, 3,4,5-trifluorophenyl and 3,5-di(trifluoromethyl)phenyl. Preferred options are trifluoroborane, tris(4-fluorophenyl)borane, tris(3,5-difluorophenyl)borane, tris(4-fluoromethylphenyl)borane, tris(2,4,6-trifluorophenyl)borane, tris(pentafluorophenyl) borane, tris(3,5-difluorophenyl)borane and/or tris(3,4,5-trifluorophenyl)borane.
    Particular preference is given to tris(pentafluorophenyl)borane.
    [0085] However it is preferred that borates are used, ie compounds of the general formula [C]+[BX4]-. Such ionic cocatalysts contain a non-coordinating anion [BX4]- such as tetrakis(pentafluorophenyl)borate. Suitable counter-ions [C]+ are protonated amine or aniline derivatives such as methylammonium, anilinium, dimethylammonium, diethylammonium, N-methylanilinium, diphenylammonium, N,N-dimethylanilinium, trimethylammonium, triethylammonium, tri-n-butylammonium, methyldiphenylammonium, pyridinium, p-bromo-N,N-dimethylanilinium or p-nitro-N,N-dimethylanilinium.
    Preferred ionic compounds that can be used in accordance with the present invention include: tributylammoniotetrakis(pentafluorophenyl)borate, tributylammoniotetrakis(trifluoromethylphenyl)borate, tributylammoniotetrakis(4-fluorophenyl)borate, N,N-dimethylcyclohexylammoniotetrakis(pentakis(pentakis) , N,N-dimethylbenzylammoniotetrakis(pentafluorophenyl)borate, N,N-dimethylaniliniumtetrakis(pentafluorophenyl)borate, N,N-di(propyl)ammoniotetrakis(pentafluorophenyl)borate, di(cyclohexyl)ammoniotetrakist(pentafluorophenyl)pentakis(pentafluorophenyl)pentakis ) borate, or ferrocenium tetrakis (pentafluorophenyl) borate.
    Preference is given to triphenylcarbeniumtetrakis(pentafluorophenyl) borate, N,N-dimethylcyclohexylammoniumtetrakis(pentafluorophenyl)borate or N,N-dimethylbenzylammoniotetrakis(pentafluorophenyl)borate.
    The use of B(C6F5)3, C6H5N(CH3)2H:B(C6F5)4, (C6H5)3C:B(C6F5)4 is especially preferred.
    [0089] The metallocene complex used in the present invention can be used in combination with a suitable cocatalyst as a catalyst for example in a solvent such as toluene or an aliphatic hydrocarbon, (i.e. for solution polymerization), as is well known in technique.
    [0090] The catalyst used in the invention can be used in supported or unsupported form. The particular support material used is preferably an organic or inorganic material such as silica, alumina or zirconia or a mixed oxide such as silica-alumina, in particular silica, alumina or silica-alumina. The use of a silica support is preferred. The person skilled in the art is aware of the procedures required to support a metallocene catalyst.
    [0091] Especially preferably the support is a porous material so that the complex can be loaded into the pores of the support, for example using a process analogous to that described in WO94/14856 (Mobil), WO95/12622 (Borealis) and WO2006/097497 . Particle size is not critical, but is preferably in the range of 5 to 200 µm, more preferably 20 to 80 µm. The use of this support is routine in the technique.
    [0092] In the preferred embodiment, no support is used at all. Such a catalyst can be prepared in solution, for example in an aromatic solvent similar to toluene, in contact with metallocene (as a solid or as a solution) with the cocatalyst, for example methylaluminoxane or a borane or a borate salt or they can be prepared by sequentially adding catalyst components to the polymerization medium. In a preferred embodiment, the metallocene (when X differs from alkyl or hydrogen) is pre-reacted with an aluminum alkyl, in a metal/aluminum ratio of 1:1 to 1:500, preferably 1:1 to 1: 250 and then combined with the borane or borate cocatalyst, in a separate container or directly in the polymerization reactor. Preferred metal/boron ratios are between 1:1 and 1:100, more preferably 1:1 to 1:10.
    [0093] In a particularly preferred embodiment, no external charger is used, but the catalyst is still presented in solid particulate form. Thus, no external support material such as an inert inorganic or organic carrier, such as for example silica, as described above, is used.
    [0094] In order to supply the catalyst used in the invention in solid form but without using an external charger, it is preferred if a liquid/liquid emulsion system is used. The process involves forming the dispersion of catalyst components (i) and (ii), i.e. the complex and cocatalyst, in a solvent and solidifying said dispersed droplets to form solid particles.
    [0095] Reference is made to WO 2006/069733 describing the principles of such a method of continuous or semi-continuous preparation of solid catalyst types, prepared by means of the emulsion/solidification method. For further details it is also referred to WO 2013/007650 A1.
    [0096] It should be noted that the present invention is preferably directed to the fiber reinforced composition in which the polymer phase forms a continuous phase being the matrix for the fibers. Since the polymer formation the matrix for the fibers in the composition is preferably single-phase. In the case of this preferred embodiment, the polymer matrix does not contain elastomeric (co)polymers that form inclusions as a second phase to improve the mechanical properties of the composite, such as elongation at break. Elastomeric (co)polymers containing the polymer phase as inserts of a second phase would be in contrast termed heterophasic and is not part of this preferred embodiment.
    [0097] The desired mechanical properties of the fiber reinforced composite are therefore preferably controlled by the random copolymer of polypropylene comprising ethylene and/or α-olefin C4 to C8 (PP-RACO) in combination with the adhesion promoter (AP) improving the adhesion of an insert of the fibers. It is believed that the polymer of such a composite forms a continuous phase. Additional inserts of second or more elastomer phases aim to improve the same mechanical properties which are preferably excluded. Fiberglass (GF)
    [0098] The second essential component of the present fiber reinforced composition is glass fibers (GF). Preferably the glass fibers are chopped glass fibers, also known as chopped fibers or chopped filaments.
    The cut or short glass fibers used in a fiber reinforced composition preferably have an average length of 1 to 10 mm, more preferably 1 to 7 mm, for example 3 to 5 mm, or 4 mm. The cut or short glass fibers used in the fiber reinforced composition preferably have an average diameter of 8 to 20 µm, more preferably 9 to 16 µm, for example 10 to 15 µm.
    Preferably, the fibers (GF) have an aspect ratio from 125 to 650, preferably from 150 to 450, more preferably 200 to 400, even more preferably 250 to 350. The aspect ratio is the ratio of the average length and average fiber diameter. Adhesion Promoter (AP)
    [00101] The fiber reinforced composition also comprises an adhesion promoter (AP).
    [00102] The adhesion promoter (AP) preferably comprises a modified (functionalized) polypropylene. Modified polypropylenes, in particular homopolymers of propylene and copolymers, similar to copolymers of propylene with ethylene or with other α-olefins, are no longer preferred, as these are highly compatible with the polymers of the fiber reinforced composition.
    [00103] In terms of structure, the modified polypropylenes are preferably selected from graft or block copolymers.
    [00104] In this context, preference is given to modified polypropylenes containing groups deriving from polar compounds, in particular selected from the group consisting of acid anhydrides, carboxylic acids, carboxylic acid derivatives, primary and secondary amines, hydroxyl compounds, oxazoline and epoxides as well as ionic compounds.
    [00105] Specific examples of said polar compounds are unsaturated cyclic anhydrides and their aliphatic diesters and diacid derivatives. In particular, one can use maleic anhydride and compounds selected from C1 to C10 branched or linear dialkyl maleates, C1 to C10 branched and linear dialkyl fumarates, itaconic anhydride, C1 to C10 branched or linear itaconic acid dialkyl esters, maleic acid, fumaric acid, itaconic acid and mixtures thereof.
    [00106] Particular preference is given using a maleic anhydride grafted polypropylene as the modified polypropylene, i.e. as the adhesion promoter (AP).
    [00107] Modified polypropylene, that is, the adhesion promoter (AP), can be produced in a simple way by reactive extrusion of the polymer, for example with maleic anhydride in the presence of free radical generators (similar organic peroxides), such as described for example in EP 0 572 028.
    [00108] The amounts of the groups derived from the polar compounds in the modified polypropylene, i.e. the adhesion promoter (AP), are from 0.5 to 5.0% by weight, preferably from 0.5 to 4.0% in weight and more preferably from 0.5 to 3.0% by weight.
    [00109] Preferred MFR2 melt flow rates (230°C) for the modified polypropylene, i.e. for the adhesion promoter (AP), are 1.0 to 500 g/10 min. Fiber reinforced composition
    [00110] In addition to the components described above, the present composition may additionally contain other typical additives useful for example in the automotive sector, similar and carbon black, other pigments, antioxidants, UV stabilizers, nucleating agents, antistatic agents and slip agents, in quantities usual in the art.
