TW200837127A - Filled polyolefin compositions - Google Patents

Abstract

Filled polyolefin compositions comprising: (A) From20% to 80% by weight of a polypropylene component. (B) From 20% to 80% by weight of a filler; 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 polypropylene fraction Ai having a Melt Felt Rate value of 500g/10min or more, and from 20% to 80 by weight of a polypropylene fraction AII) having a Melt Flow Rate value of from 0.1 to 30g/10min, 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 a polyprolene fraction Ai having a Melt Flow Rate value of 500g/10min. or more, from 15% to 70% by weight of a polypropylene fraction AII) having a Melt Flow Rate of from 0.1 to 30G/10min. and from 0.5% to 15% by weight of a compatibilizer Q, the said percentages of Ai, AII) and Q being referred to the sum of Ai, AII) and Q.

Description

200837127 IX. INSTRUCTIONS OF THE INVENTION: TECHNICAL FIELD OF THE INVENTION The present invention relates to a polyolefin composition containing a coating having a balance of improved processing properties and mechanical properties. In particular, although significant and even very high amounts of dip are present, the compositions of the present invention are capable of achieving a very high melt flow rate (hereinafter abbreviated as M F R ) with very advantageous and exceptionally balanced mechanical properties. [Prior Art] ® In order to increase the final MFR of such a composition, it has been proposed in the art to use a propylene polymer having a high MFR. In particular, according to US Patent No. 49 97 875, improved melt flow characteristics and good mechanical properties are achieved by blending up to 50% by weight of fiber reinforcement to a polymerized propylene polymerization having an MFR of from about 55 to about 430 g/10 min. Obtained from the material. According to U · S · Patent Application N 〇 · 2 0 〇 6 0 2 6 4 5 5 7, reinforced polypropylene composition with good impact resistance is blended with high amounts of organic fibers and optionally inorganic fibers Obtained in a polypropylene resin having an MFR of from about 20 to about 1 500 g/l〇min. In fact, the highest MFR 丙烯 of the propylene polymer used in the examples of this document is 400-430 g/10 min. SUMMARY OF THE INVENTION It has been found that an improved balance of flexibility modulus, impact resistance, tensile properties, and heat deflection temperature (hereinafter referred to as HDT), etc., via blending of tantalum and polymerization of propylene having a very high MFR値Realized by things. Other improved properties obtained by the compositions of the present invention are dimensionally stable 200837127, resistance to plastic deformation and resistance to environmental stress cracking. In particular, the present invention provides a rhodium-containing polyolefin composition comprising: A) 20-80% by weight of a polypropylene component; B) 20-80% by weight of a dike; wherein the percentages of 'A) and B) are Based on the sum of A) and B), A) is selected from the following compositions: a) a polypropylene composition containing 20-80% by weight of a melt flow rate of 500 g/10 min or more (MFR1) The polypropylene fraction A1), and 20-80% by weight of the melt fraction (MFR11) having a melt flow rate of 0.1 to 30 g/10 min (AFR), the percentage of A1) and A11) is A1 And the sum of A11) as a reference; or b) a polypropylene composition containing 15-72% by weight of a polypropylene fraction (AFR) having a melt flow rate (MFR1) of 500 g/10 min or more, from 15-70% by weight of a melt flow rate (MFRn) of 〇·1 to 30 g/10 min, a polypropylene fraction A11), and from 0.5 to 15% by weight of a compatibilizer Q) 'A1), A11) And the percentage of Q) is based on the sum of A1), A11) and Q); the equal parts A1) and A11) are independently selected from the group consisting of propylene homopolymers and containing up to 5 mol% of ethylene and/or Copolymer of C4-Cio α-olefin propylene; all melting The flow rate based IS square Zhi 1133, in 2 3 0 ° C, to be measured when the load g 2.1 6 k. The composition of the invention preferably comprises from 20 to 70% by weight, more preferably from 30 to 60% by weight of A), and from 30 to 80% by weight, more preferably from 40 to 40% by weight relative to the total weight of A) and B). - 70% by weight of B). 200837127 The rate of division as defined above. Is a propylene polymer or polymer composition having a very high MFR, i.e., having 500 g/10 min or more, preferably 1200 g/10 min or more, especially from 5 00 - 2 5 0 0 g / 1 0mi η Or from 1200-2500g/10min·〇, and these MFR値 are preferably obtained without any degradation treatment. In other words, the fraction A1) is preferably caused by the initial polymerization of the propylene polymer, and after the polymerization, does not undergo any treatment which substantially changes the MFR. Therefore, the molecular weight of the fraction A1) is also generally obtained directly in the polymerization method used to prepare the propylene polymer. Alternatively, but not preferred, MFR is obtained by degradation (reduction of viscosity) of a propylene polymer having a lower MFR. The co-single system of the propylene copolymer which may be present in fraction A1) is selected from the group consisting of ethylene and/or CiCio α-olefins, for example, butene-1, pentene-1, 4-methylpentene, for example 1, hexene-1, and octene-1. Preferred comonomers are ethylene and dibutyl-1. Fractions All of the propylene polymers and copolymers of Α1) can be prepared in a polymerization process via a Ziegler-Natta catalyst or a metal aromatic based catalyst system. Such catalysts and polymerization methods are well known in the art. Conventional molecular weight adjustments well known in the art, such as chain transfer agents (e.g., hydrogen or ZnEU), can be used.

