CN103827200A - Heterophasic propylene copolymer with excellent stiffness and impact balance - Google Patents

Abstract

Heterophasic propylene copolymer (HECO) comprising (a) a matrix (M) being a polypropylene (PP), said polypropylene (PP) comprises at least three polypropylene fractions (PP1), (PP2) and (PP3), the three polypropylene fractions (PP1), (PP2) and (PP3) differ from each other by the melt flow rate MFR2 (230 DEG C) measured according to ISO 1133, and (b) an elastomer (E) dispersed in said matrix (M), wherein the elastomer (E) is included in an amount of 20 wt.-% or more, based on the weight of the heterophasic propylene copolymer (HECO).

Description

There is the heterophasic propylene copolymers of excellent rigidity and shock resistance balance

The present invention relates to a kind of new heterophasic propylene copolymers (HECO), its manufacture and purposes.

Heterophasic propylene copolymers is being well-known in the art.This class heterophasic propylene copolymers comprises the matrix for alfon or atactic propene copolymer that is wherein dispersed with elastomer copolymer.Therefore, what polypropylene matrix contained (meticulous) dispersion is not the inclusion of a part for matrix, and described inclusion contains elastomerics.Term inclusion represents that matrix and inclusion form different phases in heterophasic propylene copolymers, and described inclusion is for example by high resolution microscope, if electron microscope or scanning force microscopy are visible.

Thin thickness and light weight are the market requirements continuously, and this is because it allows the saving of energy and material.For the material with these features is provided, need exploitation to there is the high rigid material of excellent impact resistance energy.The high rigidity combining with high workability makes it possible to reduce wall thickness and does not lose stability, thereby makes it possible to manufacture large parts.In addition, because need less cast gate, so can make tool design keep simple for high workability material.In addition because reach the required certain stiffness of the sample demoulding in shorter cooling time, be possible so shorten cycling time.But shock resistance need to remain on high level.High workability material shows high rigidity due to what have a less three-dimensional defect compared with short polymer chain conventionally.But shock resistance is owing to forming reducing compared with short polymer chain of less entanglement.Therefore, obtain have high workability and rigidity and excellent impact resistance can material be a challenge.

In addition, can distinguish twin shaft resistance to impact shock and three axle resistance to impact shocks.Although at heterogeneous system, in heterophasic propylene copolymers (HECO), both depend on strongly form, the resistance to impact shock that increases by two types is all quite challenging.This is due to the fact that they show best effect at different particle diameters.Especially under the particle of little fine dispersion, improve the resistance to impact shock (exposing energy) under biaxial stress state.This can realize by low-molecular-weight rubber.But this rubber is disadvantageous to the resistance to impact shock under triaxial state of stress (Charpy resistance to impact shock).

Adopt three peak matrix designs to obtain having the propylene of excellent stiffness, and obtain showing the heterophasic copolymer of outstanding shock resistance-rigidity balance.This good shock resistance-rigidity balance is considered to the fine dispersion of the rubber phase obtaining based on the high molecular part by matrix.But it is not known that this design is applied to the heterophasic propylene copolymers (HECO) with high rubber content, although they are necessary for road vehicle application.

Therefore, an object of the present invention is to obtain the material with high workability and rigidity and excellent impact resistance energy.Particularly, an object of the present invention is to obtain and there is the material that high workability, high rigidity, height are exposed energy and high Charpy resistance to impact shock.

One of the present invention is found to be a kind of heterophasic propylene copolymers is provided, and it contains the elastomerics with the matrix of wide molecular weight distribution and quite high amount, and described elastomerics preferably has quite low limiting viscosity number.

Therefore, the application relates to a kind of heterophasic propylene copolymers (HECO), it comprises: be (a) matrix (M) of polypropylene (PP), wherein said polypropylene (PP) comprises at least three kinds of polypropylene parts (PP1), (PP2) and (PP3), described three kinds of polypropylene parts (PP1), (PP2) and (PP3) at the melt flow rate (MFR) MFR measured according to ISO1133 ₂(230 ℃) aspect differs from one another; (b) be dispersed in the elastomerics (E) in described matrix (M), wherein the weight based on described heterophasic propylene copolymers (HECO) comprises described elastomerics (E) with 20 % by weight or more amount; Optionally a small amount of polyethylene (PE) and optionally mineral filler (F).

The invention still further relates to a kind ofly for the preparation of as the method for the above heterophasic propylene copolymers limiting (HECO), wherein said method comprises the step with matrix (M) blend by elastomerics (E).

The invention still further relates to a kind of comprising as the goods of the above heterophasic propylene copolymers limiting (HECO), and the especially purposes in road vehicle application of described heterophasic propylene copolymers (HECO).

The present invention is below described in more detail.

Heterophasic propylene copolymers (HECO)

Comprise as the polypropylene (PP) of matrix (M) and be dispersed in elastomerics (E) wherein according to heterophasic propylene copolymers of the present invention (HECO).Therefore, what polypropylene (PP) matrix contained (meticulous) dispersion is not the inclusion of a part for matrix (M), and described inclusion contains elastomerics (E), and optionally can also contain a small amount of crystalline polyethylene (PE).Term inclusion represents that matrix (M) forms different phases in heterophasic propylene copolymers (HECO) with inclusion, and described inclusion is for example by high resolution microscope, if electron microscope or scanning force microscopy are visible.

Preferably, only comprise polypropylene (PP) and elastomerics (E) as polymeric constituent according to heterophasic propylene copolymers of the present invention (HECO).In other words, heterophasic propylene copolymers (HECO) can also contain additive, but in a preferred embodiment, do not exceed 8.0 % by weight containing the gross weight based on heterophasic propylene copolymers (HECO), more preferably exceed other polymkeric substance of the amount of 6.0 % by weight.Can take a kind of other polymkeric substance that so low amount exist as with the well-mixed polyethylene of elastomerics (E) (PE), elastomerics (E) and optionally polyethylene (PE) in matrix (M), form inclusion.Therefore, should be appreciated that especially, heterophasic propylene copolymers of the present invention (HECO) only contain polypropylene (PP) (being matrix (M)), elastomerics (E) and optionally a small amount of polyethylene (PE) as only polymeric constituent.

Of the present invention one preferred aspect in, heterophasic propylene copolymers (HECO) is characterised in that quite high melt flow rate (MFR).Melt flow rate (MFR) depends primarily on molecular-weight average.This is because long molecule is compared short molecule and made material have lower flow tendency.Molecular weight increase means that MFR value reduces.Melt flow rate (MFR) (MFR) be under the temperature and pressure condition of regulation by limit polymkeric substance that mouthful mould discharges in gram/10 minutes measured, and be measuring of polymkeric substance viscosity, and its viscosity is affected by its molecular weight and degree of branching mainly for every kind of polymkeric substance.The melt flow rate (MFR) that (ISO1133) measures under 230 ℃ and 2.16kg load is expressed as MFR ₂(230 ℃).Therefore, preferably heterophasic propylene copolymers (HECO) has and is equal to or greater than 50 grams/10 minutes in the present invention, more preferably be equal to or greater than 70.0 grams/10 minutes, still more preferably within the scope of 70.0 grams/10 minutes to 200.0 grams/10 minutes, as the MFR within the scope of 75.0 grams/10 minutes to 180.0 grams/10 minutes ₂(230 ℃).

Preferably, expect what heterophasic propylene copolymers (HECO) was thermo-mechanical robust.Therefore, should be appreciated that, heterophasic propylene copolymers (HECO) has at least 160 ℃, and more preferably at least 162 ℃, the still more preferably melt temperature within the scope of 163 ℃ to 170 ℃.

The elastomerics (E) of heterophasic propylene copolymers (HECO) forms the major portion of the cold solvend part of dimethylbenzene of heterophasic propylene copolymers (HECO).Therefore, quite approx, the cold solvend of dimethylbenzene (XCS) part of heterophasic propylene copolymers (HECO) can be equal to elastomerics (E) content of heterophasic propylene copolymers (HECO).Therefore, based on heterophasic propylene copolymers (HECO), the cold solvend of dimethylbenzene (XCS) part of heterophasic propylene copolymers (HECO) is preferably equal to or higher than 20 % by weight, more preferably in 20 % by weight in the scope of 50 % by weight, also more preferably in 25 % in the scope of 40 % by weight, as in 25 % by weight in the scope of 35 % by weight.

In still another preferred embodiment, heterophasic propylene copolymers of the present invention (HECO) preferably has following characteristics

(i) at least 1100MPa measured according to ISO527-2, more preferably 1200MPa at least, still more preferably at 1100MPa within the scope of 2500MPa, as at 1200MPa to the tensile modulus within the scope of 2200MPa,

And/or

(ii) according to ISO179 (1eA; 23 ℃) measured at least 3.5kJ/m ², more preferably 4.5kJ/m at least ², still more preferably at 4.0kJ/m ²to 10kJ/m ²in scope, as at 4.0kJ/m ²to 8.0kJ/m ²charpy breach resistance to impact shock in scope,

And/or

(iii) according to ISO179 (1eA;-20 ℃) measured at least 1.0kJ/m ², more preferably 1.2kJ/m at least ², still more preferably at 1.5kJ/m ²to 5.0kJ/m ²charpy breach resistance to impact shock in scope,

And/or

(iv) according to ISO6603-2 use 60 × 60 × 2mm moulding with instrument drop hammer (IFW) test determine at least 6J, more preferably 12J at least, still more preferably at 8J within the scope of 28J, as at 12J to exposing energy (+23 ℃) within the scope of 25J

And/or

(iv) according to ISO6603-2 use 60 × 60 × 2mm moulding with instrument drop hammer (IFW) test determine at least 3J, more preferably 7J at least, still more preferably at 5J within the scope of 18J, as at 7J to exposing energy (20 ℃) within the scope of 15J.

The value of exposing energy is preferably applicable to not have the heterophasic propylene copolymers (HECO) of filler (F).

Below can limit in more detail each component of heterophasic propylene copolymers (HECO), i.e. matrix (M) and elastomerics (E).

As mentioned above, matrix (M) is polypropylene (PP), more preferably atactic propene copolymer (R-PP) or alfon (H-PP), especially preferably alfon (H-PP).

Therefore, the co-monomer content of polypropylene (PP) is equal to or less than 1.0 % by weight, also more preferably no more than 0.8 % by weight, still more preferably no more than 0.5 % by weight.The gross weight of above weight percent based on polypropylene (PP).

As mentioned above, polypropylene (PP) is preferably alfon (H-PP).

The statement alfon using in full in the present invention relates to the polypropylene being substantially made up of propylene units, the polypropylene being made up of the propylene units that is equal to or less than 99.5 % by weight.In a preferred embodiment, propylene units in alfon, only can be detected.Co-monomer content is determined by the FT infrared spectroscopy as described in embodiment part below.

If polypropylene (PP) is atactic propene copolymer (R-PP), should be appreciated that described atactic propene copolymer (R-PP) comprise can with the monomer of copolymerization of propylene, for example comonomer, as ethene and/or C ₄to C ₁₂alpha-olefin, particularly ethene and/or C ₄to C ₈alpha-olefin, for example 1-butylene and/or 1-hexene.Preferably, according to atactic propene copolymer of the present invention (R-PP) comprise be selected from ethene, 1-butylene and 1-hexene can with the monomer of copolymerization of propylene, especially by being selected from can forming with the monomer of copolymerization of propylene of ethene, 1-butylene and 1-hexene.More specifically, atactic propene copolymer of the present invention (R-PP) also comprises the unit of derived from ethylene and/or 1-butylene except propylene.In a preferred embodiment, atactic propene copolymer (R-PP) only comprises the unit of derived from ethylene and propylene.