    [00111] Thus a further embodiment of the present invention is a fiber reinforced composition consisting of (a) 50 to 84.5% by weight, preferably 60 to 80% by weight and more preferably 65 to 77% by weight, of the polypropylene random copolymer comprising ethylene and/or C4 to C8 α-olefin (PPRACO), (b) 15 to 45% by weight, preferably 18 to 35% by weight and more preferably 20 to 30% by weight of the glass fibers (GF) and (c) 0.5 to 5.0% by weight of a modified polypropylene as adhesion promoter (AP), preferably 1.0 to 4.0% by weight and more preferably 1.0 to 3.0 % by weight, (d) 0.0 to 3.0% by weight of a masterbatch and (e) 0.0 to 3.0% by weight of one or more additives, based on the total weight of the fortified composition. fiber, wherein (i) the polypropylene random copolymer comprising ethylene and/or α-olefin C4 to C8 (PP-RACO) raising an MFR2 melt flow (230°C) measuring in accordance with ISO 1133 of at least 2.5 g/10 minutes, (ii) glass fibers (GF) are fiber s cut glass, (iii) the complete polymer contained in the reinforced composition forms a continuous phase with the matrix of the fiber reinforced composition being
    [00112] It is believed to be understood that all combinations as described above are applicable for these modalities as well.
    [00113] Additives in this sense are for example carbon black, other pigments, antioxidants, UV stabilizers, nucleating agents, antistatic agents and slip agents.
    [00114] The term masterbatch means polymer binding additives, for example color concentrates and additives physically or chemically bound in or in the polymers. It is estimated that such standard blends contain as little polymer as possible.
    [00115] The additives as set out above are added to polypropylene random copolymer (PPRACO), which are collected from the final reactor of the polymer production process. Preferably, these additives are mixed in a polypropylene random copolymer (PP-RACO) or during the extrusion process in a single-step compounding process. Alternatively, a masterbatch can be formulated, in which polypropylene random copolymer (PP-RACO) is first blended with just a few of the additives.
    [00116] The properties of polypropylene random copolymer comprising ethylene and/or α-olefin C4 to C8 (PP-RACO), produced with the process outlined above can be adjusted and controlled with the process conditions as known to the person skilled in the art. technique, for example by one or more of the following process parameters: temperature, hydrogen feed, comonomer feed, propylene feed, catalyst, type and amount of external donor, split between two or more components of a multimodal polymer.
    [00117] For mixing the individual components of the present fibre-reinforced composition, a blending apparatus or conventional composition, for example a Banbury mixer, a 2-roll rubber mill, Buss-co-kneader or a twin screw extruder can be used. Preferably, the mixture is followed in a co-rotating twin-screw extruder. Polymer materials recovered from the extruder are usually in the form of granules. These granules are then preferably further processed, for example by injection molding to generate the articles and products of the inventive fiber reinforced composition.
    [00118] The fiber reinforced composite according to the invention has the following properties:
    [00119] The total melt flow rate MFR2 (230°C), i.e. the melt flow rate of the fiber reinforced composite is at least 1.0 g/10 minutes, preferably at least 1.5 g/10 min. The upper limit of MFR2 (230°C) is 15.0 g/10 min, preferably 10.0 g/10 min and more preferably 7.0 g/10 min.
    [00120] The total elastic modulus, i.e. the elastic modulus measured at 23°C according to ISO 527-2 (crosshead speed 1 mm/minute) of the fiber reinforced composite, is at least 2,500 MPa, preferably at least 3,000 MPa and more preferably at least 3,500 MPa.
    [00121] The upper limit of the elastic modulus of the fiber reinforced composite may be 10,000 MPa, preferably 9,000 MPa and more preferably in the range of 8,000 MPa.
    [00122] The tensile deformation at break measured at 23°C according to ISO 527-2 (crosshead speed 50 mm/minute) is at least 4.0%, preferably at least 4.5% and more preferably at least 4.8%.
    [00123] The tensile strength at break measured at 23°C according to ISO 527-2 (crosshead speed 50 mm/minute) is at least 50 MPa, preferably at least 60 MPa and more preferably at least 65 MPa.
    [00124] A value for total volatile emission measured in accordance with VDA 277:1995 equal to or below 10 ppm, preferably equal to or below 5 ppm and more preferably equal to or below 4 ppm.
    [00125] A VOC value measured in accordance with VDA 278:2002 equal to or below 50 ppm, preferably equal to or below 40 ppm and more preferably equal to or below 35 ppm. VOC is an amount of volatile organic compounds (VOC) [in ppm].
    [00126] A FOG value measured in accordance with VDA 278:2002 equal to or below 130 ppm, preferably equal to or below 110 ppm and more preferably equal to or below 100 ppm. FOG is an amount of obscuring compounds (FOG) [in ppm].
    [00127] Charpy bevel impact force at 23°C ISO 179-1 eA:2000 is at least 5.0 kJ/m2, preferably in the range of 6.5 to 15 kJ/m2 and more preferably in the range of 7, 0 to 12 kJ/m2.
    [00128] A Charpy impact force at 23°C ISO 179-1eU:2000 of at least 8.0 kJ/m2, preferably in the range of 9.0 to 18 kJ/m2 and more preferably in the range of 10.0 to 16.0 kJ/m2.
    [00129] A heat distortion temperature (HDT) determined according to a method A ISO 75-2 (load 1.80 MPa tension can surface) in the range of 95°C to 145°C, preferably in the range of 100 °C to 135°C and more preferably in the range of 105°C to 130°C.
    [00130] Thus, fiber reinforced polypropylene composites show an excellent impact/hardness balance and have very low emissions.
    [00131] The fiber reinforced composition according to the invention may be granulated and compounded using any of the variety of compounding and blending methods well known and commonly used in the resin compounding art.
    [00132] The composition of the present fiber reinforced composition can be used for the production of molded articles, preferably injection molded articles as well as foam articles. Even more preferred is the use for the production of parts of washing machines or dish washers as well as automotive articles, especially for car interiors and exteriors, similar to instrument loaders, armor, structural loaders, bumpers, side trims, running boards, body panels, spoilers, instrument panels, interior trim and others.
    [00133] According to a preferred embodiment, the article is a foam article comprising the fiber reinforced composition described above.
    [00134] Appropriate methods of preparing foam articles, by chemical or physical foaming, are commonly known to the skilled person.
    [00135] The present invention further relates to automotive articles comprising the fiber reinforced composition as defined above.
    [00136] In addition, the present invention also relates to a process for the preparation of the fiber reinforced composition as described above, which comprises the steps of adding (a) polypropylene random copolymer (PP-RACO), (b) as glass fibers (GF) and (c) polypropylene modified as adhesion promoter (AP) to an extruder and extrusion thereof obtaining said fiber reinforced composition. EXPERIMENTAL PART 1. METHODS MFR2 (230°C) is measured in accordance with ISO 1133 (230°C, 2.16 kg load). Quantification of copolymer microstructure by NMR spectroscopy
    [00137] Quantitative nuclear magnetic resonance (NMR) spectroscopy was used to quantify the comonomer content of polymers.
    [00138] The quantitative 13C{1H} NMR spectra were recorded in the solution state using a Bruker Advance III 400 NMR spectrometer operating at 400.15 and 100.62 MHz for 1H and 13C respectively. All spectra were recorded using a 13C optimized extended temperature probe head optimized to 125°C using nitrogen gas for all tyres. Approximately 200 mg of the material was dissolved in 3 ml of 1,2-tetrachloroethane-d2 (TCE-d2) together with chromium-(III)-acetylacetonate (Cr(acac)3) resulting in a 65 mM solution of the relaxing agent in solvent as described in G. Singh, A. Kothari, V. Gupta, Polymer Testing 2009, 28(5), 475. To ensure a homogeneous solution, after initial sample preparation in a heat block, the NMR tube is still was heated in a rotary oven for at least 1 hour. On insertion into the magnet, the tube was rotated at 10 Hz. This setting was chosen primarily for the high and quantitative resolution required for accurate ethylene content quantification. Standard single pulse excitation was used without NOE, using an optimized tip angle, 1 s recycling delay and a double-level WALTZ16 shutdown scheme as described in Z. Zhou, R. Kuemmerle, X. Qiu, D. Redwine , R. Cong, A. Taha, D. Baugh, B. Winniford, J. Mag. Reson. 187 (2007) 225 and V. Busico, P. Carbonniere, R. Cipullo, C. Pellecchia, J. Severn, G. Talarico, Macromol. Rapid Commun. 2007, 28, 1128. A total of 6144 (6k) transients were acquired per spectrum. Quantitative 13C{1H} NMR spectra were processed, integrated and the relevant and integrated quantitative properties determined from the integrals. All chemical changes were indirectly referenced to the central methylene group of the ethylene block (EEE) at 30.00 ppm using the chemical solvent change. This method allowed for comparable reference even when this structural unit was not present.