A preferred example of a Ziegler-Natta catalyst is a supported catalyst system comprising a trialkylaluminum compound, optionally, an electron acceptor, and a solid touch 200837127 media component comprising a halide or halogen-alcohol of Ti and It is required to be supported by an electron donor compound supported on anhydrous magnesium chloride. Catalysts having the above characteristics are well known in the patent literature; particularly preferred are the catalysts described in U S P 4, 39,058 and EP-A-45 977. Other examples are found in USP 4,472,524. A specific Ziegler-NatU catalyst and a polymerization process suitable for the preparation of the propylene polymer of fraction A1) are shown in EP06223 80. Preferably, when the propylene polymer of the 'partition ratio A1' is prepared using a Ziegler-Natta catalyst, they have a Mw of from 00,000 to 60,000 at a MFR ranging from 600 to 1000 g/lOmin, and at a high At a MFR of 1000 g/10 min, there is an Mz 高于 higher than or equal to 1 40,000, as disclosed in ΕΡ06223 80. Other preferred features of the propylene polymer prepared using the ZUgler-Natta catalyst are: Mz/Mw from 2.5 to 2.8 at a room temperature (25 ° C), in a weight fraction insoluble in xylene , above or equal to 95% of the iso-index, more preferably higher than or equal to 97%. More preferably, the propylene polymer of the ratio A1) is obtained directly in the polymerization in the presence of a catalyst system based on a metal aromatic. In general, these polymerization conditions do not have to be different from those used in the Ziegler-Natta catalyst. Preferably, the catalyst system based on the genus of the genus Golden Ring is a) the metal aryl compound of the formula (I): 200837127

(I) where: • M is a transition metal belonging to Groups 3, 4, 5, 6 or a lanthanide or lanthanide series of the Periodic Table of the Elements, preferably 钛 or Ti; X, the same or different, is hydrogen Atom, a prime atom or a R, OR, OS〇2CF3, OCOR, sR, NR2 or pR2 group wherein R is linear or branched, cyclic or acyclic Cl_c4. Alkyl, C2_C4q, and C2-C4. Alkynyl, C6-C4. Aryl, C7-C4 nonane aryl or C7-C4() aralkyl; optionally containing a hetero atom belonging to Groups 1 3 -17 of the Periodic Table of the Elements; R preferably 疋 linear or branched C 1 - C 2 0, or optionally, two X may form a substituted or unsubstituted butadienyl or fluorene R' fluorenyl group, wherein R' is selected from the group consisting of Cl-C4(), phenyl, and C6-C40 arylene And a divalent group of a C7-C4D alkylene aryl group and a C7-C40 aralkylene group; X is preferably a hydrogen atom, a halogen atom or R, and more preferably X is chlorine or Cl_Ci. An alkyl group such as a methyl group or an ethyl group; L is a divalent Ci-Cw hydrocarbon group, optionally containing a hetero atom of Groups 0-17 belonging to the Periodic Table of the Elements or a divalent methymethylene group having up to 5 ruthenium atoms, if necessary ; L is preferably a divalent bridging group's strip from Ci-C4. Affiliation, C3-C4 ◦ cycloalkyl, C6-C40 arylene, C7-C4. Alkylene aryl or C7-C4. An aralkylene group, if necessary, a hetero atom having a group of 1 3 -1 7 of the periodic table and a methylene group containing at most 5 -10 - 10,37,37,127 atom: for example, SiMe2, SiPh2; L is preferably (Z) (R") 2) n wherein Z is a carbon or germanium atom, n is 1 or 2 and R" is a Ci-Cao hydrocarbon group, optionally containing a hetero atom belonging to Groups 13-17 of the periodic table; R" is preferred. Is linear or branched, cyclic or acyclic C^C^o alkyl, C2-C2 nonenyl, C2-C2. alkynyl, C6-C2 aryl, c7-C2 decane aryl or C7 -C2 aralkyl, optionally containing a hetero atom belonging to Groups 13-17 of the Periodic Table of the Elements; more preferably, (Z(R")2) n is Si(CH3) 2, SiPh2, SiPhMe, SiMe ( SiMes), CH2, (CH2) 2 and C(CH3) 2, even better (Z (R") 2) n is Si (CH3) 2. R1 is a C^-Ce hydrocarbon group, and if necessary, belongs to the elemental period a hetero atom of the group 13-17; preferably R1 is a linear or branched, cyclic or acyclic ChC^ alkyl, C2-C4, alkenyl, C2-C4, alkynyl, C6-C4D aryl , a C7-C40 alkaryl group or a C7-C4 0 aralkyl group; if necessary, a hetero atom belonging to Groups 13-17 of the periodic table, more preferably R1 is Sexually or branched, saturated or unsaturated C i - C 2 . Alkyl. R 2 , R 3 , R 4 and R 5 are the same or different from each other and are a hydrogen atom or a ChC 4 . φ hydrocarbon group, as required, containing 13 of the periodic table. a hetero atom of group -17, or in R2, R3, R4 and R5, two R form a C4-C7 ring which may be unsaturated or saturated, and if desired, is a group belonging to the group 14-14 of the periodic table. a hetero atom; the ring formed may carry a Ci-C2. a hydrocarbon substituent. b) at least one aluminoxane or a compound capable of forming an alkyl metal aromatic cation. A specific example of the metal aromatic compound a) is racemic- Dimethylmethane alkyl bis(2-methyl-4,5-benzo-indene) zirconium dichloride. -11 - 200837127 Considering aluminoxane as a linear, branched group containing at least a group of the following types Or cyclic compound:

Among them, the substituents u' are the same or different and are a hydrogen atom, a halogen atom, a Cl-C2D yard group, a C3_C2〇fe yard group, and a C6-C2 group. Aryl, C7-C2. Courtyard aryl or C 7 - C 2 . Fangyuan base 'as needed' contains sand or helium atoms, with the condition that at least one U is different from hydrogen. In particular, aluminoxane of the formula:

I-0-(A1_0)n -A1

U is in the case of a linear compound wherein n 1 is an integer of 〇 or 1 - 40 and the substituent U is as defined above; or an aluminoxane of the following formula may be used

-12- 200837127 In the case of a cyclic compound, wherein η2 is an integer from 2 to 40 and the substituent U is as defined above. Examples of suitable aluminoxanes are methylalumoxane, tetrakis(isobutyl)aluminoxane (ΤΊΒΑΟ), tetrakis-(2,4,4-trimethyl-pentyl)aluminoxane ( ΤΙΟΑΟ), tetrakis-(2,3-dimethylbutyl)aluminum brothel (TDMBAO) and tetrakis-(2,3,3-trimethylbutyl)aluminoxane h (TTMBAO). An example of a compound capable of forming an alkyl metal aromatic cation is a compound of the formula D + E-, wherein D + is a succinic acid which gives a proton and a substituent X of the metal aryl group of the formula (I) The irreversible reaction and oxime is a compatible anion which stabilizes the active catalytic species derived from the reaction of the two compounds and is sufficiently unstable to be removed via the olefinic monomer. The anion Ε_ preferably includes one or more boron atoms. More preferably, the anion Ε· is a yttrium of the formula ,, wherein the substituents Ar which may be the same or different are aryl groups. For example: phenyl, pentafluorophenyl or bis(trifluoromethyl)phenyl. Barium borate-pentafluorophenyl ester is a particularly preferred compound, for example, as described in W09 1/02012. Further, a compound of the formula BAn φ can be conveniently used. For example, this type of compound is described in International Patent Application No. WO 92/003. Other examples of compounds capable of forming an alkyl metal aromatic cation are BAi^P wherein P is a substituted or unsubstituted pyrrolyl group. These compounds are described in WO 01/62764. All such compounds containing boron atoms may be used in molar ratios between boron and metal aromatic metals, including between about 1:1 and about 1 〇: 1, preferably between 1:1 and 2: 1, more preferably 1 : 1. Other preferred features of the propylene polymerization-13 - 200837127 prepared using a metal aromatic base-based catalyst system are: a molecular weight Mw/Mn distribution of less than 4, more preferably less than 3, most preferably less than 2.7; using 13C-NMR The measured isotactic pentads are higher than 90%, more preferably higher than 92%; at 25 ° C, the soluble matter in xylene is less than 2% by weight, more preferably less than 1.6% by weight; The melting point measured by DSC is higher than 143 °C. • Polypropylene fraction A11) may be any propylene homopolymer or a copolymer having an MFR of Q.l-30g/10min. Therefore, the fraction a11) can be prepared by a conventional polymerization method using a conventional catalyst (Ziegler-Natta or a metal aromatic substrate). The preferred characteristics of the polypropylene fraction Απ) are: MFR 自 from 0.5-20 g/10 min; φ isotactic index is high in the weight fraction which is insoluble in xylene at room temperature (about 25 ° C) Or equal to 92%, more preferably higher than or equal to 95%; the number of comonomers, up to 9 mol%, more preferably up to 5 mol%; Mw/Mn is greater than 4, more preferably Mw/Mn is greater than 7, most Good Mw / Mn is greater than 10; the melt strength measured at 230 ° C is greater than 1,50 cN, especially in the range of 1.6 0 to 12.00 cN, more preferably 1.60 to 8.00 cN; may be present in A11) Examples of co-monomers are the same as those defined above for the polypropylene fraction A1). -14- 200837127 The most preferred component used as the fraction An) is the following composition, which contains 30-70% by weight, preferably from 40-60% by weight, with a Mw/Mn ratio of 4-9. The molecular weight distribution and the fraction of 30 to 70% by weight, preferably 40 to 60% by weight ii) have a molecular weight distribution greater than 10 in terms of Mw/Mn ratio, and the fractions i) and ii) are independently selected from the group consisting of propylene homopolymerization. And random copolymers of propylene containing up to 5 mole % of ethylene and/or alpha olefins, i) and il:) are based on the sum of i) and ii). Fraction ii) can also be used as the fraction Απ). In order to obtain a fluorinated homofluorene polymer and a copolymer having 10 or more Mw/Mn?, it is possible to carry out the polymerization method in two or more stages using different amounts of molecular weight regulators (especially hydrogen). An example of such a process is disclosed in EP0573 8 62, which is preferably carried out in the gas phase. It is also possible (and preferred) to use a gas phase polymerization process carried out in at least two interconnected polymerization zones to prepare the homopolymers and copolymers. This polymerization method is described in European Patent No. EP 7 8 25 87 and International Patent Application WO 00/02929. The process is carried out in a polymerization zone of the first and second interconnects, in the presence of a catalyst system, feeding propylene and ethylene or propylene and alpha-olefin into the polymerization zone and discharging therefrom polymer. The grown polymer particles flow through the first polymerization zone (rising tube) under rapid fluidization conditions, and after leaving the first polymerization zone, enter the second polymerization zone (downcomer), through which the gravity is under the action of Flowing in a thickened form, leaving the second polymerization zone and reintroducing into the first polymerization zone' thus establishing a cycle of polymer between the two polymerization zones. Typically, the condition of rapid fluidization in the first polymerization zone