In addition, should be appreciated that, atactic propene copolymer (R-PP) preferably has and is being greater than 0.1 % by weight within the scope of 2.0 % by weight, is more preferably being greater than 0.1 % by weight within the scope of 1.6 % by weight, also more preferably in 0.1 % by weight to the co-monomer content within the scope of 1.0 % by weight.The gross weight of above weight percent based on atactic propene copolymer (R-PP).

Term " random " represents comonomer stochastic distribution in propylene copolymer of propylene copolymer (R-PP) and the first atactic propene copolymer (R-PP1), the second atactic propene copolymer (R-PP2) and the 3rd atactic propene copolymer (R-PP3).Term " random " is according to the IUPAC (nomenclature of basic terms in polymer science; IUPAC recommends, and 1996) understand.

As mentioned above, heterophasic propylene copolymers (HECO) has quite high melt flow rate (MFR).Therefore,, for its matrix (M), polypropylene (PP) is like this equally.Therefore preferably, polypropylene (PP) have according to ISO1133 measured within the scope of 30.0 grams/10 minutes to 500.0 grams/10 minutes, more preferably within the scope of 40.0 grams/10 minutes to 400.0 grams/10 minutes, the still more preferably melt flow rate MFR within the scope of 50.0 grams/10 minutes to 300.0 grams/10 minutes ₂(230 ℃).

Should be appreciated that in addition, the matrix (M) of heterophasic propylene copolymers (HECO) is take suitably wide molecular weight distribution as feature.Therefore should be appreciated that, the matrix of heterophasic propylene copolymers (HECO), be that polypropylene (PP) has and is equal to or greater than 3.0, preferably be equal to or greater than 3.5, more preferably in 3.5 to 8.0 scopes, still more preferably in 3.5 to 7.0 scopes, the molecular weight distribution (MWD) as 4.0 to 7.0.

In addition, polypropylene (PP) can be limited by its molecular weight.Therefore should be appreciated that, polypropylene (PP) has by gel permeation chromatography (GPC; ISO16014-4:2003) measured 175 kg/mol that are equal to or less than, more preferably be equal to or less than 165 kg/mol, also more preferably in 75 kg/mol within the scope of 160 kg/mol, still more preferably in 80 kg/mol to the weight-average molecular weight (Mw) within the scope of 150 kg/mol.

The cold solvend of dimethylbenzene (XCS) content of polypropylene (PP) is quite moderate.Therefore, the cold solvend of dimethylbenzene (XCS) content is preferably equal to or less than 4.0 % by weight, is more preferably equal to or less than 3.5 % by weight, still more preferably in 0.5 % by weight in the scope of 3.0 % by weight, as in 0.5 % by weight in the scope of 2.8 % by weight.The gross weight of above weight percent based on polypropylene (PP).

As mentioned above, polypropylene (PP) comprises at least three kinds, more preferably comprise three kinds of polypropylene parts (PP1), (PP2) and (PP3), also more preferably form described three kinds of polypropylene parts (PP1), (PP2) and (PP3) at the melt flow rate (MFR) MFR measured according to ISO1133 by three kinds of polypropylene parts (PP1), (PP2) with (PP3) ₂(230 ℃) aspect differs from one another.

In a preferred embodiment, the first polypropylene part (PP1) has according to measured 80 grams/10 minutes to 500 grams/10 minutes of ISO1133, more preferably 150 grams/10 minutes to 480 grams/10 minutes, also more preferably 200 grams/10 minutes to 450 grams/10 minutes, the still more preferably melt flow rate (MFR) MFR of 250 grams/10 minutes to 450 grams/10 minutes ₂(230 ℃).

In addition, the second polypropylene part (PP2) preferably has according to measured 20 grams/10 minutes to 300 grams/10 minutes of ISO1133, more preferably 50 grams/10 minutes to 250 grams/10 minutes, also more preferably 70 grams/10 minutes to 220 grams/10 minutes, the still more preferably melt flow rate (MFR) MFR of 100 grams/10 minutes to 200 grams/10 minutes ₂(230 ℃).

In addition, polypropylene part (PP3) preferably has according to measured 1 gram/10 minutes to 15 grams/10 minutes of ISO1133, more preferably 2 grams/10 minutes to 15 grams/10 minutes, also more preferably 2 grams/10 minutes to 12 grams/10 minutes, the still more preferably melt flow rate (MFR) MFR of 3 grams/10 minutes to 10 grams/10 minutes ₂(230 ℃).

Preferably, melt flow rate (MFR) MFR ₂(230 ℃) reduce to tripropylene part (PP3) from the first polypropylene part (PP1).Therefore, the melt flow rate (MFR) MFR of the first polypropylene part (PP1) and tripropylene part (PP3) ₂the ratio [MFR (PP1)/MFR (PP3)] of (230 ℃) is preferably at least 10, more preferably at least 20, also more preferably at least 30, as in 30 to 60 scope, and/or the melt flow rate (MFR) MFR of the second polypropylene part (PP2) and tripropylene part (PP3) ₂the ratio [MFR (PP2)/MFR (PP3)] of (230 ℃) is preferably at least 5, and more preferably at least 7, also more preferably at least 10.

In another preferred embodiment, melt flow rate (MFR) MFR ₂(230 ℃) reduce to the second polypropylene part (PP2) from the first polypropylene part (PP1), and reduce to tripropylene part (PP3) from the second polypropylene part (PP2).Therefore, the second polypropylene part (PP2) preferably has than the low melt flow rate (MFR) MFR of the first polypropylene part (PP1) ₂(230 ℃), but have than the high melt flow rate (MFR) MFR of tripropylene part (PP3) ₂(230 ℃).

Therefore, tripropylene part (PP3) preferably have three kinds of polypropylene parts (PP1), (PP2) and (PP3) in, minimum melt flow rate (MFR) MFR in all polymkeric substance that more preferably exist in polypropylene (PP) ₂(230 ℃).

Preferably, polypropylene part (PP1), (PP2) and (PP3) at least one be alfon, even more preferably, all polypropylene parts (PP1), (PP2) and (PP3) be all alfon.

Therefore, in a preferred embodiment, the matrix (M) of heterophasic propylene copolymers (HECO), polypropylene (PP) comprises

(a) be the first polypropylene part (PP1) of the first alfon (H-PP1) or the first atactic propene copolymer (R-PP1),

(b) be the second polypropylene part (PP2) of the second alfon (H-PP2) or the second atactic propene copolymer (R-PP2),

(c) be the tripropylene part (PP3) of the 3rd alfon (H-PP3) or the 3rd atactic propene copolymer (R-PP3),

Prerequisite is that at least one in three kinds of part PP1, PP2 and PP3 is for alfon, preferably at least the first polypropylene part (PP1) is alfon, more preferably whole three kinds of parts (PP1), (PP2) and (PP3) be all alfon.

As mentioned above, particularly preferably, at least the first polypropylene part (PP1) is alfon, i.e. so-called the first alfon (H-PP1).Even more preferably, this first polypropylene part (PP1) have three kinds of polypropylene (PP1), (PP2) and (PP3) in the highest melt flow rate (MFR) MFR ₂(230 ℃).

Still more preferably, except the first polypropylene part (PP1), the second polypropylene part (PP2) or tripropylene part (PP3) are also alfon.In other words, preferably, polypropylene (PP) only comprises a kind of polypropylene part for atactic propene copolymer, is preferably only made up of a kind of polypropylene part for atactic propene copolymer.Therefore, the second polypropylene part (PP2) is alfon, be so-called the second alfon (H-PP2), or tripropylene part (PP3) is alfon, i.e. so-called the 3rd alfon (H-PP3).

Especially preferably, whole three kinds of polypropylene parts (PP1), (PP2) and (PP3) be all alfon.

Three kinds of polypropylene parts (PP1), (PP2) and (PP3) below can be described in more detail.

As mentioned above, polypropylene part (PP1), (PP2) and (PP3) can be atactic propene copolymer or alfon.Under any circumstance, each co-monomer content for polypropylene part (PP1), (PP2) and (PP3) all should be quite low.Therefore, three kinds of polypropylene parts (PP1), (PP2) and (PP3) in each co-monomer content be all not more than 1.0 % by weight, also more preferably no more than 0.8 % by weight, still more preferably no more than 0.5 % by weight.The in the situation that of in atactic propene copolymer part (R-PP1), (R-PP2) and (R-PP3), should be appreciated that, the co-monomer content of each for atactic propene copolymer part (R-PP1), (R-PP2) and (R-PP3) is being greater than 0.2 % by weight in the scope of 3.0 % by weight, more preferably being greater than 0.2 % by weight in the scope of 2.5 % by weight, also more preferably in 0.2 % by weight in the scope of 2.0 % by weight.The weight of above weight percent based on each atactic propene copolymer part.

(R-PP1), (R-PP2) and (R-PP3) comprise independently of one another can with the monomer of copolymerization of propylene, for example comonomer, as ethene and/or C ₄to C ₁₂alpha-olefin, particularly ethene and/or C ₄to C ₈alpha-olefin, for example 1-butylene and/or 1-hexene.Preferably, (R-PP1), (R-PP2) and (R-PP3) comprise be independently of one another selected from ethene, 1-butylene and 1-hexene can with the monomer of copolymerization of propylene, especially independently of one another by being selected from can forming with the monomer of copolymerization of propylene of ethene, 1-butylene and 1-hexene.More specifically, (R-PP1), (R-PP2) and (R-PP3) also comprise independently of one another the unit of derived from ethylene and/or 1-butylene except propylene.In a preferred embodiment, (R-PP1), (R-PP2) and (R-PP3) there is identical comonomer except propylene.Therefore, in an especially preferred embodiment, (R-PP1), (R-PP2) and (R-PP3) only comprise the unit of derived from ethylene and propylene.

As mentioned above, the first polypropylene part (PP1) is atactic propene copolymer part (R-PP1) or alfon part (H-PP1), preferably alfon part (H-PP1).

The cold solvend of dimethylbenzene (XCS) content of the first polypropylene part (PP1) is preferably equal to or less than 4.0 % by weight, more preferably be equal to or less than 3.5 % by weight, still more preferably in 0.8 % by weight in the scope of 4.0 % by weight, as in 0.8 % by weight in the scope of 3.0 % by weight.The weight of above weight percent based on the first polypropylene part (PP1).

As mentioned above, the first polypropylene part (PP1) is characterised in that quite high melt flow rate (MFR) MFR ₂(230 ℃).Therefore should be appreciated that the melt flow rate (MFR) MFR measured according to ISO1133 ₂(230 ℃) are equal to or greater than 80 grams/10 minutes, preferably be equal to or greater than 150 grams/10 minutes, more preferably in the scope of 80 grams/10 minutes to 500 grams/10 minutes, still more preferably in the scope of 150 grams/10 minutes to 480 grams/10 minutes, also more preferably in the scope of 200 grams/10 minutes to 450 grams/10 minutes, still more preferably in the scope of 250 grams/10 minutes to 450 grams/10 minutes.