    [00139] With characteristic signs corresponding to 2.1 erythro regiodefects observed (as described in L. Resconi, L. Cavallo, A. Fait, F. Piemontesi, Chem. Rev. 2000, 100 (4), 1253, in Cheng, HN, Macromolecules 1984, 17, 1950 and in WJ. Wang and S. Zhu, Macromolecules 2000, 33 1157) correction for the influence of regiodefects on the determined properties was required. The characteristic signs corresponding to other types of regiodefects were not observed.
    [00140] The characteristic signs corresponding to ethylene incorporation were observed (as described in Cheng, H.N., Macromolecules 1984, 17, 1950) and the comonomer fraction calculated as the fraction of ethylene in the polymer relative to all monomers in the polymer.
    [00141] The comonomer fraction was quantified using the W-J method. Wang and S. Zhu, Macromolecules 2000, 33 1157, by integrating multiple signals across the full spectral region in the 13C{1H} spectrum. This method was chosen for its nature and ability to count on the presence of regiodefects when necessary. The integral regions were slightly adjusted to increase applicability across the full range of comonomer contents found.
    [00142] The mole percent comonomer incorporation was calculated from the mole fraction. The incorporation of the weight percent comonomer was calculated from the mol fraction. Xylene solubles (XCS, % by weight): cold xylene solubles (XCS) content is determined at 25°C in accordance with ISO 16152; first edition; 2005.
    [00143] DSC analysis, melting temperature (Tm) measured with a TA Instrument Q200 differential scanning calorimetry (DSC) on 5-7 mg samples. DSC is performed according to an ISO 11357 / part 3 / method C2 (1999) in a heat / cold / heat cycle with a scan rate of 10°C/min in the temperature range of -30 to +225°C . The melting temperature is determined from the second heating step. Size Exclusion Chromatography (SEC): Number average molecular weight (Mn), weight average molecular weight (Mw) and polydispersity (Mw/Mn) are determined by size exclusion chromatography (SEC) using Waters Alliance GPCV 2000 instrument with viscometer online. Oven temperature is 140°C. Trichlorobenzene is used as a solvent (ISO 16014: 2003). Elastic tests:
    [00144] Elastic modulus, tensile deformation at break and elastic stress at break were measured at 23°C according to an ISO 527-2 (crosshead speed 1 mm/min for elastic modulus, 50 mm/min for others) using injection molded specimens molded at 230°C in accordance with an ISO 527-2(1B), produced in accordance with EN ISO 1873-2 (dog bone shape 10, 4 mm thick). Charpy Impact Test: Charpy Impact Strength (IS) was measured according to ISO 179-1eU: 2000 at +23°C and Charpy Bevel Impact Strength (NIS) was measured according to ISO 179-1eA :2000 at +23°C, using 80 x 10 x 4 mm3 injection molded bar test specimens prepared in accordance with ISO 1873-2:2007.
    [00145] The Heat Distortion Temperature (HDT) was determined according to an ISO 75-2 A method (1.80 MPa surface tension) using 80 x 10 x 4 mm3 injection molded test specimens produced as described in EN ISO 1873-2 (80 x 10 x 4 mm). Total volatile emissions
    [00146] Total polymer emission was determined by using multiple headspace extraction according to VDA 277:1995 using a gas chromatograph and a headspace method. The equipment was a Hewlett Packard gas chromatograph with a WCOT capillary column (wax type) 30 m long and 0.25 mm x 2.5 μm internal diameter (0.25 μm film thickness). A flame ionization detector was used with hydrogen as a combustible gas.
    [00147] The GC adjustments were as follows: 3 minutes isothermal at 50°C, heat up to 200°C at 12 K/min, 4 minutes isothermal at 200°C, injection temperature: 200°C, detection temperature: 250 °C, carrier helium, flow mode split 1:20 and medium carrier speed 22 to 27 cm/sec.
    [00148] The emission potential was measured on the basis of the sum of all values provided by the substances emitted after gas chromatography analysis and flame ionization detection with acetone as the calibration standard. Sample introduction (granules, about 1 gram) was by headspace analysis (10 ml headspace vial) after conditioning at 120°C for 5 hours prior to measurement.
    [00149] The unit is μgC/g (μg of carbon per g of sample), respectively ppm. VOC/FOG Issuance
    [00150] The VOC/FOG emission was measured according to VDA 278:2002 in the granular compounds. Volatile organic compounds are measured in toluene equivalents per gram of sample (μgTE/g). Obscuration is measured in hexadecane equivalents per gram of sample (μgHD/g).
    [00151] Measurements were performed with a TDSA supplied by Gerstel using 5.0 helium as a carrier gas and a 50 m long HP Ultra 2 column of 0.32 mm diameter and 0.52 µm 5% coating Phenyl-Methyl-Siloxane.
    [00152] VOC analysis was performed according to a device setting 1 listed in the standard using the following main parameters: no flow mode split, final temperature 90°C; end time 30 min, rate 60K/min. The cooling siphon was purged with a 1:30 flow mode split over a temperature range of -150°C to + 280°C with a heating rate of 12 K/second and a final time of 5 min. The following GC settings were used for the analysis: 2 min isothermal at 40°C. heating at 3 K/min to 92°C, then at 5 K/min to 160°C and then at 10 K/min to 280°C, 10 minutes isothermal; flow 1.3 ml/min.
    [00153] The VOC amounts account for species C10 to C16.
    [00154] The FOG analysis was performed according to setting device 1 listed in the standard using the following main parameters: no flow mode split, rate 60K/min; final temperature 120°C; end time 60 min. The cooling siphon was purged with a 1:30 flow mode split over a temperature range of -150°C to + 280°C with a heating rate of 12 K/sec. The following GC settings were used for the analysis: isothermal at 50°C for 2 min, heating at 25 K/min to 160°C, then at 10 K/min to 280°C, 30 min isothermal; flow 1.3 ml/min.
    [00155] The FOG quantities account for species C16 to C30. EXAMPLES Catalyst Preparation:
    [00156] The catalyst used in Inventive Examples IE1 to 1E4 were prepared following the procedure described in WO 2013/007650 A1 for E2 catalyst, by adjusting the amounts of metallocene and MAO in order to achieve the Al/Zr ratios indicated in Table 1. The catalyst was prepolymerized off-line with propylene following the procedure described in WO 2013/007650 A1 for E2P catalyst.
    The complex used was rac-anti-Me2Si(2-Me-4-(p-tBuPh)-Ind)(2-Me-4-Ph-5-OMe-6-tBu-Ind)ZrCl2. Off-line prepolymerization degree 3.3 g/g Al/Zr molar ratio in catalyst 431 mol/mol Metallocene complex content of off-line prepolymerized catalyst 0.696% by weight
    [00158] The same catalyst was used to prepare the polymer of Comparative Examples CE1 and CE2.
    [00159] For Comparative Examples CE3 and CE4, commercially available base polymers based on ZN catalysts were used.
    [00160] For Comparative Example CE5, the catalyst used in the polymerization process of the base polymer for CE5 was produced as follows: First, 0.1 mol of MgCl2 x 3 EtOH was suspended under inert conditions in 250 ml of decane in a reactor at atmospheric pressure. The solution was cooled to a temperature of -15°C and 300 ml of cold TiCl4 was added while maintaining the temperature at that level. Then, the slurry temperature was slightly increased to 20°C. At this temperature, 0.02 mol of dioctyl phthalate (DOP) was added to the slurry. After addition of the phthalate, the temperature was raised to 135°C for 90 minutes and the slurry was allowed to settle for 60 minutes. Then another 300 ml of TiCl4 was added and the temperature was maintained at 135°C for 120 minutes. After this, the catalyst was filtered from the liquid and washed six times with 300 ml of heptane at 80°C. Then, the solid catalyst component was filtered and dried. The catalyst and its concept of preparation is generally described, for example, in patent publications EP491566, EP591224 to EP586390. As the aluminum triethyl cocatalyst (TEAL) and as the dicyclopentyl dimethyl silane donor (D donor) was used. The aluminum to donor ratio was 5 mol/mol. Prior to polymerization, the catalyst was prepolymerized with vinyl cyclohexane in an amount to achieve a concentration of 200 ppm poly(vinyl cyclohexane) (PVCH) in the final polymer. The respective process is described in EP 1 028 984 and EP 1 183 307. Preparation of base polymer (PP-RACO)
    [00161] Base polymers for IE1 to IE4 and base polymer CE1 and CE2 were prepared in a Borstar® PP pilot plant with a prepolymerization reactor, a loop reactor and 2 gas phase reactors (GPR1 and GPR2 ) connected in series. Table 1: Preparation of base polymers for IE1 to IE 4 and for CE1 and CE2
    [00162] The base polymers (BP1) for IE1 and IE2 are the same, the base polymers for IE3 and 1E4 (BP2) are the same and the base polymers for CE1 and CE2 (BP3) are the same

    not applicable, as long as not used
    [00163] The base polymer (BP4) for CE3 is a mixture of 79.2% by weight of HF700SA, being a commercially available PP homopolymer from Borealis AG, Austria, having an MFR (230°C/2.16 kg ) of 21 g/10 minutes, a density of 905 kg/m3 and a melting point (DSC) of 165°C and 20.8% by weight BE50, being a PP homopolymer commercially available from Borealis AG, Austria, having an MFR (230°C/2.16 kg) of 0.3 g/10 minutes, a density of 905 kg/m3 and a melting point (DSC) of 165°C.