enters the first polymerization zone via a feed mono-15-200837127 body gas mixture below the reintroduction point of the growing polymer. The velocity of the transport gas entering the first polymerization zone is higher than the transport velocity under operating conditions, typically between 2-15 m/s. In the second polymerization zone, the polymer flows in a thickened form under the action of gravity to reach a high density of solid density, which is close to the bulk density of the polymer, so that the positive gain of the pressure can be obtained along the direction of the flow. The polymer can be reintroduced into the first reaction zone without the assistance of a mechanical tool. In this way a "loop" cycle is established which is defined by the pressure equalization of the two polymerization zones and by the ® height difference loss introduced into the system. If desired, one or more inert gases, such as nitrogen or aliphatic hydrocarbons, are maintained in each polymerization zone in an amount such that the sum of the partial pressures of the inert gases is preferably between 5 and 80% of the total gas pressure. Operating parameters, for example, temperature are typical users of vapor phase olefin polymerization processes, for example: 50 ° C - 120 ° C, preferably 70 ° C - 9 0 ° C. The process can be carried out at an operating pressure of from 0.5 to 10 MPa, preferably from 1.5 to 6 MPa. Preferably, different catalyst components are fed to the first polymerization zone at any location in the first polymerization zone. However, φ can also feed them to any location in the second polymerization zone. Providing a device in a polymerization process that completely or partially prevents a gas and/or liquid mixture present in the riser from entering the downcomer and will present a gas of a different composition than the gas mixture present in the riser and / or a liquid mixture is introduced into the downcomer. According to a preferred embodiment, a gas and/or liquid mixture having a different composition than the gas mixture present in the riser is introduced into the downcomer through one or more inlet lines to prevent the latter mixture from entering the downcomer. effective. The gas and/or liquid mixture consisting of -16 - 200837127, which is transported to the downcomer, can be transported in partial or complete liquefaction as needed. The molecular weight distribution of the growing polymer can be illustrated in the reactor of tjk illustrated in Figure 4 of the International Patent Application WO 0 0 / 0 2 9 2 9 and via separate metered comonomers and conventional molecular weight regulators, in particular hydrogen It is convenient to enter the at least one polymerization zone in different proportions, preferably into the riser tube for the polymerization method. The tanning component B) used in the composition of the present invention may be organic or inorganic. Preferred are organic and inorganic fibers and other inorganic materials (as opposed to fibers) such as metal flakes, glass flakes, honed glass, glass spheres and mineral coatings. For example: talc, calcium carbonate, mica, ash, or strontium, in general, kaolin, barium sulfate, metal oxides and hydroxides. Another suitable material is wood chips. Suitable fibers suitable for the present invention include fibers derived from glass, metals, ceramics, graphite, and organic polymers such as polyesters and nylons, such as aromatic polyamines in the form of filaments, all of which are commercially available. Available. It is preferred to use glass fibers. The glass fiber may be in the form of cut glass fibers or long glass fibers or may be in the form of continuous filament fibers, with the exception of the use of glass fibers, also referred to as staple fibers or staple fibers. In general, glass fibers can have a length of from 1 to 50 mm. The cut or short glass fibers used in the composition of the present invention have an idmm length of -17-.200837127 ► - 'Wa-degree, more preferably 3-4.5 mm and a diameter of l〇-20 um, more preferably 12-14 um. As described previously, the polypropylene composition of the present invention may also include a compatibilizing agent Q). One type that can be used is a low molecular weight compound having a reactive polar group, the function of which is to make the tanning less hydrophilic and thus More compatible with polymers. For example, suitable compounds are decane, such as amino decane, epoxy decane, decyl decane, or propylene decane. However, the compatibilizer preferably comprises a modified (functionalized) polymer and, if desired, a low molecular weight compound having a reactive polar group. Modified olefin polymers, especially propylene homopolymers and copolymers, such as copolymers of ethylene and propylene with each other or with other alpha olefins, because they are compatible with the composition of the present invention. Highly compatible. It is also possible to use modified polyethylene. The modified polymer is preferably selected from the group consisting of graft or block copolymers by structure. In this connection, preference is given to modifying polymers comprising groups derived from polar compounds, in particular selected from the group consisting of anhydrides, carboxylic acids, carboxylic acid derivatives, primary amines and secondary amines, via compounds, porphyrins and rings. Oxides and ionic compounds. Specific examples of polar compounds are unsaturated cyclic anhydrides and their aliphatic diesters, and diacid derivatives. In particular, maleic anhydride and a compound selected from the group consisting of:

Ci-Ci. Linear and branched dialkyl maleate, 匕-Cm linear and branched dialkyl fumarate, itaconic anhydride, C! - C!. Linear and branched diacontanates, maleic acid, fumaric acid, itaconic acid, and mixtures thereof. It is particularly preferred to use a propylene polymer grafted with maleic anhydride as a modified polymer. -18- 200837127 Low molecular weight compounds are used to couple the dip to the modified polymer and thus firmly bond it to the propylene polymer component A). Typically, these are difunctional compounds, in which case one functional group can enter into a binding interaction with the dip. The second functional group can enter into a binding interaction with the modified polymer. The low molecular weight compound is preferably an amine group or an epoxy broth, more preferably an amino decane. When the bake material B) comprises glass fibers, the amine decane having a decane hydroxy group is bonded to the glass fibers, while the amine group, for example, forms a stable amide bond with the polypropylene grafted with maleic anhydride. It is particularly advantageous to apply a low molecular weight compound to the glass fibers prior to their incorporation into the composition. The modified polymer can be produced in a simple manner by reactive extrusion of the polymer with, for example, maleic anhydride in the presence of a free radical generator (for example, an organic peroxide), as disclosed in, for example, EP 05 7 2028 . The preferred amount of the group derived from the polar compound in the modified polymer is from 5 to 3% by weight. A preferred enthalpy of the MFR of the modified polymer is 50-400 g/10 min. It is also possible to use a masterbatch which comprises a premixed form of the dip and compatibilizer. The polyolefin composition according to the present invention can be obtained by melting and mixing the components. The mixing can be carried out efficiently at a temperature of usually from 180 ° C to 310 ° C in a mixing apparatus, preferably from 190 ° C to 28 ° C (TC, more Good for 20 (TC-25 (TC. For this purpose, any well-known device can be used. -19-.200837127) In this regard, useful mixing devices, especially extruders or kneading machines, especially for twin-screw extrusion It is also possible to premix the ingredients in the mixing device at room temperature. In order to reduce the abrasion and fiber breakage in the mixing device (when using fiber as a material), the preferred initial melting component A), and, if desired, the composition Q), component B) is subsequently mixed with the melt. In addition to the two main components A) and B) and possibly some compatibilizers Q) during the preparation of the polypropylene composition of the present invention, it is possible to introduce additives which are generally used in the art, such as stabilizers. Heat, light, UV) plasticizer, antistatic agent and water repellent. Particularly preferred features of the composition of the invention are: Density: from 1.1 to 4 kg/dm3, more preferably from 1.1 to 1.8 kg/dm3; flexural modulus: from 2500 to 1 9000 MPa, more preferably from 5,000 to 17,000 MPa; tensile modulus: 2500-20000MPa, better 5,000-1 8,000MPa; φ 23°C, no inspection of the skin (chapi): from 30-200kJ/m2, better 35-65 kJ/m2; at -30°C, check No gap in the skin: from 30-150 U/m2, better 40-70 kJ/m2; at 23 °C, the inspection gap: from 5-200 kJ/m2, more preferably from 10-20kJ/m2; 30 °C When, the inspection gap: from 50 - 1 50 kJ / m2, better from 10-25kJ / m2; tensile strength at break: from 50-150 MPa, more preferably from 80-140 MPa; -20- 200837127 elongation at break Rate: from 1 - 200%, especially from 1 / 5 %; HDT 1.8MPa: from 60 - 1 55 ° C, more preferably from 1 3 5 - 1 5 5 °C. Due to the advantageous balance of its various properties, the compositions of the invention can be used in a number of applications, for example, injection molded articles, especially automotive components, electrical appliances, furniture, or, in general, shaped articles, particularly sheets, Electrical appliance components, furniture, household appliances, or as a masterbatch for super-filling. In particular, when the amount of component B) is particularly high, the composition of the invention may advantageously be blended with from 50 to 80% by weight, based on the total weight of A) and B), by blending with additional polymer. Used as a concentrate to direct the feed into the polymeric composition, especially into the polyolefin composition. For purposes of illustration, the following examples are shown but are not limiting. The following analytical methods were used to determine the various properties described in the examples and in the examples. Solution flow rate (MFR): IS01133, load 2.16 kg at 230 ° C; • ultimate viscosity: measured in tetralin at 135 ° C; density: IS01 183; calcined modulus (positive Cut): IS0178 on 80xl〇x4mm rectangular sample, measured from T-rod IS0527-1 1A type; tensile modulus (cutting): IS0527/-1, -2 has lmm/ on sample of type A Min speed, 50mm span; no skin gap = ISO 179 (type 1, edge), on 80x10x4mm rectangular sample, from T-bar, IS0 527-1 1A; -21- 200837127 No skin: ISO 179 (type 1, edge, notch A) on 80x1 0x4mm rectangular specimen, from T-bar, IS0527-1 1A; tensile strength at break: IS0527/-1, -2, on type 1A, with Speed of 50 mm/min, span of 50 mm; length of splitting_breaking: IS〇5 27/- 1, 2, with a speed of 50 mm/min and a span of 50 mm on a type A sample; HDT ( 1.80 MPa): (heat deflection temperature) IS〇7 5 A -1, -2 on sample Clause6. • T-rod preparation (injection molding) The test sample is injection molded according to the ISO 1 87 3 -2 test method (1 989). Determination of the 篕 degree index (solubility in dimethyl bitterness at room temperature, in % by weight) 2.5 g of the polymer and 250 cm 3 of xylene were introduced into a glass flask equipped with a freezer and a magnetic stirrer. Within 30 minutes, the temperature is raised until the boiling point of the solvent. The clear solution thus obtained was kept under reflux and stirred for another 30 minutes. The closed flask was then kept in a constant temperature water bath of ice and water for 30 minutes. And keep it in a constant temperature water bath at 25 ° C for 30 minutes. The solid thus formed was filtered on a fast filter paper. The 丨〇〇cm3 filtered liquid was poured into a previously weighed aluminum container, which was heated under a nitrogen flow to remove the solvent via evaporation. The vessel was then held in an 80 ° C oven under vacuum until a constant weight was obtained. The weight % of the polymer soluble in xylene at room temperature is then calculated. -22- 200837127 The weight % of the polymer insoluble in xylene at room temperature is taken as the isotactic index of the polymer. This number is substantially equivalent to the isocratic index determined by boiling n-heptane extraction, which by definition constitutes the isotactic index of polypropylene. MWD measurement