Alternately or additionally, the first polypropylene part (PP1) is defined as low molecular weight.Therefore should be appreciated that, the first polypropylene part (PP1) has by gel permeation chromatography (GPC; ISO16014-4:2003) measured 130 kg/mol that are equal to or less than, more preferably be equal to or less than 110 kg/mol, also more preferably in 72 kg/mol within the scope of 110 kg/mol, still more preferably in 75 kg/mol to the weight-average molecular weight (Mw) in double centner/molar range.

The second polypropylene part (PP2) can be atactic propene copolymer part (the second atactic propene copolymer part (R-PP2)) or alfon part (the second alfon part (H-PP2)), preferably alfon part (the second alfon part (H-PP2)).

The cold solvend of dimethylbenzene (XCS) content of the second polypropylene part (PP2) is preferably equal to or less than 4.0 % by weight, more preferably be equal to or less than 3.5 % by weight, still more preferably in 0.8 % by weight in the scope of 4.0 % by weight, as in 0.8 % by weight in the scope of 3.0 % by weight.The weight of above weight percent based on the second polypropylene part (PP2).

As mentioned above, the second polypropylene part (PP2) has than the high melt flow rate (MFR) MFR of tripropylene part (PP3) ₂(230 ℃).On the other hand, the melt flow rate (MFR) MFR of the first polypropylene part (PP1) ₂(230 ℃) can greater than or equal to, preferably higher than the melt flow rate (MFR) MFR of the second polypropylene part (PP2) ₂(230 ℃).Therefore should be appreciated that, the second polypropylene part (PP2) have according to ISO1133 measured within the scope of 20 grams/10 minutes to 300 grams/10 minutes, preferably within the scope of 50 grams/10 minutes to 250 grams/10 minutes, more preferably at 70 grams/10 minutes to being less than within the scope of 220 grams/10 minutes, the also more preferably melt flow rate (MFR) MFR within the scope of 100 grams/10 minutes to 200 grams/10 minutes ₂(230 ℃).

Tripropylene part (PP3) can be atactic propene copolymer part (the 3rd atactic propene copolymer part (R-PP3)) or alfon part (the 3rd alfon part (H-PP3)), preferably alfon part (the 3rd alfon part (H-PP3)).

The cold solvend of dimethylbenzene (XCS) content of tripropylene part (PP3) is preferably equal to or less than 4.0 % by weight, more preferably be equal to or less than 3.5 % by weight, still more preferably in 0.8 % by weight in the scope of 4.0 % by weight, as in 0.8 % by weight in the scope of 3.0 % by weight.The weight of above weight percent based on tripropylene part (PP3).

As mentioned above, tripropylene (PP3) preferably have three kinds of polypropylene parts (PP1), (PP2) and (PP3) in minimum melt flow rate (MFR) MFR ₂(230 ℃), more preferably have minimum melt flow rate (MFR) MFR in the polymer moieties existing in polypropylene (PP) ₂(230 ℃).Therefore should be appreciated that, tripropylene (PP3) have according to ISO1133 measured within the scope of 1.0 grams/10 minutes to 15.0 grams/10 minutes, preferably within the scope of 2.0 grams/10 minutes to 15.0 grams/10 minutes, still more preferably within the scope of 2.0 grams/10 minutes to 12.0 grams/10 minutes, as the melt flow rate (MFR) MFR of 3 grams/10 minutes to 10 grams/10 minutes ₂(230 ℃).

If various piece, specifically to measure and to exist, can obtain fabulous result so.Therefore preferably, the melt flow rate (MFR) MFR measured according to ISO1133 ₂(230 ℃) melt flow rate (MFR) MFR of (preferably within the scope of 2.0 grams/10 minutes to 15.0 grams/10 minutes, still more preferably within the scope of 2.0 grams/10 minutes to 12.0 grams/10 minutes) within the scope of 1.0 grams/10 minutes to 15.0 grams/10 minutes ₂the amount of (230 ℃) polypropylene part, preferably the amount of tripropylene part (PP3) in 10 % by weight in the scope of 30 % by weight, more preferably in 10 % by weight in the scope of 25 % by weight, still more preferably in 15 % by weight in the scope of 25 % by weight.The gross weight of above numerical value based on matrix (M), preferably based on polypropylene part (PP1), (PP2) and (PP3) amount together.

Should be appreciated that in addition the melt flow rate (MFR) MFR measured according to ISO1133 ₂the amount of (230 ℃) polypropylene part within the scope of 80.0 grams/10 minutes to 500.0 grams/10 minutes, preferably the amount of the first polypropylene part (PP1) in 20 % by weight in the scope of 55 % by weight, preferably in 25 % by weight in the scope of 45 % by weight, more preferably in 30 % by weight in the scope of 45 % by weight, still more preferably 35 % by weight to 45 % by weight.The gross weight of above numerical value based on matrix (M), preferably based on polypropylene part (PP1), (PP2) and (PP3) amount together.

Finally, three kinds of polypropylene parts (PP1), (PP2) and (PP3) in rest part, preferably the second polypropylene part (PP2) with in 20 % by weight in the scope of 55 % by weight, preferably in 25 % by weight in the scope of 55 % by weight, more preferably in 30 % by weight in the scope of 45 % by weight, still more preferably 35 % by weight exist to the amount of 45 % by weight.Above numerical value is based on matrix (M), i.e. the total amount of polypropylene (PP), preferably based on polypropylene part (PP1), (PP2) and (PP3) amount together.

Therefore, in a preferred embodiment, the melt flow rate (MFR) MFR measured according to ISO1133 ₂(230 ℃) polypropylene part within the scope of 1.0 grams/10 minutes to 15.0 grams/10 minutes, preferably tripropylene part (PP3) and the melt flow rate (MFR) MFR measured according to ISO1133 ₂(230 ℃) polypropylene part within the scope of 80.0 grams/10 minutes to 500.0 grams/10 minutes, preferably the weight ratio [PP3/PP1] of the first polypropylene part (PP1) is in 10/45 to 25/30 scope, more preferably in 1/3 to 5/7 scope.

Can obtain extraordinary result, prerequisite is the total amount based on the first polypropylene part (PP1), the second polypropylene part (PP2) and tripropylene part (PP3), and polypropylene (PP) comprises

(a) 20.0 % by weight are to 55.0 % by weight, and preferably 25.0 % by weight are to first polypropylene (PP1) of 45.0 % by weight,

(b) 20.0 % by weight are to 55.0 % by weight, and preferably 25.0 % by weight are to second polypropylene (PP2) of 55.0 % by weight, and

(c) 10.0 % by weight are to 30.0 % by weight, and preferably 15.0 % by weight are to the tripropylene (PP3) of 25.0 % by weight.

In one embodiment, polypropylene (PP) is prepared with sequential polymerization processes, preferably as described in detail below.Therefore, three kinds of polypropylene parts (PP1), (PP2) and (PP3) be uniform mixture, this cannot obtain by mechanical blending.In another embodiment, polypropylene (PP) by by polypropylene part (PP1), (PP2) and (PP3) blend obtain.

Another necessary component of the present invention is elastomerics (E).

As mentioned above, the cold solvend of dimethylbenzene (XCS) of the final heterophasic propylene copolymers of performance major effect (HECO) of elastomerics (E).In other words, the performance limiting for elastomerics (E) below is equally applicable to the cold solvend of dimethylbenzene (XCS) part of heterophasic propylene copolymers (HECO).

Described elastomerics can be any elastomerics.But, in a preferred embodiment of the invention, the Toughening Effect of Ethylene Copolymer Elastomer of elastomerics (E) for comprising ethylene monomer unit and comonomer unit, wherein said comonomer is selected from C ₃to C ₂₀alpha-olefin, preferably propylene, 1-butylene, 1-hexene and 1-octene; Or C ₅to C ₂₀α, ω-diolefine, preferably 1,7-octadiene.In a preferred embodiment, comonomer is selected from propylene, 1-butylene, 1-hexene and 1-octene, especially preferably 1-octene.

In one embodiment, elastomerics (E) has the melt flow rate (MFR) MFR of 10 gram/10 minute to 80 gram/10 minute measured according to ISO1133 ₂(190 ℃).More preferably, elastomerics (E) has 15 grams/10 minutes to 70 grams/10 minutes, and still more preferably 20 grams/10 minutes to 60 grams/10 minutes, the also more preferably melt flow rate (MFR) MFR of 20 grams/10 minutes to 50 grams/10 minutes ₂(190 ℃).

In another preferred embodiment, elastomerics (E) has 0.7dl/g to 2.5dl/g, and preferably 0.8dl/g is to 2.0dl/g, and more preferably 0.8dl/g is to the limiting viscosity number of 1.5dl/g.Limiting viscosity number is according to DIN ISO1628/1, and measure in October, 1999 (at 135 ℃ in naphthalane).

In addition, elastomerics (E) preferably has lower than 940kg/m ³, more preferably 920kg/m ³or lower, still more preferably at 850kg/m ³to 920kg/m ³in scope, also more preferably at 860kg/m ³to 910kg/m ³density in scope.As mentioned above, heterophasic propylene copolymers (HECO) can also comprise polyethylene (PE), particularly as the following polyethylene limiting (PE).In this case, preferably, the mixture of elastomerics and polyethylene (PE) demonstrates as given density at this paragraph.

An important aspect of the present invention is that the be hit by a bullet amount of gonosome (E) of heterophasic propylene copolymers (HECO) is quite high.Therefore, preferably, based on the gross weight of heterophasic propylene copolymers (HECO), be preferably polypropylene (PP) and elastomerics (E) weight together based on matrix (M), elastomerics (E) is to be equal to or greater than the amount of 20.0 % by weight, more preferably, to be equal to or greater than the amount of 20.0 % by weight to 50.0 % by weight, be also more preferably present in heterophasic propylene copolymers (HECO) to the amount of 40.0 % by weight with 25.0 % by weight.

Therefore, preferably, the weight ratio ([M]/[E]) between matrix (M) and elastomerics (E) is less than 4.0, and more preferably 1.0 to being less than 4.0, and also more preferably 1.5 to 3.0.

Therefore, preferably, based on heterophasic propylene copolymers (HECO), the preferably total amount based on polypropylene (PP) and elastomerics (E), heterophasic propylene copolymers (HECO) comprises

(a) be less than 80 % by weight, more preferably 50.0 % by weight are to 80.0 % by weight, still more preferably 60.0 % by weight to the matrix (M) of 75.0 % by weight, i.e. polypropylene (PP), and

(b) be equal to or greater than 20 % by weight, more preferably 20.0 % by weight are to 50.0 % by weight, still more preferably 25.0 % by weight to the elastomerics (E) of 40.0 % by weight.

Polyethylene (PE)

Optionally also comprise crystalline polyethylene (PE) according to heterophasic propylene copolymers of the present invention (HECO).Statement " crystallization " represents that polyethylene (PE) is different from elastomerics (E).Polyethylene (PE) be crystallization and be insoluble to cold xylene, and elastomerics (E) is mainly amorphous and is dissolved in thus cold xylene.In a preferred embodiment, polyethylene (PE) is high density polyethylene(HDPE) (HDPE).Be well-known in the art according to high density polyethylene(HDPE) used in the present invention (HDPE), and can be commercially available.