    [00164] The base polymer (BP5) for CE4 is a mixture of 79.1% by weight of HF700SA, being a commercially available PP homopolymer from Borealis AG, Austria, having an MFR (230°C/2.16 kg ) of 21 g/10 minutes, a density of 905 kg/m3 and a melting point (DSC) of 165°C and 20.9% by weight BE50, being a PP homopolymer commercially available from Borealis AG, Austria, having an MFR (230°C/2.16 kg) of 0.3 g/10 minutes, a density of 905 kg/m3 and a melting point (DSC) of 165°C. Polymerization conditions for base polymer (BP6) for CE5

    [00165] The base polymer (BP7) for CE6 is the commercial polypropylene random copolymer (PP-RACO) "RF366MO" from Borealis AG with an MFR2 of 20 g/10 minutes, a melting temperature of 151°C, a methylene content of 3.3% by weight, an XCS content of 6.0% by weight, a density of 905 kg/m3 and an elastic modulus of 1,200 MPa; Preparation of combinations
    [00166] The following inventive examples from IE1 to 1E4 and comparative examples from CE1 to CE6 were prepared by compounding in a co-rotating twin screw extruder with a typical screw configuration for fiberglass blending using a temperature range between 200 and 240°C. Composition compost recipe

    [00167] AP-1 is the commercial maleic anhydride functionalized polypropylene "Exxelor P01020" from Exxon Mobil with a density of 0.9 g/cm3, an MFR2 of 430 g/10 minutes and a MAH content of 1.0% in mol;
    [00168] AP-2 is the commercial maleic anhydride functionalized polypropylene "Scona TPPP 2112FA" from Kometra GmbH, Germany with a density of 0.9 g/cm3, having an MFR2 of 5 g/10 minutes and a MAH content of 1.2% by mol.
    DSTDP is Di-stearyl-thio-dipropionate heat stabilizer (CAS No. 693-36-7) commercially available as Irganox PS-802 FL from BASF AG, Germany.
    [00170] AO3 is the primary antioxidant Bis-(3,3-bis(4'-hydroxy-3'-tert-butylphenyl)butanic acid)-glycoester (CAS No. 32509-66-3) commercially available as Hostanox 03 from Clariant SE, Switzerland
    [00171] P168 is the secondary antioxidant Tris (2,4-di-t-butylphenyl) phosphite (CAS No. 31570-04-4) commercially available as Irgafos 168 from BASF AG, Germany
    [00172] MB-1 is the standard blend of commercial carbon black “Plasblak PE4103” from Cabot Corporation, Germany
    [00173] GF are Johns Manville's commercial “Thermo Flow ® Chopped Strand 636 for PP” glass fibers, which are E-glass fibers coated with a silane-based coating, a length of 4 mm and an average diameter of 13 µm
    [00174] The compositions have the following properties
    CV...volatile content TM...elastic modulus Bstress elastic stress in breaking Bstrain tensile deformation in breaking IS Charpy impact force (ISO 179-1eU) at 23°C NIS Charpy bevel impact force (ISO 179-1eA) at 23°C HDT heat deflection temperature na - not determined
    [00175] As can be seen from Figure 1 and 2, the compositions of the Inventive Examples show much better impact/hardness balance as the compositions of Comparative Examples CE1 to CE4.
    [00176] Additionally, the compositions of the Inventive Examples have clearly much lower emissions.
    权利要求:
    Claims (12)
    [0001]
    1. Fiber reinforced composition, characterized in that it comprises (a) 50.0 to 84.5% by weight of a metallocene catalyzed random polypropylene copolymer comprising ethylene and/or α-olefin C4 to C8 (PP- RACO), (b) 15.0 to 45.0% by weight of glass fibers (GF) and (c) 0.5 to 5.0% by weight of a modified polypropylene as adhesion promoter (AP), with based on the total weight of the fiber reinforced composition, wherein (i) the polypropylene random copolymer comprising 1.0 to 10.0% by weight of ethylene and/or C4 to C8 α-olefin (PP-RACO) having a melt flow rate of MFR2 (230°C) measured in accordance with ISO 1133 of at least 2.5 g/10 minutes up to 15.0 g/10 minutes, and has a cold soluble xylene content (XCS) measured in accordance with with ISO 16152 (25°C) in the range of 10 to 25% by weight. (ii) the glass fibers (GF) are cut glass fibers and (iii) the complete polymer contained in the reinforced composition forms a single-phase continuous phase being the matrix of the fiber reinforced composition.
    [0002]
    2. Fiber reinforced composition according to claim 1, characterized in that it has a polydispersity (Mw/Mn) as determined by size exclusion chromatography in the range of 1.5 to 6.5.
    [0003]
    3. Fiber reinforced composition according to claim 1 or 2, characterized in that the adhesion promoter (AP) is a polypropylene homo or copolymer with grafted polar groups, preferably with maleic anhydride groups.
    [0004]
    4. Fiber-reinforced composition according to any one of the preceding claims, characterized in that the total elastic modulus measured at 23°C according to ISO 527-2 (crosshead speed of 1 mm/minute) is pile minus 2,500 MPa.
    [0005]
    5. Fiber reinforced composition according to any one of the preceding claims, characterized in that the tensile deformation at break measured at 23°C according to ISO 527-2 (crosshead speed 50 mm/minute) is at least 4.0%.
    [0006]
    6. Fiber reinforced composition according to any one of the preceding claims, characterized in that the amount of volatile organic compounds (VOC) measured in accordance with VDA 278:2002 is equal to or below 50 ppm.
    [0007]
    7. Fiber reinforced composition according to any one of the preceding claims, characterized in that the amount of obscuring compounds (FOG) measured in accordance with VDA 278:2002 is equal to or below 130 ppm.
    [0008]
    8. Fiber reinforced composition according to claim 1, characterized in that polypropylene random copolymer (PP-RACO) is prepared by polymerizing propylene and ethylene and/or α-olefin C4-8 in the presence of a catalyst , said catalyst comprises an asymmetric complex of formula (I)
    [0009]
    9. Fiber reinforced composition according to claim 8, characterized in that the polypropylene random copolymer (PP-RACO) is prepared by the polymerization of propylene and ethylene and/or α-olefin C4-8 in the presence of a catalyst , said catalyst comprises an asymmetric complex of formula (V) or (V')
    [0010]
    10. Process for preparing a fiber reinforced composition as defined in any one of claims 1 to 9, characterized in that it comprises the steps of adding (a) polypropylene random copolymer (PP-RACO), (b) the fibers of glass (GF) and (c) polar modified polypropylene as adhesion promoter (AP) to an extruder and extruding them obtaining said fiber reinforced composition.
    [0011]
    11. Automotive article, characterized in that it comprises the fiber reinforced composition as defined in any one of claims 1 to 9.
    [0012]
    12. Foam article, characterized in that it comprises the fiber reinforced composition as defined in any one of claims 1 to 9.