Mn/Mw lanthanum was measured by gel permeation chromatography (GPC) at 145 °C. The Alliance GPCV2000 Instrument I (Waters) with three mixed bed columns TosoHaasTSK GMHXL-HT with a particle size of 13 μm was used. The size of the string is 300x7.8mm. The mobile phase used was vacuum distilled 1,2,4-trichlorobenzene (TCB) and the flow rate was maintained at 1.0 ml/min. The sample solution was prepared by heating the sample in TCB for two hours at 145 Torr with stirring. The concentration is 1 mg/ml. To prevent degradation, 0.1 g/Ι of 2,6-di-t-butyl-p-cresol was added. A solution of 3 26.5 from L was injected into the column set. A calibration curve was obtained using 10 polystyrene standards (EasiCal kit manufactured by Polymer 0 Laboratories) having a molecular weight in the range of 580 to 7,50 Å, ;; from the same manufacturer having 11,600,000 to Two other standards for the peak molecular weight of 13,200,000 are also included. Assuming the K値 of the Mark-Houwink relationship is: • For polystyrene standards K = 1.21xl (T4dL/g and α = 0.706. For polypropylene samples K = 1.90xl (T4dL/g and α = 0.7 25. The propylene copolymer sample K = 1.93xl0_4dL/g and α = 0.7 25. The third-order polynomial was used to interpolate the experimental data and obtain the -23-200837127 positive curve. The data was obtained and processed by using Waters' GPCV. The selected E m ρ 〇wer 1.0 was completed. The melt temperature was measured according to IS03 146 using a heating rate of 20 K/min and determined by DSC. 13 C-NMR (for propylene polymers of metal aromatics ▲) NMR The "C-NMR spectrum of the analysis PP was obtained on a DPX-400/spectrometer operating at 100.61 MHz in a Fourier conversion mode at 120 ° C. The peak of 21.8 ppm and 29.9 ppm was used as the peak of the mmmm pentad carbon Internal reference. The sample was dissolved in 1,1,2,2,-tetrachloroethane-d2 at 120 ° C and had a concentration of 8% wt/v in a 5 mm tube. Each spectrum was obtained using a 90° pulse. There is a 12 second delay between pulses and CPD (WALTZ 16) to remove 1H-13C coupling. Use 6000Hz spectrum , about 2500 transients are stored in 32K data points. The identification of PP spectra is based on "Selectivity in Propylene • Polymerization with Metallocene Catalysts, L. Resconi, L. Cavallo, A. Fait, F. Piemontesi, Chem. Rev, 1 00, 1 253, (2000)) The mmmm content was obtained by simulating the experimental pentads distribution using the mirror position model. The mmmm content of the high content PP with 2,1 (E) and 1,3 (H) errors was obtained as [mmmm] = 100 (Σ[CH3]·5[ mrrm] -5[E]-5[H])/ ( Σ [CH3]) wherein Σ [CH3] is the sum of CH3 groups. 2, 1 and 3, 1 The error content is obtained as: -24- 200837127 [E]= 100 ( Ε9/Σ [CH2]) [Η] = 100 (0.5Π2/ Σ [CH2]) where E9 is the peak at 42.14ppm and H2 is at The peak of 30.82 ppm and Σ [CH2] is the sum of all CH2. The device used for melt strength is a melt tension tester manufactured by Toyo-Sieki Seisakusho Co., Ltd., an electronic computer for data processing. The method consists in measuring the tensile strength of the molten polymer single yarn stretched at a specific stretching speed. Specifically, the polymer to be tested was extruded at 0.2 mm/min through a mold having pores of 8 mm in length and 1 mm in diameter at 0.2 mm/min, and then the single yarn of the outlet was passed through a system using a traction sheave. Stretch at a fixed acceleration of 0.000 6 m/sec 2 and measure the tension until the break point. The device records the tension of the green single yarn as a function of stretching. The melt strength corresponds to the melt tension at which the polymer breaks. Examples 1 to 15 and Comparative Sinus Case 1 辛 3 φ The following materials were used as the components A), B) and Q). Ingredient A) PP-1: propylene homopolymer having an MFR of 2300 g/10 min, Mw/Mn of 2.6 and an isotactic index of 98.5% in xylene at room temperature (isotactic pentad ( Mmmm) is higher than 92%), DSC melting temperature at 146 °C, intrinsic viscosity of 0.47 dl/g, in the form of nine particles. PP-2: a propylene homopolymer having an MFR of Ug/lOmin, an Mw/Mn of 5.4, and an isotactic index of 96.7% in the form of nine particles. -25- 200837127 PP-3: a propylene copolymer containing 1.6% by weight of ethylene, an MFR of 3g/10min, an Mw/Mn of 19.2 and an isotactic index of 96%, in the form of nine particles. PP-4: a generic polymer of propylene, having an MFR of 550 g/10 min, an M w/Mn of 2,3, and an isotactic index (isotactic pentads) in xylene at room temperature at 98.7%. (mmmm) higher than 92%), 145.3 ° C DSC melting temperature, 0.69 dl / g of intrinsic viscosity, in the form of nine. PP-5: a propylene homopolymer having an MFR of 2.5 g/10 min, a Mw/Mn of 8.4, and a melt strength of 6.74 cN in the form of nine particles. PP-1 is via the use of racemic-dimethylformamidinium bis(2-methyl-4,5-benzo-indene) pin dichloride, using the touch as described in PCT/EP2004/007061 Obtained by the media system. The catalyst system obtained in the form of a catalyst slurry is fed into a precontacted vessel as described in the form of PCT/EP2004/00706 1 in which it is diluted with about 5 (Kg/h) of propane. From the precontacted vessel, the catalyst system is fed φ to the prepolymerization loop while propylene is fed therein. The prepolymerization temperature is 45 °C. The residence time of the catalyst in the prepolymerization loop is 8 minutes. The prepolymerized catalyst obtained in the prepolymerization loop was then continuously fed into the loop reactor, and propylene was fed therein at a rate of 340 Kg/h. The polymerization temperature was 70 °C. The polymer is discharged from the loop reactor, separated from the unreacted monomer and dried. The MFR of the product is controlled by the feed hydrogen, and the feed rate is adjusted to obtain the MFR required for the polymer. In the case of PP-1, the hydrogen concentration was 1080 ppm. 〇-26-200837127 pp_4 was prepared in the same manner as ΡΡ-1. The difference was that propylene was fed at a rate of 329 Kg/h, and the hydrogen feed was 550 ppm. Ingredient B): GF: Glass fiber, white ECS 03T 480 (Japan Electric Glass Co., Ltd.) has a fiber length of 3 mm and a diameter of 13//m. Ingredient Q): PP-MA: a propylene homopolymer polymer grafted with maleic anhydride (MA) having an MFR of 115 g/10 min and an MA content of 1 wt% (Polybond 3200 sold by Chemtura Company). Ingredient A) also contains about 0.3% by weight of a conventional antioxidant additive. In Example 13, it also contained 300 ppm by weight of phthalocyanine blue (PV-Echtblau 2GLSP, Clariant). In Example 14, it also contained 0.18 % of Mi llad 3988 3,4-dimethylbenzylidenesterol. The composition was prepared by extrusion using a twin-screw extruder, Werner & Pfleiderer ZSK40SC. This line has a length of 43L/D plus φ processing length and has a weight feeder. The components A) and Q) are fed into the first bobbin via the force-feeding side, and the component B) is fed into the fifth bobbin, using a single bath with a cooling bath and a single yarn cutter Scheer SGS100 The yarn template is used to form nine particles; vacuum degassing (bobbin Νο·8) is also applied to extract gas and decomposition products. Operating conditions: Screw speed: 200rpm· -27-