High density polyethylene(HDPE) (HDPE) preferably has 15 grams/10 minutes to 45 grams/10 minutes, and preferably 20 grams/10 minutes to 40 grams/10 minutes, the melt flow rate (MFR) MFR of more preferably 25 grams/10 minutes to 35 grams/10 minutes ₂(190 ℃).

High density polyethylene(HDPE) (HDPE) generally has at least 940kg/m ³, preferably 945kg/m at least ³, more preferably 955kg/m at least ³, still more preferably at 945kg/m ³to 970kg/m ³in scope, also more preferably at 950kg/m ³to 965kg/m ³density in scope.

Based on the gross weight of heterophasic propylene copolymers (HECO), high density polyethylene(HDPE) (HDPE) can be with maximum 8 % by weight, preferably maximum 5 % by weight, more preferably within the scope of 0 to 8 % by weight, as in 1 % by weight within the scope of 8 % by weight, also more preferably within the scope of 0 to 6 % by weight, as existed to the amount within the scope of 6 % by weight in 1 % by weight.

In the time existing, polyethylene (PE), high density polyethylene(HDPE) (HDPE) is also dispersed in the matrix (M) of heterophasic propylene copolymers (HECO), in polypropylene (PP).More properly, polyethylene (PE), high density polyethylene(HDPE) (HDPE) fully mixes with elastomerics, thereby forms the inclusion of heterophasic propylene copolymers (HECO) together with elastomerics (E).

Mineral filler

Except polymeric constituent discussed above, based on the gross weight of heterophasic propylene copolymers (HECO), heterophasic propylene copolymers (HECO) can also optionally comprise maximum 25 % by weight, preferably maximum 22 % by weight, more preferably in 4 % by weight within the scope of 25 % by weight, still more preferably 5 % by weight to the mineral filler (F) of the amount of 20 % by weight.Preferably, mineral filler (F) is phyllosilicate, mica or wollastonite.Even more preferably, mineral filler (F) is selected from mica, wollastonite, kaolinite, smectite, montmorillonite and talcum.Most preferably, mineral filler (F) is talcum.

Mineral filler (F) preferably has and is equal to or less than 20 μ m, more preferably at 2.5 μ m within the scope of 10 μ m, as at 2.5 μ m to the cut-off particle diameter d95[mass percent within the scope of 8.0 μ m].

Usually, mineral filler (F) has according to known BET method and utilizes N ₂gas as analyze adsorptive measured be less than 22m ²/ g, is more preferably less than 20m ²/ g, is also more preferably less than 18m ²the surface-area of/g.The mineral filler (F) that meets these requirements is preferably anisotropic mineral filler (F), as talcum, mica and wollastonite.

Other components

Heterophasic propylene copolymers of the present invention (HECO) can comprise typical additive, as acid scavenger (AS), antioxidant (AO), nucleator (NA), hindered amine as light stabilizer (HALS), surface slip agent (SA) and pigment.Preferably, in heterophasic propylene copolymers of the present invention (HECO), the amount of getting rid of the additive of mineral filler (F) should be no more than 7 % by weight, more preferably should be no more than 5 % by weight, as be no more than 3 % by weight.

Therefore,, based on the gross weight of heterophasic propylene copolymers (HECO), heterophasic propylene copolymers (HECO) preferably comprises

(a) be less than 75.0 % by weight, more preferably 50.0 % by weight are to 70.0 % by weight, still more preferably 60.0 % by weight to the matrix (M) of 65.0 % by weight, i.e. polypropylene (PP), and

(b) be equal to or greater than 20.0 % by weight, more preferably 20.0 % by weight are to 50.0 % by weight, still more preferably 25.0 % by weight to the elastomerics (E) of 40.0 % by weight,

(c) maximum 8 % by weight, more preferably 0 to 8 % by weight, as in 1 % by weight within the scope of 8 % by weight, the still more preferably polyethylene (PE) within the scope of 0 to 6 % by weight, preferably high density polyethylene(HDPE) (HDPE),

(d) maximum 25 % by weight, more preferably 4 % by weight are to 25 % by weight, still more preferably 5 % by weight to the mineral filler (F) of 20 % by weight, preferably talc.

The goods of being made by heterophasic propylene copolymers (HECO)

Heterophasic propylene copolymers of the present invention (HECO) is preferably used for producing motor vehicle goods, as motor vehicle moulded parts, and preferably motor vehicle injection-molded item.Even be more preferably used in and produce automotive interior and external articles, as collision bumper, return moldings part, foot-operated supplementary unit, body panel, interceptor, dashboard, inner gadget etc., especially collision bumper.

The present invention also provides (motor vehicle) goods, as injection-molded item, it comprises at least 60 % by weight, more preferably at least 70 % by weight, the also heterophasic propylene copolymers of the present invention (HECO) of at least 75 % by weight more preferably, as being made up of heterophasic propylene copolymers of the present invention (HECO).Therefore, the invention particularly relates to motor vehicle goods, relate in particular to automotive interior and external articles, as collision bumper, return moldings part, foot-operated supplementary unit, body panel, interceptor, dashboard, inner gadget etc., particularly collision bumper, it comprises at least 60 % by weight, more preferably at least 70 % by weight, the also more preferably heterophasic propylene copolymers of the present invention (HECO) of at least 75 % by weight, as being made up of heterophasic propylene copolymers of the present invention (HECO).

According to purposes of the present invention

The invention still further relates to the purposes of heterophasic propylene copolymers as above (HECO) in road vehicle application.In a preferred embodiment, heterophasic propylene copolymers (HECO) uses in collision bumper.

Now the embodiment by below providing is described to the present invention in further detail.

The preparation of heterophasic propylene copolymers (HECO)

As heterophasic propylene copolymers defined above (HECO) can be by being prepared as the method below being limited.

Can be prepared by elastomerics (E) and the method for the step of matrix (M) blend by comprising according to heterophasic propylene copolymers of the present invention (HECO).Term " blend " refers to the action of the blend that at least two kinds of different materials that existed are provided according to the present invention.On the other hand, term " mixing " comprises blend, forms blend but be also included under a kind of material existence by making another kind of substance reaction carry out original position.

The method according to this invention can also comprise will be selected from (PP1), (PP2) thereby and a kind of polypropylene part (PP3) and the mixture blend that contains all the other two kinds of polypropylene parts obtain the step of polypropylene (PP).In another embodiment, method for the preparation of polypropylene (PP) comprises the following steps: (a) by a kind of polypropylene part that is selected from (PP1), (PP2) and (PP3) from be selected from (PP1), polypropylene part blend that (PP2) is different with another kind (PP3), then add be selected from (PP1), (PP2) and remaining part (PP3), or (b) in a step by polypropylene part (PP1), (PP2) and (PP3) blend each other.Each polypropylene part (PP1), (PP2) and (PP3) can use traditional way, for example, be prepared in loop reactor or in ring type/liquid-gas phase reactor system.

In another embodiment, the present invention relates to a kind of sequential polymerization processes for the preparation of polypropylene according to the present invention (PP), described polypropylene (PP) comprises the first polypropylene part (PP1), the second polypropylene part (PP2) and tripropylene part (PP3).Described method can comprise the following steps:

(a1) in the first reactor (R1), make propylene and optionally at least one ethene and/or C ₄to C ₁₂alpha-olefine polymerizing, obtain the first polypropylene part (PP1),

(b1) described the first polypropylene part (PP1) is transferred in the second reactor (R2),

(c1), in described the second reactor (R2) and under the existence of described the first polypropylene part (PP1), make propylene and optionally at least one ethene and/or C ₄to C ₁₂alpha-olefine polymerizing, thereby obtain the second polypropylene part (PP2), described the first polypropylene part (PP1) is mixed with described the second polypropylene part (PP2),

(d1) mixture of step (c1) is transferred in the 3rd reactor (R3),

(e1), in described the 3rd reactor (R3) and under the existence of the mixture obtaining, make propylene and optionally at least one ethene and/or C in step (c1) ₄to C ₁₂alpha-olefine polymerizing, thereby obtain tripropylene part (PP3), wherein said the first polypropylene part (PP1), described the second polypropylene part (PP2) and described tripropylene part (PP3) be mixed with each other and form polypropylene (PP);

Or

(a2) in the first reactor (R1), make propylene and optionally at least one ethene and/or C ₄to C ₁₂alpha-olefine polymerizing, obtain the first polypropylene part (PP1),

(b2) described the first polypropylene part (PP1) is transferred in the second reactor (R2),

(c2), in described the second reactor (R2) and under the existence of described the first polypropylene part (PP1), make propylene and optionally at least one ethene and/or C ₄to C ₁₂alpha-olefine polymerizing, thereby obtain tripropylene part (PP3), described the first polypropylene part (PP1) is mixed with described tripropylene part (PP3),

(d2) mixture of step (c2) is transferred in the 3rd reactor (R3),

(e2), in described the 3rd reactor (R3) and under the existence of the mixture obtaining, make propylene and optionally at least one ethene and/or C in step (c2) ₄to C ₁₂alpha-olefine polymerizing, thereby obtain the second polypropylene part (PP2), wherein said the first polypropylene part (PP1), described the second polypropylene part (PP2) and described tripropylene part (PP3) be mixed with each other and form polypropylene (PP);

Or

(a3) in the first reactor (R1), make propylene and optionally at least one ethene and/or C ₄to C ₁₂alpha-olefine polymerizing, obtain the second polypropylene part (PP2),

(b3) described the second polypropylene part (PP2) is transferred in the second reactor (R2),

(c3), in described the second reactor (R2) and under the existence of described the second polypropylene part (PP2), make propylene and optionally at least one ethene and/or C ₄to C ₁₂alpha-olefine polymerizing, thereby obtain tripropylene part (PP3), described the second polypropylene part (PP2) is mixed with described tripropylene part (PP3),

(d3) mixture of step (c3) is transferred in the 3rd reactor (R3),

(e3), in described the 3rd reactor (R3) and under the existence of the mixture obtaining, make propylene and optionally at least one ethene and/or C in step (c3) ₄to C ₁₂alpha-olefine polymerizing, thereby obtain the first polypropylene part (PP1), wherein said the first polypropylene part (PP1), described the second polypropylene part (PP2) and described tripropylene part (PP3) be mixed with each other and form polypropylene (PP);

Or

(a4) in the first reactor (R1), make propylene and optionally at least one ethene and/or C ₄to C ₁₂alpha-olefine polymerizing, obtain the second polypropylene part (PP2),

(b4) described the second polypropylene part (PP2) is transferred in the second reactor (R2),

(c4), in described the second reactor (R2) and under the existence of described the second polypropylene part (PP2), make propylene and optionally at least one ethene and/or C ₄to C ₁₂alpha-olefine polymerizing, thereby obtain the first polypropylene part (PP1), described the second polypropylene part (PP2) is mixed with described the first polypropylene part (PP1),