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    同族专利:
    公开号 | 公开日
    CN106255718B|2018-09-21|
    US10030109B2|2018-07-24|
    CA2938228C|2018-01-02|
    US20170166711A1|2017-06-15|
    ES2674238T3|2018-06-28|
    WO2015121160A1|2015-08-20|
    EP2907841A1|2015-08-19|
    MX352067B|2017-11-08|
    KR20160110526A|2016-09-21|
    CA2938228A1|2015-08-20|
    ZA201604861B|2017-08-30|
    KR101759857B1|2017-07-19|
    EP3105287B1|2018-04-04|
    EA201600565A1|2016-12-30|
    MX2016009938A|2016-10-31|
    EP3105287A1|2016-12-21|
    CN106255718A|2016-12-21|
    EA031496B1|2019-01-31|
    JP2017509742A|2017-04-06|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    US4226963A|1971-06-25|1980-10-07|Montedison S.P.A.|Process for the stereoregular polymerization of alpha-olephins|
    US4107414A|1971-06-25|1978-08-15|Montecatini Edison S.P.A.|Process for the stereoregular polymerization of alpha olefins|
    US4186107A|1978-04-14|1980-01-29|Hercules Incorporated|Solid catalyst component for olefin polymerization|
    US4347160A|1980-06-27|1982-08-31|Stauffer Chemical Company|Titanium halide catalyst system|
    IT1209255B|1980-08-13|1989-07-16|Montedison Spa|CATALYSTS FOR THE POLYMERIZATION OF OLEFINE.|
    JPS57153005A|1981-03-19|1982-09-21|Ube Ind Ltd|Polymerization of alpha-olefin|
    US4530912A|1981-06-04|1985-07-23|Chemplex Company|Polymerization catalyst and method|
    EP0072129B2|1981-08-07|1990-02-28|Imperial Chemical Industries Plc|Supported transition metal composition|
    US4382019A|1981-09-10|1983-05-03|Stauffer Chemical Company|Purified catalyst support|
    IT1190683B|1982-02-12|1988-02-24|Montedison Spa|COMPONENTS AND CATALYSTS FOR THE POLYMERIZATION OF OLEFINE|
    IT1190681B|1982-02-12|1988-02-24|Montedison Spa|COMPONENTS AND CATALYSTS FOR THE POLYMERIZATION OF OLEFINE|
    IT1190682B|1982-02-12|1988-02-24|Montedison Spa|CATALYSTS FOR THE POLYMERIZATION OF OLEFINE|
    US4532313A|1982-10-13|1985-07-30|Himont Incorporated|Method for preparing an improved catalyst support, Ziegler-Natta catalyst utilizing said support and polymerization of 1-olefins utilizing said catalyst|
    US4560671A|1983-07-01|1985-12-24|Union Carbide Corporation|Olefin polymerization catalysts adapted for gas phase processes|
    US4657882A|1984-11-26|1987-04-14|Amoco Corporation|Supported olefin polymerization catalyst produced from a magnesium alkyl/organophosphoryl complex|
    US4581342A|1984-11-26|1986-04-08|Standard Oil Company |Supported olefin polymerization catalyst|
    US4665208A|1985-07-11|1987-05-12|Exxon Chemical Patents Inc.|Process for the preparation of alumoxanes|
    FI80055C|1986-06-09|1990-04-10|Neste Oy|Process for preparing catalytic components for polymerization of olefins|
    US5077255A|1986-09-09|1991-12-31|Exxon Chemical Patents Inc.|New supported polymerization catalyst|
    EP0287666B1|1986-09-24|1993-05-26|Mitsui Petrochemical Industries, Ltd.|Process for polymerizing olefins|
    JPH0780933B2|1986-11-20|1995-08-30|三井石油化学工業株式会社|Olefin Polymerization Method|
    JPH0742301B2|1987-02-14|1995-05-10|三井石油化学工業株式会社|Particulate aluminoxane, its manufacturing method and its use|
    JP2538588B2|1987-04-03|1996-09-25|三井石油化学工業株式会社|Method for producing solid catalyst for olefin polymerization|
    US5206199A|1987-04-20|1993-04-27|Mitsui Petrochemical Industries, Ltd.|Catalyst for polymerizing an olefin and process for polymerizing an olefin|
    US5091352A|1988-09-14|1992-02-25|Mitsui Petrochemical Industries, Ltd.|Olefin polymerization catalyst component, olefin polymerization catalyst and process for the polymerization of olefins|
    IT1227260B|1988-09-30|1991-03-28|Himont Inc|DIETTERS THAT CAN BE USED IN THE PREPARATION OF ZIEGLER-NATTA CATALYSTS|
    US4908463A|1988-12-05|1990-03-13|Ethyl Corporation|Aluminoxane process|
    US5103031A|1989-02-21|1992-04-07|Ethyl Corporation|Falling film aluminoxane process|
    US4968827A|1989-06-06|1990-11-06|Ethyl Corporation|Alkylaluminoxane process|
    US4924018A|1989-06-26|1990-05-08|Ethyl Corporation|Alkylaluminoxane process|
    US5036034A|1989-10-10|1991-07-30|Fina Technology, Inc.|Catalyst for producing hemiisotactic polypropylene|
    JPH0813826B2|1990-11-29|1996-02-14|信越化学工業株式会社|Thexyltrialkoxysilane|
    FI86866C|1990-12-19|1992-10-26|Neste Oy|FOERFARANDE FOER MODIFIERING AV CATALYSTATOR AVSEDDA FOER POLYMERISATION AV OLEFINER|
    FI86867C|1990-12-28|1992-10-26|Neste Oy|FLERSTEGSPROCESS FOR FRAMSTAELLNING AV POLYETEN|
    SE467825B|1991-01-22|1992-09-21|Neste Oy|SETTING OUT OF PLASTIC MATERIALS ELIMINATE SMELLING / TASTEING OBJECTS|
    FI88049C|1991-05-09|1993-03-25|Neste Oy|Large pore polyolefin, process for its preparation and a catalyst used in the process|
    FI88047C|1991-05-09|1993-03-25|Neste Oy|Catalyst-based catalyst for polymerization of olivines|
    FI88048C|1991-05-09|1993-03-25|Neste Oy|Coarse-grained polyolefin, its method of preparation and a catalyst used in the method|
    FI90247C|1991-05-31|1994-01-10|Borealis As|Process for the preparation of active and uniform carrier particles for polymerization catalysts|
    US5308815A|1991-07-26|1994-05-03|Ethyl Corporation|Heterogeneous methylaluminoxane catalyst system|
    US5157137A|1991-07-26|1992-10-20|Ethyl Corporation|Method of making gel free alkylaluminoxane solutions|
    US5416228A|1991-10-07|1995-05-16|Fina Technology, Inc.|Process and catalyst for producing isotactic polyolefins|
    FI91967C|1991-11-29|1994-09-12|Borealis Polymers Oy|Process for the preparation of olefin polymerization catalysts|
    FI90248C|1991-11-29|1994-01-10|Borealis As|A process for preparing a particulate support for an olefin polymerization catalyst|
    US5329032A|1992-03-18|1994-07-12|Akzo Chemicals Inc.|Polymethylaluminoxane of enhanced solution stability|
    US5235081A|1992-03-18|1993-08-10|Ethyl Corporation|Method of removing gel forming materials from methylaluminoxanes|
    FI95715C|1992-03-24|1996-03-11|Neste Oy|Preparation of polymerization catalyst support prepared by spray crystallization|
    IT1260495B|1992-05-29|1996-04-09|Himont Inc|CONCENTRATES SUITABLE FOR THE PREPARATION OF FUNCTIONALIZED POLYOLEFINS AND FUNCTIONALIZATION PROCESS THROUGH THOSE CONCENTRATES|
    US5248801A|1992-08-27|1993-09-28|Ethyl Corporation|Preparation of methylaluminoxanes|
    US5939346A|1992-11-02|1999-08-17|Akzo Nobel N.V.|Catalyst system comprising an aryloxyaluminoxane containing an electron withdrawing group|
    US5391793A|1992-11-02|1995-02-21|Akzo Nobel N.V.|Aryloxyaluminoxanes|
    US5332706A|1992-12-28|1994-07-26|Mobil Oil Corporation|Process and a catalyst for preventing reactor fouling|
    EP0841371B1|1993-01-11|2002-11-20|Mitsui Chemicals, Inc.|Propylene polymer compositions|
    US5391529A|1993-02-01|1995-02-21|Albemarle Corporation|Siloxy-aluminoxane compositions, and catalysts which include such compositions with a metallocene|
    US5529850A|1994-07-05|1996-06-25|Montell North America Inc.|Fibers produced from crystalline propylene polymers having high melt flow rate values and a narrow molecular weight distribution|
    CA2121721C|1993-04-29|2004-11-23|Giampiero Morini|Crystalline propylene polymers having high melt flow rate values and a narrow molecular weight distribution|
    DE69431222T2|1993-06-07|2003-04-17|Mitsui Chemicals Inc|Transition metal compound, and polymerization catalyst containing the same|
    DE4337251A1|1993-09-27|1995-03-30|Hoechst Ag|Biaxially oriented polypropylene film with improved properties in terms of mechanics and barrier|