.200837127 Capacity: 5 0 Bobbin temperature * This will be listed in Tables I to V 60 kg / h. : 200-220 ° C. The final properties of the resulting composition together with the relative amount of ingredients.

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Table I Sample No. 1 2 3 4 Composition (% by weight) PP4 17.6 23.75 23,75 15.9 PP-2 17.6 23.75 Shot 15.8 PP-3 17.6 - 23.75 15.8 GF 45 50 50 50 PP-MA 2.2 2.5 2.5 2.5 A) 55 50 50 50 B) . 45 50 50 50 A丨) 32 47.5 47.5 31.8 A11) 64 47.5 47.5 63.2 Q) 4 5 5 5 i) 50 100 • 50 ϋ) 50 - 100 50 Nature density (kg/dm3) 1.275 1.334 1.333 1.330 MFR(dg/min) 5.3 14.6 6 6.5 Flexural modulus (MPa) 10090 11630 11370 11470 Tensile modulus (MPa) 10440 12010 12100 12110 23°C inspection without gap (k〗/m2) 61.2 51 63.8 56.4 -30°C No peeling of skin (kJ/m2) 67.5 52 68.9 61 23°C Inspection gap (1^/1112) 13 13.7 13.8 13 -30°C Inspection gap (1^/1112) 16.8 18, 1 17.9 19 Tensile strength at break (MPa) 121.1 127 130 129 Elongation at break (%) 2.5 1.8 2.4 1.9 HDT 1.82N (〇C) 150 148 146 149 -29- 200837127

Table II Sample No. 5 6 7 Composition (% by weight) PP-1 14 14.1 12.34 PP-2 15.8 14.1 12.33 PP-3 17.7 14.1 12.33 GF 50 55 60 PP-MA 2.5 2.7 3 A) 50 45 40 B) 50 55 60 A丨) 28 31.3 30.8 A11) 67 62.7 61.7 Q) 5 6 7.5 i) 47.2 50 50 ii) 52.8 50 50 Properties Density (kg/dm3) 1.335 1.404 1.453 MFR(dg/min) 5.9 4.7 3,4 Deflection Modulus (MPa) 11360 12500 14080 Tensile modulus (MPa) 12150 12960 14250 23°C no-notch (kJ/m2) 57.2 49.4 46 -30°C No-notch (ld/m2) 61 57 49 23 °C Inspection gap (kJ/m2) 13.1 12.7 12.2 -30°C Inspection gap (U/m2) 19.3 19 18.5 Tensile strength at break (MPa) 126.6 126.3 122 Elongation at break (%) 2.2 1.7 1.7 HDT 1· 82ΝΓ〇148 149.2 148 -30- 200837127

Table III Sample No. 8 9 10 11 Composition (% by weight) PP4 35.5 12.8 18,5 PP-4 18.5 PP-3 12 34.2 18.5 PP-5 - - 18.5 GF 50 50 60 60 PP-MA 2.5 3 3 3 A) 50 50 40 40 B) 50 50 60 60 A1) 71 25.6 46.25 46.25 A11) 24 68.4 46.25 46.25 Q) 5 6 7.5 7.5 Property density (kg/dm3) 1.330 1.331 1.469 1.476 MFR(dg/min) 6.2 1.3 4.6 10.2 Variance (MPa) 11250 11130 14350 13770 Tensile modulus (MPa) 12020 11800 14570 13890 23°C no gap (k]/m2) 59 62 52 55 -30°C No gap (kJ/m2) 61 65 54 52 23°C inspection snips 1/1112) 13.8 13.7 13.4 13.6 -3CTC inspection gap (kJ/m2) 17.4 18.1 21 20 tensile strength at break (MPa) 129 127 131 120 elongation at break (%) ) 2.2 2.5 2 1.2 HDT 1.82N (〇C) 146 147 150 148 -31- 200837127