(d4) mixture of step (c4) is transferred in the 3rd reactor (R3),

(e4), in described the 3rd reactor (R3) and under the existence of the mixture obtaining, make propylene and optionally at least one ethene and/or C in step (c4) ₄to C ₁₂alpha-olefine polymerizing, thereby obtain tripropylene part (PP3), wherein said the first polypropylene part (PP1), described the second polypropylene part (PP2) and described tripropylene part (PP3) be mixed with each other and form polypropylene (PP);

Or

(a5) in the first reactor (R1), make propylene and optionally at least one ethene and/or C ₄to C ₁₂alpha-olefine polymerizing, obtain tripropylene part (PP3),

(b5) described tripropylene part (PP3) is transferred in the second reactor (R2),

(c5), in described the second reactor (R2) and under the existence of described tripropylene part (PP3), make propylene and optionally at least one ethene and/or C ₄to C ₁₂alpha-olefine polymerizing, thereby obtain the first polypropylene part (PP1), described tripropylene part (PP3) is mixed with described the first polypropylene part (PP1),

(d5) mixture of step (c5) is transferred in the 3rd reactor (R3),

(e5), in described the 3rd reactor (R3) and under the existence of the mixture obtaining, make propylene and optionally at least one ethene and/or C in step (c5) ₄to C ₁₂alpha-olefine polymerizing, thereby obtain the second polypropylene part (PP2), wherein said the first polypropylene part (PP1), described the second polypropylene part (PP2) and described tripropylene part (PP3) be mixed with each other and form polypropylene (PP);

Or

(a6) in the first reactor (R1), make propylene and optionally at least one ethene and/or C ₄to C ₁₂alpha-olefine polymerizing, obtain tripropylene part (PP3),

(b6) described tripropylene part (PP3) is transferred in the second reactor (R2),

(c6), in described the second reactor (R2) and under the existence of described tripropylene part (PP3), make propylene and optionally at least one ethene and/or C ₄to C ₁₂alpha-olefine polymerizing, thereby obtain the second polypropylene part (PP2), described tripropylene part (PP3) is mixed with described the second polypropylene part (PP2),

(d6) mixture of step (c6) is transferred in the 3rd reactor (R3),

(e6), in described the 3rd reactor (R3) and under the existence of the mixture obtaining, make propylene and optionally at least one ethene and/or C in step (c6) ₄to C ₁₂alpha-olefine polymerizing, thereby obtain the first polypropylene part (PP1), wherein said the first polypropylene part (PP1), described the second polypropylene part (PP2) and described tripropylene part (PP3) be mixed with each other and form polypropylene (PP).

Preferably, between the second reactor (R2) and the 3rd reactor (R3), comonomer is flashed out.

For the preferred embodiment of polypropylene (PP), the first polypropylene part (PP1), the second polypropylene part (PP2) and tripropylene part (PP3), with reference to restriction given above.

Term " sequential polymerization processes " represents that polypropylene is to prepare at least three reactors that are connected in series.Therefore, present method at least comprises the first reactor (R1), the second reactor (R2) and the 3rd reactor (R3).Term " polymerization reactor " should represent to occur main polymerization part.Therefore,, if method is made up of four polymerization reactors, the selection that whole method comprises the prepolymerization step in pre-polymerization reactor for example is not got rid of in this definition.Term " by ... form " aspect main polymerization reactor, be only closing form.

The first reactor (R1) is preferably slurry reactor (SR), and can be the tank reactor or loop reactor at intermittence arbitrary continuation or simple agitation with the operation of body or slurry.The polymerization of ontology representation in the reaction medium that comprises at least 60% (w/w) monomer.According to the present invention, slurry reactor (SR) is preferably (body) loop reactor (LR).

The second reactor (R2) and the 3rd reactor (R3) are preferably Gas-phase reactor (GPR).This gas-like phase reactor (GPR) can be any churned mechanically reactor or fluidized-bed reactor.Preferably, Gas-phase reactor (GPR) comprises the mechanical stirring fluidized-bed reactor of the gas velocity with 0.2m/ at least second.Therefore should be appreciated that, Gas-phase reactor is the fluid bed-type of reactor preferably with mechanical stirrer.

Therefore, in a preferred embodiment, the first reactor (R1) is slurry reactor (SR), as loop reactor (LR), and the second reactor (R2) and the 3rd reactor (R3) are Gas-phase reactor (GPR).Therefore,, for present method, use at least three that are connected in series, preferably three polymerization reactors, be slurry reactor (SR), as loop reactor (LR), the first Gas-phase reactor (GPR-1), and the second Gas-phase reactor (GPR-2).As required, place before pre-polymerization reactor at slurry reactor (SR).

A kind of preferred multi-stage method is " ring type-gas phase " method, and that is for example developed by the BorealisA/S of Denmark (is called as

technology), for example, in patent documentation, described in EP0887379, WO92/12182WO2004/000899, WO2004/111095, WO99/24478, WO99/24479 or WO00/68315.

Another suitable slurry-gas phase process is Basell

method.

Preferably, in the present invention for the preparation of in as the method for the above polypropylene limiting (PP), first reactor (R1) of step (a), i.e. slurry reactor (SR), as the condition of loop reactor (LR) can be as follows:

-temperature in the scope of 50 ℃ to 110 ℃, preferably between 60 ℃ and 100 ℃, more preferably between 68 ℃ and 95 ℃,

-pressure at 20 bar in the scope of 80 bar, preferably at 40 bar between 70 bar,

-can add hydrogen for controlling in a manner known way molar mass.

Then, will transfer to the second reactor (R2) from the reaction mixture of step (a), i.e. Gas-phase reactor (GPR-1), transfers to step (c), and condition optimization in step (c) is as follows:

-temperature in the scope of 50 ℃ to 130 ℃, preferably between 60 ℃ and 100 ℃,

-pressure at 5 bar in the scope of 50 bar, preferably at 15 bar between 35 bar,

-can add hydrogen for controlling in a manner known way molar mass.

The 3rd reactor (R3), preferably the condition in the second Gas-phase reactor (GPR-2) and the second reactor (R2) is similar.

In three reactor area, the residence time can change.

In an embodiment for the preparation of polyacrylic method, bulk reaction device, for example the residence time in loop reactor is in the scope of 0.1 hour to 2.5 hours, for example 0.15 hour to 1.5 hours, the residence time in Gas-phase reactor can be generally 0.2 hour to 6.0 hours, as 0.5 hour to 4.0 hours.

If needed, can be at the first reactor (R1), be slurry reactor (SR), as carried out polymerization with condensation mode in known manner and/or in Gas-phase reactor (GPR) in loop reactor (LR) under super critical condition.

Preferably, method also comprises to be utilized as the below prepolymerization of catalyst system described in detail, and described catalyst system comprises Z-N Primary Catalysts, external donor and promotor optionally.

In a preferred embodiment, prepolymerization mode with body slurry polymerisation in liquid propene is carried out, and liquid phase mainly comprises propylene, and other a small amount of reactants and be optionally dissolved in inert component wherein.

Prepolymerization, generally at 10 ℃ to 60 ℃, preferably 15 ℃ to 50 ℃, more preferably carries out at the temperature of 20 ℃ to 45 ℃.

Pressure in pre-polymerization reactor is not crucial, but must be enough high to maintain reaction mixture in liquid phase.Therefore, pressure can be 20 bar to 100 bar, for example 30 bar to 70 bar.

Preferably catalyst component is all incorporated into prepolymerization step.But, in the time that ingredient of solid catalyst (i) and promotor (ii) can be distinguished charging, can only a part of promotor be incorporated in prepolymerisation stage, remainder is incorporated in follow-up polymerization stage.In addition, in this case, so many promotor must be incorporated in prepolymerisation stage to make wherein to obtain enough polyreactions.

Can also add other components to prepolymerisation stage.Therefore, as known in the art, hydrogen can be added in prepolymerisation stage to control the molecular weight of prepolymer.In addition, can use anti static additive to stop particle stick each other or be attached on reactor wall.

In the scope that is accurately controlled at the art of prepolymerization condition and reaction parameter.

According to the present invention, polypropylene (PP) preferably obtains by multistage polymerization method as above under the existence of catalyst system, described catalyst system comprises Z-N Primary Catalysts as component (i), the ester exchange offspring that described Z-N Primary Catalysts contains lower alcohol and phthalic ester.

Prepare by following steps according to Primary Catalysts used in the present invention

A) make through spray crystallization or the curing MgCl of emulsion ₂and C ₁to C ₂adducts and the TiCl of alcohol ₄reaction

B) at described C ₁to C ₂the condition of alcohol and the bialkyl ortho phthalate generation transesterify of formula (I) under make stage product a) react to form internal donor with the bialkyl ortho phthalate of described formula (I)

Wherein R ^{1 '}and R ^{2 '}be C at least independently ₅alkyl

C) wash phase product b), or

D) optionally make step product c) and other TiCl ₄reaction.

Primary Catalysts as for example prepared defined in patent application WO87/07620, WO92/19653, WO92/19658 and EP0491566.The content of these files is included in herein by reference.

First form formula MgCl ₂* the MgCl of nROH ₂and C ₁to C ₂the adducts of alcohol, wherein R is that methyl or ethyl and n are 1 to 6.Ethanol is preferably as alcohol.

First melting then spray crystallization or the curing adducts of emulsion as support of the catalyst.

In next step, formula MgCl ₂* nROH through spray crystallization or curing adducts and the TiCl of emulsion ₄contact is to form titanizing carrier, and wherein R is methyl or ethyl, and preferably ethyl and n are 1 to 6, are then following steps

Add described titanizing carrier to form the first product following material

(i) bialkyl ortho phthalate of formula (I), wherein R ¹' and R ²' be C at least independently ₅alkyl, as C at least ₈alkyl,

Or preferably

(ii) bialkyl ortho phthalate of formula (I), wherein R ^{1 '}and R ^{2 '}for identical, and be C at least ₅alkyl, as C at least ₈alkyl,

Or more preferably

(iii) bialkyl ortho phthalate of formula (I), it is selected from phthalic acid propyl group polyhexamethylene (PrHP), dioctyl phthalate (DOP) (DOP), Di Iso Decyl Phthalate (DIDP) and phthalic acid two (tridecyl) ester (DTDP), also more preferably the bialkyl ortho phthalate of formula (I) is that dioctyl phthalate (DOP) (DOP) is as dimixo-octyl phthalate or phthalic acid two (ethyl hexyl) ester, especially phthalic acid two (ethyl hexyl) ester

Make described the first product experience suitable transesterification conditions, experience higher than 100 ℃, preferably between 100 ℃ to 150 ℃, more preferably the temperature between 130 ℃ to 150 ℃, so that the described ester group of the bialkyl ortho phthalate of described methyl alcohol or ethanol and described formula (I) carries out transesterify, to form preferably at least 80 % by mole, more preferably at least 90 % by mole, the most preferably bialkyl ortho phthalate of the formula of at least 95 % by mole (II)

Wherein R ¹and R ²for methyl or ethyl, preferably ethyl,

The bialkyl ortho phthalate of formula (II) is internal donor, and

Reclaim described ester exchange offspring as Primary Catalysts composition (component (i)).

Formula MgCl ₂* the adducts of nROH (wherein R is that methyl or ethyl and n are 1 to 6) melting in a preferred embodiment, then melt preferably by gas inject in cooling solvent or cooling gas, thereby described adducts crystallization is the form that form is favourable, as for example described in the WO87/07620.

Described at WO92/19658 and WO92/19653, the adducts of this crystallization is preferably the Primary Catalysts can be used in the present invention as support of the catalyst reaction.

In the time removing catalyst residue by extraction, obtain the adducts of titanizing carrier and internal donor, the group that wherein derives from ester alcohol changes.

If sufficient titanium is retained on carrier, it can be as the active element of Primary Catalysts.

Otherwise repeat afterwards titanizing to guarantee sufficient titanium concentration and to guarantee thus activity in above-mentioned processing.

Preferably, contain 2.5 % by weight at the most according to Primary Catalysts used in the present invention, preferably 2.2 % by weight at the most, the more preferably titanium of 2.0 % by weight at the most.Its donor content preferably in 4 % by weight between 12 % by weight, more preferably in 6 % by weight between 10 % by weight.

More preferably, by using ethanol to prepare as the bialkyl ortho phthalate of formula (I) as alcohol and dioctyl phthalate (DOP) (DOP), generate diethyl phthalate (DEP) as internal donor compound according to Primary Catalysts used in the present invention.

Still more preferably, the BCF20P catalyzer that is Borealis according to catalyzer used in the present invention is (as disclosed prepared according to WO92/19653 in WO99/24479; Especially use dioctyl phthalate (DOP) as the bialkyl ortho phthalate of formula (I) according to WO92/19658) or the catalyst P olytrack8502 that is purchased from Grace.

In order to prepare according to polypropylene of the present invention (PP), the catalyst system using preferably also comprises organic metal promoters as component (ii) except specific Z-N Primary Catalysts.

Therefore, promotor is preferably selected from trialkylaluminium as triethyl aluminum (TEA), dialkylaluminum chloride and alkyl sesquialter aluminum chloride.

The component (iii) of the catalyst system using is for by formula (IIIa) or (IIIb) represented external donor.Formula (IIIa) is defined by following formula

Si(OCH ₃) ₂R ₂ ⁵(IIIa)

Wherein R ⁵the alkyl that represents the branching with 3 to 12 carbon atoms, preferably has the alkyl of the branching of 3 to 6 carbon atoms, or has the cycloalkyl of 4 to 12 carbon atoms, preferably has the cycloalkyl of 5 to 8 carbon atoms.

Particularly preferably, R ⁵be selected from sec.-propyl, isobutyl-, isopentyl, the tertiary butyl, tert-pentyl, neo-pentyl, cyclopentyl, cyclohexyl, methylcyclopentyl and suberyl.

Formula (IIIb) is defined by following formula

Si(OCH ₂CH ₃) ₃(NR ^xR ^y)(IIIb)

Wherein R ^xand R ^ycan be identical or different, and represent to have the alkyl of 1 to 12 carbon atom.

R ^xand R ^yindependently selected from have 1 to 12 carbon atom linear aliphatic family alkyl, there is the branching aliphatic alkyl of 1 to 12 carbon atom and there is the annular aliphatic alkyl of 1 to 12 carbon atom.Particularly preferably, R ^xand R ^yindependently selected from methyl, ethyl, n-propyl, normal-butyl, octyl group, decyl, sec.-propyl, isobutyl-, isopentyl, the tertiary butyl, tert-pentyl, neo-pentyl, cyclopentyl, cyclohexyl, methylcyclopentyl and suberyl.

More preferably, R ^xand R ^yfor identical, also more preferably, R ^xand R ^yit is all ethyl.

More preferably, the external donor of formula (IIIb) is diethylin triethoxyl silane.

More preferably, external donor is selected from diethylin triethoxyl silane [Si (OCH ₂cH ₃) ₃(N (CH ₂cH ₃) ₂)], dicyclopentyl dimethoxyl silane [Si (OCH ₃) ₂(cyclopentyl) ₂], diisopropyl dimethoxy silane [Si (OCH ₃) ₂(CH (CH ₃) ₂) ₂] and composition thereof.

In another embodiment, Z-N Primary Catalysts can be by making polymerization of vinyl compound carry out modification under the existence of catalyst system, described catalyst system comprises specific Z-N Primary Catalysts (component (i)), external donor (component (iii)) and promotor (component (iii)) optionally, and described vinyl compound has following formula:

CH ₂=CH-CHR ³R ⁴

Wherein R ³and R ⁴form together 5 yuan or 6 yuan of saturated, undersaturated or aromatic nucleus, or represent independently the alkyl that comprises 1 to 4 carbon atom, through the catalyzer of modification for the preparation of heterophasic propylene copolymers according to the present invention.Vinyl compound through polymerization can be used as α-nucleator.

About the modification of catalyzer, with reference to International Application No. WO 99/24478, WO99/24479 and particularly WO00/68315, at the reaction conditions about catalyst modification and be incorporated to by reference aspect polyreaction herein.

Then, by obtained polypropylene (PP) and elastomerics (E) and optional additive blend.The general forcing machine that uses, if single screw extrusion machine and twin screw extruder are for blend.Other suitable devices comprise planetary extruder and single screw rod kneader altogether.Especially preferred is the twin screw extruder that comprises high strength mixing section and kneading block.For the preparation of the suitable melt temperature of heterophasic propylene copolymers (HECO) in the scope of 170 ℃ to 300 ℃, preferably in the scope of 200 ℃ to 260 ℃.Normally pill form of the heterophasic propylene copolymers (HECO) reclaiming from forcing machine.Then preferably further process these pills, for example by injection moulding to obtain goods, as above more in detail limit goods.

To further illustrate the present invention by embodiment below.

Embodiment

A. measuring method

Unless otherwise defined, otherwise the definition of following term and measuring method is applicable to above general description of the present invention and following embodiment.

Calculate the co-monomer content of the second polypropylene part (PP2):

$\frac{C\left(R2\right)-w\left(\mathrm{PP}1\right)\mathrm{xC}\left(\mathrm{PP}1\right)}{w\left(\mathrm{PP}2\right)}=C\left(\mathrm{PP}2\right)$

Wherein

W (PP1) is the first polypropylene part (PP1), i.e. the weight fraction of the product of the first reactor (R1),

W (PP2) is the second polypropylene part (PP2), i.e. the weight fraction of prepared polymkeric substance in the second reactor (R2),

C (PP1) is the first polypropylene part (PP1), i.e. the co-monomer content [% by weight] of the product of the first reactor (R1),

The product of C (R2) for obtaining in the second reactor (R2), i.e. the co-monomer content [% by weight] of the mixture of the first polypropylene part (PP1) and the second polypropylene part (PP2),

The co-monomer content [% by weight] that C (PP2) is the second polypropylene (PP2) of calculating.

Calculate the cold solvend of dimethylbenzene (XCS) content of the second polypropylene part (PP2):

$\frac{\mathrm{XS}\left(R2\right)-w\left(\mathrm{PP}1\right)\mathrm{xXS}\left(\mathrm{PP}1\right)}{w\left(\mathrm{PP}2\right)}=\mathrm{XS}\left(\mathrm{PP}2\right)$

Wherein

W (PP1) is the first polypropylene part (PP1), i.e. the weight fraction of the product of the first reactor (R1),

W (PP2) is the second polypropylene part (PP2), i.e. the weight fraction of prepared polymkeric substance in the second reactor (R2),

XS (PP1) is the first polypropylene part (PP1), i.e. the cold solvend of dimethylbenzene (XCS) content [% by weight] of the product of the first reactor (R1),

The product of XS (R2) for obtaining in the second reactor (R2), the i.e. cold solvend of dimethylbenzene (XCS) content [% by weight] of the mixture of the first polypropylene part (PP1) and the second polypropylene part (PP2)

The cold solvend of dimethylbenzene (XCS) content [% by weight] that XS (PP2) is the second polypropylene part (PP2) of calculating.

Calculate the melt flow rate (MFR) MFR of the second polypropylene part (PP2) ₂(230 ℃):

$\mathrm{MFR}\left(\mathrm{PP}2\right)={10}^{\left[\frac{\log \left(\mathrm{MFR}\left(R2\right)\right)-w\left(\mathrm{PP}1\right)x\log \left(\mathrm{MFR}\left(\mathrm{PP}1\right)\right)}{w\left(\mathrm{PP}2\right)}\right]}$

Wherein

W (PP1) is the first polypropylene part (PP1), i.e. the weight fraction of the product of the first reactor (R1),

W (PP2) is the second polypropylene part (PP2), i.e. the weight fraction of prepared polymkeric substance in the second reactor (R2),

MFR (PP1) is the first polypropylene part (PP1), i.e. the melt flow rate (MFR) MFR of the product of the first reactor (R1) ₂(230 ℃) [gram/10 minutes],

The product of MFR (R2) for obtaining in the second reactor (R2), i.e. the melt flow rate (MFR) MFR of the mixture of the first polypropylene part (PP1) and the second polypropylene part (PP2) ₂(230 ℃) [gram/10 minutes],

The melt flow rate (MFR) MFR that MFR (PP2) is the second polypropylene part (PP2) of calculating ₂(230 ℃) [gram/10 minutes].

Calculate the co-monomer content of tripropylene part (PP3):

$\frac{C\left(R3\right)-w\left(R2\right)\mathrm{xC}\left(R2\right)}{w\left(\mathrm{PP}3\right)}=C\left(\mathrm{PP}3\right)$

Wherein

W (R2) is the product of the second reactor (R2), i.e. the weight fraction of the mixture of the first polypropylene part (PP1) and the second polypropylene part (PP2),

W (PP3) is tripropylene part (PP3), i.e. the weight fraction of prepared polymkeric substance in the 3rd reactor (R3),

C (R2) is the product of the second reactor (R2), i.e. the co-monomer content [% by weight] of the mixture of the first polypropylene part (PP1) and the second polypropylene part (PP2),

The product of C (R3) for obtaining in the 3rd reactor (R3), the i.e. co-monomer content [% by weight] of the mixture of the first polypropylene part (PP1), the second polypropylene part (PP2) and tripropylene part (PP3)

The co-monomer content [% by weight] that C (PP3) is the tripropylene part (PP2) that calculates.

Calculate the cold solvend of dimethylbenzene (XCS) content of tripropylene part (PP3):

$\frac{\mathrm{XS}\left(R3\right)-w\left(R2\right)\mathrm{xXS}\left(R2\right)}{w\left(\mathrm{PP}3\right)}=\mathrm{XS}\left(\mathrm{PP}3\right)$

Wherein

W (R2) is the product of the second reactor (R2), i.e. the weight fraction of the mixture of the first polypropylene part (PP1) and the second polypropylene part (PP2),

W (PP3) is tripropylene part (PP3), i.e. the weight fraction of prepared polymkeric substance in the 3rd reactor (R3),

XS (R2) is the product of the second reactor (R2), i.e. the cold solvend of dimethylbenzene (XCS) content [% by weight] of the mixture of the first polypropylene part (PP1) and the second polypropylene part (PP2),

The product of XS (R3) for obtaining in the 3rd reactor (R3), the i.e. cold solvend of dimethylbenzene (XCS) content [% by weight] of the mixture of the first polypropylene part (PP1), the second polypropylene part (PP2) and tripropylene part (PP3)

The cold solvend of dimethylbenzene (XCS) content [% by weight] that XS (PP3) is the tripropylene part (PP3) that calculates.

Calculate the melt flow rate (MFR) MFR of tripropylene part (PP3) ₂(230 ℃):

$\mathrm{MFR}\left(\mathrm{PP}3\right)={10}^{\left[\frac{\log \left(\mathrm{MFR}\left(R3\right)\right)-w\left(R2\right)x\log \left(\mathrm{MFR}\left(R2\right)\right)}{w\left(\mathrm{PP}3\right)}\right]}$

Wherein

W (R2) is the product of the second reactor (R2), i.e. the weight fraction of the mixture of the first polypropylene part (PP1) and the second polypropylene part (PP2),

W (PP3) is tripropylene part (PP3), i.e. the weight fraction of prepared polymkeric substance in the 3rd reactor (R3),

MFR (R2) is the product of the second reactor (R2), i.e. the melt flow rate (MFR) MFR of the mixture of the first polypropylene part (PP1) and the second polypropylene part (PP2) ₂(230 ℃) [gram/10 minutes],

The product of MFR (R3) for obtaining in the 3rd reactor (R3), i.e. the melt flow rate (MFR) MFR of the mixture of the first polypropylene part (PP1), the second polypropylene part (PP2) and tripropylene part (PP3) ₂(230 ℃) [gram/10 minutes],

The melt flow rate (MFR) MFR that MFR (PP3) is the tripropylene part (PP3) that calculates ₂(230 ℃) [gram/10 minutes].

Number-average molecular weight (M _n), weight-average molecular weight (M _w) and molecular weight distribution (MWD) determine by gel permeation chromatography (GPC) according to following methods:

Weight-average molecular weight Mw and molecular weight distribution (MWD=Mw/Mn, wherein Mn is number-average molecular weight, Mw is weight-average molecular weight) measure by the method based on ISO16014-1:2003 and ISO16014-4:2003.Be equipped with the Waters Alliance GPCV2000 of refractive index detector and online viscosmeter to adopt the 3x TSK-gel column (GMHXL-HT) and 1 of TosoHaas, 2,4-trichlorobenzene (TCB, with 200mg/L2,6-di-t-butyl-4-methyl-phenol is stable) used with constant flow rate 1mL/ minute at 145 ℃ as solvent.Each analysis injected 216.5 μ L sample solutions.Post group is calibrated to 19 narrow MWD polystyrene (PS) standard substances within the scope of 11500 kg/mol and the relative scale of one group of wide polypropylene standard substance fully characterizing with having in 0.5 kg/mol.By by 5mg, to 10mg polymer dissolution to 10mL, (at 160 ℃) were keeping preparing for 3 hours all samples under shake continuously in stable TCB (identical with moving phase) and at sample introduction before in GPC instrument.

Density is measured according to ISO1183-1-method A (2004).Sample preparation completes by the compression molding according to ISO1872-2:2007.

MFR ₂(230 ℃) are measured according to ISO1133 (230 ℃, 2.16kg load).

MFR ₂(190 ℃) are measured according to ISO1133 (190 ℃, 2.16kg load).

The co-monomer content of being undertaken by FTIR spectrography quantizes

In mode well-known in the art, via quantitatively ¹³after the basic ownership of C nucleus magnetic resonance (NMR) spectral method calibration, determine co-monomer content by quantitative fourier transform infrared spectroscopy (FTIR).Film is pressed at 100 μ m to the thickness between 500 μ m, and with transmission mode spectra re-recorded.

Particularly, use at 720cm ^-1to 722cm ^-1and 730cm ^-1to 733cm ^-1the peak area through baseline correction of the quantitative band that place finds is determined the ethylene content of propylene-ethylene copolymers.Particularly, use at 1377cm ^-1to 1379cm ^-1the peak area through baseline correction of the quantitative band that place finds is determined butylene or the hexene content of polyethylene and ethylene copolymers.Based on obtaining quantitative result with reference to film thickness.

The cold solvend of dimethylbenzene (XCS, % by weight): the content of the cold solvend of dimethylbenzene (XCS) is according to ISO16152: first version; 2005-07-01 determines at 25 ℃.

Limiting viscosity number is according to DIN ISO1628/1, and measure in October, 1999 (at 135 ℃ in naphthalane).

Melt temperature T _m, Tc T _cutilize Mettler TA820 differential scanning calorimeter (DSC) 5mg to 10mg sample measurement.Crystallization curve and melting curve both obtain in the cooling and heating scanning process of 10 ℃/min between 30 ℃ and 225 ℃.Melt temperature and Tc are taken as endotherm(ic)peak and exothermic peak.

Melting enthalpy and crystallization enthalpy (Hm and Hc) are also measured by DSC method according to ISO11357-3.

Tensile modulus is measuring according to the injection moulding sample of ISO527-2 (1B) (dog bone shape 10, thickness is 4mm) of manufacturing according to EN ISO1873-2 23 ℃ of uses according to ISO527-1 (pinblock speed=1mm/ minute).

Charpy otch resistance to impact shock according to ISO179/1eA 23 ℃ and at-20 ℃ by using injection moulding sample (80 × 10 × 4mm) described in EN ISO1873-2 to determine.

Exposing energy uses (IFW) test of dropping hammer of the moulding of 60 × 60 × 2mm and the trial speed of 4.4m/s instrument to determine according to ISO6603-2.That reports exposes energy by obtaining with the integration of-20 ℃ of measured failure energy curves at+23 ℃.

Shrinking percentage is upper definite at the injection moulding disk (diameter 180mm, thickness 3mm have the flow angle of 355 ° and the cut-out angle of 5 °) of trumpet assembly.Apply two samples of two different maintenance pressure times (being respectively 10s and 20s) molding.The melt temperature at cast gate place is 260 ℃, and average flow forward position speed in mould is 100mm/s.Tool temperature: 40 ℃, back-pressure: 600 bar.

At room temperature make sample adapt to after 96 hours, two disks are measured to the dimensional change radially and on tangential with respect to flow direction.The mean value of the value separately from two disks is reported as to net result.

Particle diameter (d50 and cut-off particle diameter d95 (sedimentation)) is by passing through size distribution [mass percent] calculating definite according to the gravity liquid sedimentation (sedigraph) of ISO13317-3.

BET measures according to ISO9277.

B. embodiment

All polymkeric substance are prepared in the Borstar pilot plant with pre-polymerization reactor, a slurry loop reactor and two Gas-phase reactor.The catalyst P olytrack8502 being purchased from Grace (US) with as the diethylin triethoxyl silane [Si (OCH of external donor ₂cH ₃) ₃(N (CH ₂cH ₃) ₂)] (U donor) and be used in combination with the ratio shown in table 1 as the triethyl aluminum (TEAL) of activator and scavenging agent.Catalyzer by making polymerization of vinyl compound carry out modification under the existence of catalyst system.

Table 1: the preparation of polypropylene (PP)

Parameter	Unit	H-PP
			Donor type	?	U
Al/ donor ratio	[moles/mole]	9
			Ring type	?	?
MFR 2(230℃)	[gram/10 minutes]	343
			XCS	[% by weight]	2.1
GPR1	?	?
			MFR 2(230℃)	[gram/10 minutes]	218
XCS	[% by weight]	2.0
			MFR 2*	[gram/10 minutes]	134
XCS*	[% by weight]	1.8
			GPR2	?	?
MFR 2(230℃)	[gram/10 minutes]	125
			XCS	[% by weight]	1.8
MFR 2**	[gram/10 minutes]	6.5
			XCS**	[% by weight]	1.5
MWD	[-]	6.5
			Distribute ring type/GPR1/GPR2	[% by weight]	42/42/16

* the polymkeric substance of preparing in GPR1

The polymkeric substance of preparing in * GPR2

Table 1 has been summarized the three polyacrylic polymer design in peak that use in work embodiment.Use has the three peak polypropylene (PP) of the MFR identical with the unimodal polyacrylic polymer (HK060AE) being purchased.

Table 2: for the compound prescription of work embodiment and comparative example

Component	E1	E2	E3	CE1	CE2
						HK060AE	-	-	-	67.1	53.7
H-PP	67.1	67.1	53.7	-	-
						Engage8400	30	25	24	30	24
HDPE	-	5	-	-	-
						Talcum	-	-	20	-	20

Rest part is additive to 100 % by weight, for example, as antioxidant and pigment (carbon black)

HK060AE is the commodity of Borealis AG, and it is to have the MFR of 125 grams/10 minutes ₂(230 ℃/2.16kg) and 905kg/m ³the homopolymer polypropylene of density.

Engage8400 is the commodity of Dow Elastomers, and it is to have the MFR of 30 grams/10 minutes ₂(190 ℃, 2.16kg) and 870kg/m ³the ethylene-octene copolymer of density.

HDPE is the commercial high density polyethylene(HDPE) (HDPE) " MG9601 " of Borealis, and it has MFR (190 ℃/2.16kg) and the 960kg/m of 30 grams/10 minutes ³density.

Talcum is the commercial talcum " SteamicT1CA " that can obtain from Luzenac, and it has the d50 of 1.8 μ m, the cut-off particle diameter (d of 6.2 μ m ₉₅) and 8.0m ²the BET of/g.

The performance characteristic of resulting materials is summarized in table 3.

Table 3: the performance characteristic of polypropylene elastomer blend

Component	Unit	E1	E2	E3	CE1	CE2
							MFR 2(230℃)	[gram/10 minutes]	92	100	80	86	75
Tensile modulus	[MPa]	1330	1450	1860	1060	1680
							Resistance to impact shock+23 ℃	[kJ/m 2]	5.2	4.1	4.0	4.1	4.5
Resistance to impact shock-20 ℃	[kJ/m 2]	2.0	1.6	2.0	2.0	2.0
							Expose energy+23 ℃	[J]	19	18	12	6	12
Expose energy-20 ℃	[J]	10	9	4	1.3	4
							Radial shrinkage ratio	[%]	1.0	1.3	0.9	1.1	0.9
Tangential shrinking percentage	[%]	1.1	1.4	0.9	1.1	1.0

Although work embodiment shows similar melt flow rate (MFR) with comparative example, according to the Charpy resistance to impact shock that at room temperature demonstrates the rigidity levels of remarkable improvement and improve a little based on the three polyacrylic work embodiment in peak of the present invention.More obviously improve by using three peak matrixes to expose energy, the energy of exposing with elastomeric blend is more than expose energy three times of business object of reference.

Claims (16)

1. a heterophasic propylene copolymers (HECO), it comprises

(a) be the matrix (M) of polypropylene (PP), described polypropylene (PP) comprises at least three kinds of polypropylene parts (PP1), (PP2) and (PP3), described three kinds of polypropylene parts (PP1), (PP2) and (PP3) at the melt flow rate (MFR) MFR measured according to ISO1133 ₂(230 ℃) aspect differs from one another,

With

(b) be dispersed in the elastomerics (E) in described matrix (M), wherein the weight package based on described heterophasic propylene copolymers (HECO) is containing the described elastomerics (E) of 20 % by weight or more amount.

2. heterophasic propylene copolymers according to claim 1 (HECO), wherein said heterophasic propylene copolymers (HECO) has the melt flow rate (MFR) MFR of at least 50 gram/10 minute measured according to ISO1133 ₂(230 ℃).

3. heterophasic propylene copolymers according to claim 1 and 2 (HECO), wherein said polypropylene part (PP1), (PP2) and (PP3) at least one be alfon, preferably, wherein said polypropylene part (PP1), (PP2) and (PP3) at least two kinds be alfon, more preferably, wherein said polypropylene part (PP1), (PP2) and (PP3) be alfon.

4. according to heterophasic propylene copolymers in any one of the preceding claims wherein (HECO), wherein

(a) the first polypropylene part (PP1) has according to measured 80 grams/10 minutes to 500 grams/10 minutes of ISO1133, the melt flow rate (MFR) MFR of preferably 250 grams/10 minutes to 450 grams/10 minutes ₂(230 ℃), and/or

(b) the second polypropylene part (PP2) has according to measured 20 grams/10 minutes to 300 grams/10 minutes of ISO1133, the melt flow rate (MFR) MFR of preferably 100 grams/10 minutes to 200 grams/10 minutes ₂(230 ℃), and/or

(c) tripropylene part (PP3) has according to measured 1 gram/10 minutes to 15 grams/10 minutes of ISO1133, the melt flow rate (MFR) MFR of preferably 2.0 grams/10 minutes to 12.0 grams/10 minutes ₂(230 ℃).

5. according to heterophasic propylene copolymers in any one of the preceding claims wherein (HECO), wherein said polypropylene (PP) comprises

(a) gross weight 20.0 % by weight based on described matrix (M) are to the first polypropylene part (PP1) of the amount of 55 % by weight, and/or

(b) gross weight 20 % by weight based on described matrix (M) are to the second polypropylene part (PP2) of the amount of 55 % by weight, and/or

(c) gross weight 10 % by weight based on described matrix (M) are to the tripropylene part (PP3) of the amount of 30 % by weight.

6. according to heterophasic propylene copolymers in any one of the preceding claims wherein (HECO), wherein said elastomerics (E)

(a) there is the melt flow rate (MFR) MFR of 10 gram/10 minute to 80 gram/10 minute measured according to ISO1133 ₂(190 ℃), and/or

(b) there is the limiting viscosity number of 0.7dl/g to 2.5dl/g, and/or

(c) gross weight based on described heterophasic propylene copolymers (HECO), is included in described heterophasic propylene copolymers (HECO) to the amount of 50 % by weight with 20 % by weight, and/or

(d) have lower than 940kg/m ³density.

7. according to heterophasic propylene copolymers in any one of the preceding claims wherein (HECO), the Toughening Effect of Ethylene Copolymer Elastomer of wherein said elastomerics (E) for comprising ethylene monomer unit and comonomer unit, wherein said comonomer is selected from C ₃to C ₂₀alpha-olefin, preferably propylene, 1-butylene, 1-hexene and 1-octene; Or C ₅to C ₂₀α, ω-diolefine, preferably wherein said comonomer is selected from propylene, 1-butylene, 1-hexene, 1-octene and 1,7-octadiene.

8. according to heterophasic propylene copolymers in any one of the preceding claims wherein (HECO), wherein said polypropylene (PP) has the cold solvend of dimethylbenzene (XCS) part that is equal to or less than 3.5 % by weight.

9. according to heterophasic propylene copolymers in any one of the preceding claims wherein (HECO), wherein said three kinds of polypropylene parts (PP1), (PP2) and (PP3) in each all there is the cold solvend of dimethylbenzene (XCS) content that is equal to or less than 4.0 % by weight.

10. according to heterophasic propylene copolymers in any one of the preceding claims wherein (HECO), wherein said heterophasic propylene copolymers (HECO) also comprises

(a) high density polyethylene(HDPE) (HDPE)

And/or

(b) mineral filler (F).

11. 1 kinds for the preparation of according to the method for heterophasic propylene copolymers in any one of the preceding claims wherein (HECO), and it comprises the following steps:

By matrix (M) and elastomerics (E) and optional high density polyethylene(HDPE) (HDPE) and mineral filler (F) blend.

12. methods for the preparation of heterophasic propylene copolymers (HECO) according to claim 11, it is further comprising the steps of:

(PP1), (PP2) and a kind of polypropylene part (PP3) and the mixture blend that contains all the other two kinds of polypropylene parts will be selected from.

13. according to the method for the preparation of heterophasic propylene copolymers (HECO) described in claim 11 or 12, and it is further comprising the steps of:

(a) by a kind of polypropylene part that is selected from (PP1), (PP2) and (PP3) from be selected from (PP1), polypropylene part blend that (PP2) is different with another kind (PP3), then add (PP1), (PP2) and remaining part (PP3), or

(b) by described polypropylene part (PP1), (PP2) and (PP3) blend each other.

14. methods for the preparation of heterophasic propylene copolymers (HECO) according to claim 12, it is further comprising the steps of:

(a1) in the first reactor (R1), make propylene and optionally at least one ethene and/or C ₄to C ₁₂alpha-olefine polymerizing, obtain the first polypropylene part (PP1),

(b1) described the first polypropylene part (PP1) is transferred in the second reactor (R2),

(c1), in described the second reactor (R2) and under the existence of described the first polypropylene part (PP1), make propylene and optionally at least one ethene and/or C ₄to C ₁₂alpha-olefine polymerizing, thereby obtain the second polypropylene part (PP2), described the first polypropylene part (PP1) is mixed with described the second polypropylene part (PP2),

(d1) mixture of step (c1) is transferred in the 3rd reactor (R3),

(e1), in described the 3rd reactor (R3) and under the existence of the mixture obtaining, make propylene and optionally at least one ethene and/or C in step (c1) ₄to C ₁₂alpha-olefine polymerizing, thereby obtain tripropylene part (PP3), wherein said the first polypropylene part (PP1), described the second polypropylene part (PP2) and described tripropylene part (PP3) be mixed with each other and form polypropylene (PP);

Or

(a2) in the first reactor (R1), make propylene and optionally at least one ethene and/or C ₄to C ₁₂alpha-olefine polymerizing, obtain the first polypropylene part (PP1),

(b2) described the first polypropylene part (PP1) is transferred in the second reactor (R2),

(c2), in described the second reactor (R2) and under the existence of described the first polypropylene part (PP1), make propylene and optionally at least one ethene and/or C ₄to C ₁₂alpha-olefine polymerizing, thereby obtain tripropylene part (PP3), described the first polypropylene part (PP1) is mixed with described tripropylene part (PP3),

(d2) mixture of step (c2) is transferred in the 3rd reactor (R3),

(e2), in described the 3rd reactor (R3) and under the existence of the mixture obtaining, make propylene and optionally at least one ethene and/or C in step (c2) ₄to C ₁₂alpha-olefine polymerizing, thereby obtain the second polypropylene part (PP2), wherein said the first polypropylene part (PP1), described the second polypropylene part (PP2) and described tripropylene part (PP3) be mixed with each other and form polypropylene (PP);

Or

(a3) in the first reactor (R1), make propylene and optionally at least one ethene and/or C ₄to C ₁₂alpha-olefine polymerizing, obtain the second polypropylene part (PP2),

(b3) described the second polypropylene part (PP2) is transferred in the second reactor (R2),

(c3), in described the second reactor (R2) and under the existence of described the second polypropylene part (PP2), make propylene and optionally at least one ethene and/or C ₄to C ₁₂alpha-olefine polymerizing, thereby obtain tripropylene part (PP3), described the second polypropylene part (PP2) is mixed with described tripropylene part (PP3),

(d3) mixture of step (c3) is transferred in the 3rd reactor (R3),

(e3), in described the 3rd reactor (R3) and under the existence of the mixture obtaining, make propylene and optionally at least one ethene and/or C in step (c3) ₄to C ₁₂alpha-olefine polymerizing, thereby obtain the first polypropylene part (PP1), wherein said the first polypropylene part (PP1), described the second polypropylene part (PP2) and described tripropylene part (PP3) be mixed with each other and form polypropylene (PP);

Or

(a4) in the first reactor (R1), make propylene and optionally at least one ethene and/or C ₄to C ₁₂alpha-olefine polymerizing, obtain the second polypropylene part (PP2),

(b4) described the second polypropylene part (PP2) is transferred in the second reactor (R2),

(c4), in described the second reactor (R2) and under the existence of described the second polypropylene part (PP2), make propylene and optionally at least one ethene and/or C ₄to C ₁₂alpha-olefine polymerizing, thereby obtain the first polypropylene part (PP1), described the second polypropylene part (PP2) is mixed with described the first polypropylene part (PP1),

(d4) mixture of step (c4) is transferred in the 3rd reactor (R3),

(e4), in described the 3rd reactor (R3) and under the existence of the mixture obtaining, make propylene and optionally at least one ethene and/or C in step (c4) ₄to C ₁₂alpha-olefine polymerizing, thereby obtain tripropylene part (PP3), wherein said the first polypropylene part (PP1), described the second polypropylene part (PP2) and described tripropylene part (PP3) be mixed with each other and form polypropylene (PP);

Or

(a5) in the first reactor (R1), make propylene and optionally at least one ethene and/or C ₄to C ₁₂alpha-olefine polymerizing, obtain tripropylene part (PP3),

(b5) described tripropylene part (PP3) is transferred in the second reactor (R2),

(c5), in described the second reactor (R2) and under the existence of described tripropylene part (PP3), make propylene and optionally at least one ethene and/or C ₄to C ₁₂alpha-olefine polymerizing, thereby obtain the first polypropylene part (PP1), described tripropylene part (PP3) is mixed with described the first polypropylene part (PP1),

(d5) mixture of step (c5) is transferred in the 3rd reactor (R3),

(e5), in described the 3rd reactor (R3) and under the existence of the mixture obtaining, make propylene and optionally at least one ethene and/or C in step (c5) ₄to C ₁₂alpha-olefine polymerizing, thereby obtain the second polypropylene part (PP2), wherein said the first polypropylene part (PP1), described the second polypropylene part (PP2) and described tripropylene part (PP3) be mixed with each other and form polypropylene (PP);

Or

(a6) in the first reactor (R1), make propylene and optionally at least one ethene and/or C ₄to C ₁₂alpha-olefine polymerizing, obtain tripropylene part (PP3),

(b6) described tripropylene part (PP3) is transferred in the second reactor (R2),

(c6), in described the second reactor (R2) and under the existence of described tripropylene part (PP3), make propylene and optionally at least one ethene and/or C ₄to C ₁₂alpha-olefine polymerizing, thereby obtain the second polypropylene part (PP2), described tripropylene part (PP3) is mixed with described the second polypropylene part (PP2),

(d6) mixture of step (c6) is transferred in the 3rd reactor (R3),

(e6), in described the 3rd reactor (R3) and under the existence of the mixture obtaining, make propylene and optionally at least one ethene and/or C in step (c6) ₄to C ₁₂alpha-olefine polymerizing, thereby obtain the first polypropylene part (PP1), wherein said the first polypropylene part (PP1), described the second polypropylene part (PP2) and described tripropylene part (PP3) be mixed with each other and form polypropylene (PP).

15. 1 kinds of goods, it comprises according to the heterophasic propylene copolymers described in any one in claim 1 to 10 (HECO).

16. according to the heterophasic propylene copolymers described in any one in claim 1 to 10 (HECO) purposes in road vehicle application.