    FI96866C|1993-11-05|1996-09-10|Borealis As|Support olefin polymerization catalyst, its preparation and use|
    FI96214C|1994-05-31|1996-05-27|Borealis As|Stereospecific catalyst system for the polymerization of olefins|
    US6322883B1|1994-07-15|2001-11-27|Exxonmobil Oil Corporation|Uniaxially shrinkable biaxially oriented polypropylene film with HDPE skin|
    IL117114A|1995-02-21|2000-02-17|Montell North America Inc|Components and catalysts for the polymerization ofolefins|
    US5731253A|1995-07-27|1998-03-24|Albemarle Corporation|Hydrocarbylsilloxy - aluminoxane compositions|
    US6403772B1|1995-09-11|2002-06-11|Montell Technology Company, Bv|Open-pentadienyl metallocenes, precursors thereof and polymerization catalysts therefrom|
    US5922631A|1995-10-19|1999-07-13|Albemarle Corporation|Liquid clathrate aluminoxane compositions as co-catalysts with transition metal catalyst compounds|
    US5670682A|1995-10-19|1997-09-23|Albemarle Corporation|Liquid clathrate aluminoxane compositions|
    US5693838A|1995-11-13|1997-12-02|Albemarle Corporation|Aluminoxane process and product|
    FI104826B|1996-01-30|2000-04-14|Borealis As|Heteroatom-substituted metallose compounds for catalytic systems in olefin polymerization and process for their preparation|
    JPH09268248A|1996-03-29|1997-10-14|Tonen Chem Corp|Thermoplastic resin composition|
    FI102070B1|1996-03-29|1998-10-15|Borealis As|New complex compound, its preparation and use|
    US5731451A|1996-07-12|1998-03-24|Akzo Nobel Nv|Modified polyalkylauminoxane composition formed using reagent containing aluminum trialkyl siloxide|
    FI963707A0|1996-09-19|1996-09-19|Borealis Polymers Oy|Free polymerization of an alpha-olefin, by polymerization with an optional catalyst and further preparation of a polymer|
    JP2001504401A|1996-10-14|2001-04-03|ディーエスエムエヌ．ブイ．|Rod-shaped pellets|
    US5744656A|1996-10-25|1998-04-28|Boulder Scientific Company|Conversion of hexafluorobenzene to bromopentafluorobenzene|
    BR9808827B1|1997-03-07|2009-12-01|process for the preparation of indanones, and use of an indanone.|
    FI971565A|1997-04-14|1998-10-15|Borealis As|Substituted metallocene compounds for catalyst systems intended for polymerization of olefins, intermediates and processes for their preparation|
    GB9708487D0|1997-04-25|1997-06-18|Bp Chem Int Ltd|Novel catalysts for olefin polymerisation|
    WO1998056831A1|1997-06-10|1998-12-17|Peroxid-Chemie Gmbh & Co. Kg.|New catalyst systems for polymerization reactions, metallocene amide halogenides, the production and use thereof|
    FI111846B|1997-06-24|2003-09-30|Borealis Tech Oy|Process and apparatus for preparing mixtures of polypropylene|
    FI104824B|1997-06-24|2000-04-14|Borealis As|Process for producing propylene polymers|
    CN1140554C|1997-06-24|2004-03-03|波里阿利斯有限公司|Process for preparing propylene copolymers|
    FI111848B|1997-06-24|2003-09-30|Borealis Tech Oy|Process and equipment for the preparation of homopolymers and copolymers of propylene|
    FI111847B|1997-06-24|2003-09-30|Borealis Tech Oy|A process for the preparation of copolymers of propylene|
    FI111845B|1997-06-24|2003-09-30|Borealis Tech Oy|Process for producing propylene homopolymers and polymers with modified impact strength|
    FI973451A0|1997-08-22|1997-08-22|Borealis As|New organometallic processes and methods For the polymerization of olefins with the aid of a catalytic composition with an organic compound|
    ID24448A|1997-09-05|2000-07-20|Bp Chemical Ltd|POLYMERIZATION CATALYSTS|
    FI980342A0|1997-11-07|1998-02-13|Borealis As|Polymerroer och -roerkopplingar|
    GB9721559D0|1997-10-11|1997-12-10|Bp Chem Int Ltd|Novel polymerisation catalysts|
    FI974175A|1997-11-07|1999-05-08|Borealis As|Process for producing polypropylene|
    JP2001527136A|1997-12-23|2001-12-25|ボレアリステクノロジーオイ|Catalyst component containing magnesium, titanium, halogen and electron donor, method of making and using the same|
    WO1999041290A1|1998-02-12|1999-08-19|University Of Delaware|Catalyst compounds with beta-diiminate anionic ligands and processes for polymerizing olefins|
    GB9826874D0|1998-12-07|1999-01-27|Borealis As|Process|
    FI991057A0|1999-05-07|1999-05-07|Borealis As|High stiffness propylene polymers and process for their preparation|
    BRPI0016723B1|1999-12-23|2018-02-27|Basell Polyolefine Gmbh.|METALOCENE, CATALYST SYSTEM, AND PROCESS FOR THE COPOLIMERIZATION OF PROPYLENE WITH ETHYLENE|
    US6384142B1|2000-02-08|2002-05-07|Exxonmobil Chemical Patents Inc.|Propylene impact copolymers|
    GB0007002D0|2000-03-22|2000-05-10|Borealis Polymers Oy|Catalysts|
    EP1313746B1|2000-06-30|2005-07-27|ExxonMobil Chemical Patents Inc.|Metallocenes with a bridged 4-phenyl-indenyl-ligand for olefin polymerisation|
    US6642317B1|2000-11-15|2003-11-04|Polypropylene Belgium Naamlose Vennootschap|Composition based on propylene polymers and process for obtaining same|
    US6586528B1|2000-11-15|2003-07-01|Polypropylene Belgium |Composition based on propylene polymers and process for obtaining same|
    CA2406611A1|2000-12-22|2002-07-04|Basell Poliolefine Italia S.P.A.|Polyolefin sheets for thermoforming|
    TWI238169B|2000-12-22|2005-08-21|Basell Technology Co Bv|Bioriented polypropylene films|
    ES2265376T3|2001-06-20|2007-02-16|Borealis Technology Oy|PREPARATION OF CATALYST COMPONENT FOR POLYMERIZATION OF OLEFINS.|
    AT328912T|2001-06-20|2006-06-15|Borealis Tech Oy|Preparation of a catalyst component for olefin polymerisation|
    EP1359171B1|2001-06-27|2005-10-26|Borealis Technology Oy|Propylene polymer resin with improved properties|
    JP2003128854A|2001-10-19|2003-05-08|Grand Polymer Co Ltd|Polypropylene resin composition, its manufacturing method and foamed material from the same|
    DE60211012T2|2001-11-27|2007-05-03|Basell Poliolefine Italia S.R.L.|Transparent and flexible polypropylene compositions|
    TWI268939B|2001-12-12|2006-12-21|Basell Poliolefine Spa|Process for the polymerization of olefins|
    EP1323747A1|2001-12-19|2003-07-02|Borealis Technology Oy|Production of olefin polymerisation catalysts|
    ES2236371T5|2002-02-04|2011-08-01|Borealis Technology Oy|LAMINARY MATERIAL WITH HIGH IMPACT RESISTANCE.|
    WO2003082879A1|2002-03-28|2003-10-09|Albemarle Corporation|Ionic aluminoxanate compositions and their use in catalysis|
    BR0215768A|2002-06-25|2005-03-15|Borealis Tech Oy|Process for the preparation of a biomodal rubber polypropylene polymer composition, polymer product, use of polymer, and molded article|
    AT396472T|2002-06-26|2008-06-15|Avery Dennison Corp|LENGTH-ORIENTED POLYMER FILMS|
    AU2003250201B2|2002-08-01|2008-12-11|Basell Poliolefine Italia S.P.A.|Highly stereoregular polypropylene with improved properties|
    US7807769B2|2002-09-20|2010-10-05|Exxonmobil Chemical Patents Inc.|Isotactic polypropylene produced from supercritical polymerization process|
    EP1403292B1|2002-09-30|2016-04-13|Borealis Polymers Oy|Process for preparing an olefin polymerisation catalyst component with improved high temperature activity|
    EP1452630A1|2003-02-26|2004-09-01|Borealis Technology OY|Polypropylene fibres|
    EP1484343A1|2003-06-06|2004-12-08|Universiteit Twente|Process for the catalytic polymerization of olefins, a reactor system and its use in the same process|
    DE10359366A1|2003-12-18|2005-07-21|Nordenia Deutschland Gronau Gmbh|Labeling film laminate|
    EP1697445A1|2003-12-24|2006-09-06|Petroquimica Cuyo S.A.I.C.|Sealing layer resin compositions|
    US20050187367A1|2004-02-19|2005-08-25|Sumitomo Chemical Company, Limited|Biaxially oriented polypropylene film|
    US20050200046A1|2004-03-10|2005-09-15|Breese D. R.|Machine-direction oriented multilayer films|
    US7285608B2|2004-04-21|2007-10-23|Novolen Technology Holdings C.V.|Metallocene ligands, metallocene compounds and metallocene catalysts, their synthesis and their use for the polymerization of olefins|
    ES2399823T3|2004-09-02|2013-04-03|Borealis Technology Oy|A polymer pipe without pressure, a composition for it, and a process for its preparation|
    US8222175B2|2004-12-31|2012-07-17|Borealis Technology Oy|Process for the preparation of an olefin polymerisation catalyst|
    CN100363417C|2005-01-28|2008-01-23|中国石油化工股份有限公司|Polypropylene composition and the biaxial stretching film prepared thereof|
    US20060177641A1|2005-02-09|2006-08-10|Breese D R|Multilayer polyethylene thin films|
    US20060211801A1|2005-03-16|2006-09-21|Fina Technology, Inc.|Polyolefin film and production thereof|
    ES2316050T3|2005-03-18|2009-04-01|Basell Polyolefine Gmbh|METALOCENE COMPOUNDS.|
    EP1726602A1|2005-05-27|2006-11-29|Borealis Technology Oy|Propylene polymer with high crystallinity|
    EP1741725B1|2005-07-08|2014-04-09|Borealis Technology Oy|Propylene polymer composition|
    EP1788023A1|2005-11-21|2007-05-23|Borealis Technology Oy|Multimodal polypropylene polymer composition|
    ES2588577T3|2005-12-30|2016-11-03|Borealis Technology Oy|Catalyst particles|
    EP1996600B1|2006-03-17|2011-09-28|Basell Polyolefine GmbH|Metallocene compounds|
    US20070235896A1|2006-04-06|2007-10-11|Fina Technology, Inc.|High shrink high modulus biaxially oriented films|
    EP2004664B1|2006-04-12|2016-12-14|Basell Polyolefine GmbH|Metallocene compounds|
    US7772338B2|2006-04-24|2010-08-10|Total Petrochemicals Research Feluy|Use of a Ziegler-Natta catalyst to make a polypropylene homopolymer or random copolymer having a high melt flow rate|
    ES2594859T3|2006-05-31|2016-12-23|Borealis Technology Oy|Catalyst with Al-alkoxy component|
    AT421760T|2006-07-10|2009-02-15|Borealis Tech Oy|ELECTRIC INSULATION FILM|
    US7977435B2|2006-07-12|2011-07-12|Lin Chon-Yie|Propylene polymer compositions and processes for making the same|
    EP1892264A1|2006-08-25|2008-02-27|Borealis Technology Oy|Extrusion coated substrate|
    EP1902837A1|2006-09-22|2008-03-26|Borealis Technology OY|Multilayer film|
    EP1923200A1|2006-11-20|2008-05-21|Borealis Technology Oy|Article|
    AT432165T|2006-12-18|2009-06-15|Borealis Tech Oy|TERPOLYMER WITH HIGH MELTING POINT|
    WO2008074713A1|2006-12-20|2008-06-26|Basell Poliolefine Italia S.R.L.|Filled polyolefin compositions|
    US8309659B2|2006-12-20|2012-11-13|Basell Poliolefine Italia S.R.L.|Filled polyolefin compositions|
    DE602006009412D1|2006-12-21|2009-11-05|Borealis Tech Oy|Movie|
    EP1947143A1|2007-01-19|2008-07-23|Borealis Technology Oy|Polypropylene-based resin composition and molded article thereof|
    EP1950241A1|2007-01-25|2008-07-30|Borealis Technology Oy|Multimodal medium density polyethylene polymer composition|
    EP1950233A1|2007-01-25|2008-07-30|Borealis Technology Oy|polymer|
    KR101497726B1|2007-04-27|2015-03-02|바셀 폴리올레핀 이탈리아 에스.알.엘|Butene-1 terpolymers and process for their preparation|
    AT438666T|2007-05-08|2009-08-15|Borealis Tech Oy|FOIL FOR ELECTRICAL INSULATION|
    EP2014714A1|2007-07-11|2009-01-14|Borealis Technology Oy|Heterophasic polyolefin composition|
    RU2458734C2|2007-08-03|2012-08-20|Базелль Полиолефин Италия С.Р.Л.|Method of producing propylene terpolymers|
    RU2487897C2|2008-08-21|2013-07-20|ДАУ ГЛОБАЛ ТЕКНОЛОДЖИЗ ЭлЭлСи|High melt flow rate, impact-resistant propylene copolymer and method for production thereof|
    CN101815727B|2007-08-27|2013-05-15|保瑞利斯科技公司|Catalysts|
    WO2009054832A1|2007-10-25|2009-04-30|Novolen Technology Holdings, C.V.|Metallocene compounds, catalysts comprising them, process for producing an olefin polymer by use of the catalysts, and olefin homo-and copolymers|
    CN101855289A|2007-11-13|2010-10-06|普瑞曼聚合物株式会社|Propylene resin composition for stretched sheet, and stretched sheet and thermally molded article each comprising the composition|
    EP2062936A1|2007-11-20|2009-05-27|Borealis Technology OY|Improved glass fiber reinforced polypropylene|
    AT539815T|2007-11-30|2012-01-15|Borealis Tech Oy|PROCESS FOR THE PREPARATION OF RANDOM PROPYLENE COPOLYMERS|
    EP2363433B1|2007-12-17|2018-02-07|Borealis Technology OY|Heterophasic polypropylene with high flowability and excellent low temperature impact properties|
    CN101903424A|2007-12-18|2010-12-01|巴塞尔聚烯烃意大利有限责任公司|Copolymers of propylene with hexene-1 and blown films obtained from them|
    EP2350145B1|2008-11-04|2018-08-15|ExxonMobil Chemical Patents Inc.|Homogeneous propylene polymerization in supercritical state and polypropylenes made therefrom|
    EP2147939A1|2008-07-22|2010-01-27|Borealis AG|Polypropylene composition with improved optics for film and moulding applications|
    US20100081760A1|2008-10-01|2010-04-01|Sunoco, Inc. |Film comprising a random copolymer with enhanced ethylene content|
    WO2010039715A1|2008-10-01|2010-04-08|Sunoco Chemicals, Inc.|Random copolymer with enhanced ethylene content|
    EP2174980B2|2008-10-07|2018-10-24|Borealis AG|High flowable heterophasic polypropylene|
    EP2361267B1|2008-11-07|2015-03-04|Borealis AG|Process to prepare a solid catalyst composition|
    EP2251361B1|2009-05-04|2013-10-02|Borealis AG|Preparation of precipitated ZN PP catalysts with internal pore structure using nanoparticles|
    EP2275476A1|2009-06-09|2011-01-19|Borealis AG|Automotive material with excellent flow, high stiffness, excellent ductility and low CLTE|
    US20110031645A1|2009-08-07|2011-02-10|Dow Global Technologies Inc.|Polypropylene for use in bopp applications|
    EP2530116B1|2009-08-28|2017-10-11|Borealis AG|Polypropylene-talc composite with reduced malodour|
    EP2305723A1|2009-10-01|2011-04-06|Total Petrochemicals Research Feluy|Propylene polymer with improved processability in thermoforming.|
    SI2308923T1|2009-10-09|2012-08-31|Borealis Ag|Glass fibre composite of improved processability|
    JP5441778B2|2010-03-18|2014-03-12|三井化学株式会社|Propylene-based resin composition and molded product obtained therefrom|
    ES2392240T3|2010-04-20|2012-12-07|Borealis Ag|Car interior compound|
    ES2710606T3|2010-04-20|2019-04-26|Borealis Ag|Polypropylene bottles|
    JP5785609B2|2010-04-28|2015-09-30|ボレアリス エージー|catalyst|
    CN103025767B|2010-04-28|2015-01-14|博瑞立斯有限公司|Solid particulate catalysts comprising bridged metallocenes|
    EP2386583A1|2010-05-07|2011-11-16|Borealis AG|Process for the preparation of a solid metallocene catalyst system and its use in polymerisation of olefins|
    ES2564189T3|2010-05-07|2016-03-18|Borealis Ag|Preparation of a solid catalyst system|
    KR20150027234A|2010-05-12|2015-03-11|보레알리스 아게|Polypropylene with specific calcium stearate content for special capacitors|
    EP2571932B1|2010-05-21|2017-07-05|Borealis AG|Composition|
    BR112012033011B1|2010-06-24|2020-05-26|Basell Poliolefine Italia S.R.L.|CATALYST SYSTEM AND PROCESS FOR POLYMERIZING OLEFINS USING SUCH SYSTEM|
    EP2402353B1|2010-07-01|2018-04-25|Borealis AG|Group 4 metallocenes useful as catalysts for the polymerization of olefins|
    ES2525554T3|2010-07-13|2014-12-26|Borealis Ag|Catalyst component|
    EP2410007B1|2010-07-22|2014-06-11|Borealis AG|Polypropylene/talc composition with improved impact behavior|
    EP2415831A1|2010-08-06|2012-02-08|Borealis AG|Heterophasic propylene copolymer with excellent impact/stiffness balance|
    ES2397547T3|2010-08-27|2013-03-07|Borealis Ag|Rigid polypropylene composition with excellent break elongation|
    US9062232B2|2011-01-03|2015-06-23|Borealis Ag|Sealing material of polypropylene with improved optical performance|
    EP2479025B1|2011-01-25|2019-03-06|Mondi Gronau GmbH|Sticker film|
    EP2532687A3|2011-06-10|2013-04-10|Borealis AG|Bridged Metallocene Catalysts|
    US9969820B2|2011-07-01|2018-05-15|Basell Poliolefine Italia S.R.L.|Polypropylene films and sheets|
    ES2643158T3|2011-07-08|2017-11-21|Borealis Ag|Catalysts|
    ES2552779T3|2011-07-15|2015-12-02|Borealis Ag|Composition of high fluid polyolefin with low shrinkage and CLTE|
    ES2628836T3|2011-07-15|2017-08-04|Borealis Ag|Non-oriented film|
    ES2626661T3|2011-07-27|2017-07-25|Borealis Ag|Lightweight polypropylene resin with superior surface characteristics for use in automotive interior applications|
    EP2565221B2|2011-08-30|2018-08-08|Borealis AG|Process for the manufacture of a capacitor film|
    EP3181637B1|2011-09-21|2017-11-29|Borealis AG|Moulding composition|
    EP2578395A1|2011-10-04|2013-04-10|Rkw Se|Multilayer label film construction for pressure sensitive labels|
    EP2589623A1|2011-11-02|2013-05-08|Basell Poliolefine Italia S.r.l.|Polypropylene composition for foaming|
    EP2592112A1|2011-11-11|2013-05-15|Basell Poliolefine Italia S.r.l.|Polymer composition for bumpers and interiors and polyethylene-based resin precursor|
    CN103890081B|2011-12-23|2016-09-07|博里利斯股份公司|For the method preparing heterophasic propylene copolymer|
    PL2794689T3|2011-12-23|2016-10-31|Propylene copolymer for injection molded articles or films|
    EP2610273B1|2011-12-30|2018-02-07|Borealis AG|Catalyst component|
    EP2610270B1|2011-12-30|2015-10-07|Borealis AG|Catalyst component|
    EP2610271B1|2011-12-30|2019-03-20|Borealis AG|Preparation of phthalate free ZN PP catalysts|
    EP2610272B1|2011-12-30|2017-05-10|Borealis AG|Catalyst component|
    EP2820053B1|2012-02-27|2016-12-21|Borealis AG|Process for the preparation of polypropylene with low ash content|
    EP2666818B1|2012-05-21|2016-10-26|Borealis AG|High flow polypropylene with excellent mechanical properties|
    CA2878998C|2012-08-07|2016-09-27|Borealis Ag|Process for the preparation of polypropylene with improved productivity|
    BR112015001309A2|2012-08-07|2017-07-04|Borealis Ag|process for preparing improved productivity polypropylene|
    EP3033389B1|2013-08-14|2017-10-11|Borealis AG|Propylene composition with improved impact resistance at low temperature|
    KR101805396B1|2013-08-21|2017-12-06|보레알리스 아게|High flow polyolefin composition with high stiffness and toughness|
    WO2015024887A1|2013-08-21|2015-02-26|Borealis Ag|High flow polyolefin composition with high stiffness and toughness|
    PL2853563T3|2013-09-27|2016-12-30|Films suitable for BOPP processing from polymers with high XS and high Tm|
    ES2568615T3|2013-10-11|2016-05-03|Borealis Ag|Label film oriented in the machine direction|
    ES2574428T3|2013-10-24|2016-06-17|Borealis Ag|Blow molded article based on bimodal random copolymer|
    WO2015059229A1|2013-10-24|2015-04-30|Borealis Ag|Low melting pp homopolymer with high content of regioerrors and high molecular weight|
    US9670293B2|2013-10-29|2017-06-06|Borealis Ag|Solid single site catalysts with high polymerisation activity|
    CN105722872B|2013-11-22|2017-10-13|博里利斯股份公司|Low emission Noblen with high melt flows|
    US9828698B2|2013-12-04|2017-11-28|Borealis Ag|Phthalate-free PP homopolymers for meltblown fibers|
    MX2016007438A|2013-12-18|2016-10-03|Borealis Ag|Bopp film with improved stiffness/toughness balance.|
    WO2015091829A1|2013-12-18|2015-06-25|Borealis Ag|Bopp film having low shrinkage|
    EP2886600B1|2013-12-19|2018-05-30|Abu Dhabi Polymers Co. Ltd LLC.|Multimodal polypropylene with respect to comonomer content|
    US20160312018A1|2013-12-31|2016-10-27|Borealis Ag|Process for producing propylene terpolymer|
    CN105829364B|2014-01-17|2017-11-10|博里利斯股份公司|Method for preparing the butylene copolymer of propylene/1|
    ES2571587T3|2014-01-29|2016-05-26|Borealis Ag|High fluid polyolefin composition with high rigidity and puncture resistance|
    JP6474417B2|2014-02-06|2019-02-27|ボレアリス エージー|Soft and transparent impact copolymers|
    JP2017508032A|2014-02-06|2017-03-23|ボレアリス エージー|Soft copolymer with high impact strength|
    EP2907841A1|2014-02-14|2015-08-19|Borealis AG|Polypropylene composite|
    EP2947118B1|2014-05-20|2017-11-29|Borealis AG|Polypropylene composition for automotive interior applications|
    EP3006472A1|2014-10-07|2016-04-13|Borealis AG|Process for the preparation of an alpha nucleated polypropylene|EP3033389B1|2013-08-14|2017-10-11|Borealis AG|Propylene composition with improved impact resistance at low temperature|
    WO2015024887A1|2013-08-21|2015-02-26|Borealis Ag|High flow polyolefin composition with high stiffness and toughness|
    KR101805396B1|2013-08-21|2017-12-06|보레알리스 아게|High flow polyolefin composition with high stiffness and toughness|
    PL2853563T3|2013-09-27|2016-12-30|Films suitable for BOPP processing from polymers with high XS and high Tm|
    ES2568615T3|2013-10-11|2016-05-03|Borealis Ag|Label film oriented in the machine direction|
    WO2015059229A1|2013-10-24|2015-04-30|Borealis Ag|Low melting pp homopolymer with high content of regioerrors and high molecular weight|
    US9828698B2|2013-12-04|2017-11-28|Borealis Ag|Phthalate-free PP homopolymers for meltblown fibers|
    MX2016007438A|2013-12-18|2016-10-03|Borealis Ag|Bopp film with improved stiffness/toughness balance.|
    CN105829364B|2014-01-17|2017-11-10|博里利斯股份公司|Method for preparing the butylene copolymer of propylene/1|
    JP6474417B2|2014-02-06|2019-02-27|ボレアリス エージー|Soft and transparent impact copolymers|
    JP2017508032A|2014-02-06|2017-03-23|ボレアリス エージー|Soft copolymer with high impact strength|
    EP2907841A1|2014-02-14|2015-08-19|Borealis AG|Polypropylene composite|
    WO2015169653A1|2014-05-06|2015-11-12|Basell Poliolefine Italia S.R.L.|Random propylene-ethylene copolymers|
    EP2947118B1|2014-05-20|2017-11-29|Borealis AG|Polypropylene composition for automotive interior applications|
    EP3371256A4|2015-11-02|2019-07-03|Braskem America, Inc.|Low emission propylene-based polymer resins|
    EP3568430A4|2017-01-10|2020-07-01|Celanese International Corporation|Long fiber-reinforced propylene composition for use in a thin part|
    CN110291140A|2017-01-10|2019-09-27|国际人造丝公司|The propylene compositions of high flow fiber enhancing with low emission|
    法律状态:
    2019-12-17| B06U| Preliminary requirement: requests with searches performed by other patent offices: procedure suspended [chapter 6.21 patent gazette]|
    2021-03-23| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|
    2021-05-04| B16A| Patent or certificate of addition of invention granted|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 06/02/2015, OBSERVADAS AS CONDICOES LEGAIS. |
    优先权:
    申请号 | 申请日 | 专利标题
    EP14155222.4|2014-02-14|
    EP14155222.4A|EP2907841A1|2014-02-14|2014-02-14|Polypropylene composite|
    PCT/EP2015/052476|WO2015121160A1|2014-02-14|2015-02-06|Polypropylene composite|
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