Table IV Sample No. 12 13 14 15 Composition (% by weight) PP-1 18.5 18.5 18.5 15.85 PP-2 18.5 - • Nutrient PP-3 - 18.5 18.5 15.85 GF 60 60 60 65 PP-MA 3 3 3 3.3 A) 40 40 40 35 B) 60 60 60 65 A1) 46.25 46.25 46.25 45.29 A11) 46.25 46.25 46.25 45.29 Q) 7.5 7.5 7.5 9.42 Property density (kg/dm3) 1.470 1.476 1.475 1.557 MFR(dg/min) 9.9 5.9 6.8 3.8 Flexing Modulus (MPa) 14110 14420 14350 15050 Tensile modulus (MPa) 14200 14630 14750 16060 23DC uncovered (kJ/m2) 43 45 44 40 -30°C No gap (kJ/m2) 46 47 47 41 23°C Chapi gap (kJ/m2) 13,1 12.7 13,7 12.4 -30°C inspection gap (k)/m2) 21 22 21 21.5 Tensile strength at break (MPa) 121 127 130 121 Elongation at break Rate (%) 1.7 2.2 2 L6 HDT 1.82N (〇C) 150 148 148 150 -32- 200837127

Table V • 30°C inspection gap (kJ/m2)

HDT 1.82N (〇C) is also measured on some of the above materials according to the following ast method

Flexibility, impact resistance, and tensile properties. Flexing ( MPa ) : ASTM D790 ; Flexing ( MPa ) : ASTM D790 ; 23 ° C , Ehrlich notch ( J / m ) · · ASTM D256A ; -30 〇 C 篆 , 1 Zhuang . Gap ( J / m) : ASTM D25 6A ; -33- 200837127 Tensile strength (MPa ) : ASTM D63 8 ; Elongation at break (%) : ASTM D63 8. The results are shown in Table VI, where the materials tested were referred to by reference Examples are identified. Sample No. 2 3 4 7 15 Property Flexural Modulus (MPa) 8480 11310 11420 14100 15450 Flexural Strength (MPa) 168 192 177 165 183 23°C Ehrlich Defect (kJ/m2) 98.5 129 130 116 107 -30 °C Ehrlich notch (1^/1112) 125 139 144 140 134 Tensile strength (MPa) 116 115 123 118 98 Elongation at break (%) 2.8 1.5 2 1.6 1.5

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Claims (1)

200837127 X. Patent application scope: 1. A blushing polyolefin composition 'comprising: A) from 20% by weight to 80% by weight of the polypropylene component; B) from 20% by weight to 80% by weight of the mash; The percentages of A) and B) are based on the sum of human) and 6) and A is selected from the following compositions: a) a polypropylene composition containing from 20 to 80% by weight with 500 g/10 min Or greater melt flow rate (MFR1) 聚丙烯 of the polypropylene fraction • VIII 1), and from 20-8 〇 wt% of the melt flow rate from 〇.1 to 302/1〇11^11 ( MFR11) The percentage of polypropylene fraction A11), A1), A11)) is based on the sum of Α1) and Α11); or b) the polypropylene composition contains 15-72% by weight with 500g/ Polypropylene fraction A1 of MFR1 of 10 min or more, from 15-70 wt% of polypropylene fraction A11 of MFR11 having 0.1-30 g/10 min and compatibilizer Q of from 0.5% to 15 wt% The percentages of A1), A11) and Q) are based on the sum of A1), A11) and Q); • The fractions A1) and A11) are independently selected from propylene homopolymers and containing at most 5% of Mo, and/or C4-Ci〇a-copolymer of propylene storage, all MFR lanthanides according to ISO 1 133, at 230. (3) Measured at a load of 2.16 kg. 2. The composition of the first aspect of the patent application, wherein the MFR1 of the polypropylene fraction A1 is obtained without degradation treatment. 3 · As in the composition of the scope of claim 1, wherein the copolymer of propylene homopolymer and polypropylene fraction A1) is present in the presence of a metal aromatic-based -35-200837127 catalyst, during polymerization Get it directly. 4. The composition of claim 1, wherein the copolymer of propylene homopolymer and polypropylene fraction A1) has a molecular weight distribution of less than 4 in terms of Mw/Mn ratio. 5. The composition of claim 1, wherein the copolymer of propylene homopolymer and polypropylene fraction A11) has a molecular weight distribution higher than 10 in terms of Mw/Mn ratio. 6. The composition of claim 1 wherein the polypropylene fraction A11) • contains 30-70% by weight of fraction i having a molecular weight distribution from 4 to 9 in terms of Mw/Mn ratio, and from 3 0-7 0% by weight of fraction ii having a molecular weight distribution above 10 in terms of M w / η η, the radicals i and ii being independently selected from the group consisting of propylene homopolymers and containing up to 5 moles % ethylene and / or C4-C! The random copolymer of propylene of α-olefin; the percentages of i) and ii) are based on the sum of i) and ii). 7. The composition of claim 1 wherein the bake material B) is selected from the group consisting of inorganic tanning materials and fibers, or a combination thereof. ^ 8. The composition of claim 1 wherein the bake material B) consists essentially of glass fibers and the polypropylene component A) has the composition b). 9. The composition of claim 1 wherein the bake material B) consists essentially of mineral tanning material and the polypropylene component A) has composition a). 10. Use of a composition as claimed in claim 1 for the manufacture of articles by injection molding, extrusion or hot press forming. 11. Use of a composition as claimed in item 1 of the patent application 'as a concentrate 0 - 36 - 200837127 VII. Designation of representative drawings: (1) The representative representative of the case is: None. (2) A brief description of the symbol of the representative figure: Μ y yv vn 8. If there is a chemical formula in this case, please disclose the chemical formula that best shows the characteristics of the invention: