CN103827200B - There is the heterophasic propylene copolymers of excellent rigidity and shock resistance balance - Google Patents

Abstract

A kind of heterophasic propylene copolymers (HECO), it comprises the matrix (M) that (a) is 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 ISO1133₂(230 DEG C) aspect differs from one another, (b) be dispersed in the elastomer (E) in described matrix (M), wherein the weight package based on described heterophasic propylene copolymers (HECO) is containing the described elastomer (E) of 20 % by weight or more amount.

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 wherein and dividesWhat fall apart flexible precursor copolymer is the matrix of Noblen or atactic propene copolymer. Therefore, polypropylene matrix contains (essenceWhat carefully) disperse is not the inclusion of a part for matrix, and described inclusion contains elastomer. Term inclusion represents matrixIn heterophasic propylene copolymers, form different phases with inclusion, described inclusion is for example by high-resolution microscope, as electronicsMicroscope or scanning force microscopy are visible.

Thin thickness and light weight are the market demands continuously, and this is because it allows the joint of energy and materialEconomize. For the material with these features is provided, need exploitation to there is the high rigid material of excellent impact resistance energy. Flow with heightThe high rigidity that property combines 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 fluidity material. In addition, becauseReaching the required certain stiffness of the sample demoulding shorter cool time, is possible so shorten circulation timei. But, shock resistancePerformance need remains on high level. High fluidity material is conventionally owing to having showing compared with short polymer chain of less three-dimensional defectShow high rigidity. But shock resistance is owing to forming reducing compared with short polymer chain of less entanglement. Therefore, acquisition hasThe material of high fluidity and rigidity and excellent impact resistance energy is a challenge.

In addition, can distinguish twin shaft impact strength and three axle impact strengths. Although at heterogeneous system, as heterophasic propyleneIn copolymer (HECO), both depend on strongly form, the impact strength that still increases by two types is all quite to haveChallenging. This is due to the fact that they show optimum efficiency at different particle diameters. Especially in little fine dispersionUnder particle, improve the impact strength (exposing energy) under biaxial stress state. This can come by low-molecular-weight rubber realExisting. But this rubber is disadvantageous to the impact strength under triaxial state of stress (Charpy impact strength).

Adopt three peak matrix designs to obtain having the propylene of excellent stiffness, and obtain showing that outstanding shock resistance-rigidity is flatThe heterophasic copolymer of weighing apparatus. This good shock resistance-rigidity balance is considered to obtain based on the HMW part by matrixThe fine dispersion of rubber phase. But, this design is applied to the heterophasic propylene copolymers (HECO) with high rubber contentNot known, although they are necessary for road vehicle application.

Therefore, an object of the present invention is to obtain the material with high fluidity and rigidity and excellent impact resistance energyMaterial. Particularly, an object of the present invention is to obtain and there is high fluidity, high rigidity, height and expose energy and high Charpy anti-impactThe material of hit intensity.

One of the present invention is found to be a kind of heterophasic propylene copolymers is provided, and it contains the base with wide molecular weight distributionThe elastomer of body and quite high amount, described elastomer preferably has quite low intrinsic viscosity.

Therefore, the application relates to a kind of heterophasic propylene copolymers (HECO), and it comprises: be (a) matrix of polypropylene (PP)(M), wherein said polypropylene (PP) comprises at least three kinds of polypropylene parts (PP1), (PP2) and (PP3), described three kinds of polypropylenePartly (PP1), (PP2) and (PP3) at the melt flow rate (MFR) MFR measured according to ISO1133₂(230 DEG C) aspect is not each otherWith; (b) be dispersed in the elastomer (E) in described matrix (M), the wherein weight based on described heterophasic propylene copolymers (HECO)Comprise described elastomer (E) with 20 % by weight or more amount; Optionally a small amount of polyethylene (PE) and optionally inorganic filler (F).

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

The invention still further relates to a kind of comprising as the goods of the above heterophasic propylene copolymers limiting (HECO), and described manyThe especially purposes in road vehicle application of phase propylene copolymer (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 it according to heterophasic propylene copolymers of the present invention (HECO)In elastomer (E). Therefore, what polypropylene (PP) matrix contained (meticulous) dispersion is not the inclusion of a part for matrix (M),And described inclusion contains elastomer (E), and optionally can also contain a small amount of crystalline polyethylene (PE). Term inclusion tableShow that matrix (M) forms different phases in heterophasic propylene copolymers (HECO) with inclusion, described inclusion for example passes through high scoreDistinguish microscope, if electron microscope or scanning force microscopy are visible.

Preferably, only comprise polypropylene (PP) and elastomer (E) work according to heterophasic propylene copolymers of the present invention (HECO)For polymers compositions. In other words, heterophasic propylene copolymers (HECO) can also contain additive, but preferred an enforcementIn scheme, do not exceed 8.0 % by weight containing the gross weight based on heterophasic propylene copolymers (HECO), more preferably exceed 6.0 % by weightOther polymer of amount. A kind of other polymer that can exist taking low amount like this is as fully mixing with elastomer (E)Polyethylene (PE), elastomer (E) and optionally polyethylene (PE) in matrix (M), form inclusion. Therefore, answered especiallySeparate, heterophasic propylene copolymers of the present invention (HECO) only contains polypropylene (PP) (being matrix (M)), elastomer (E) and optionallyA small amount of polyethylene (PE) is as only polymers compositions.

Of the present invention one preferred aspect in, heterophasic propylene copolymers (HECO) is characterised in that quite high meltFlow rate. Melt flow rate (MFR) depends primarily on mean molecule quantity. This is because long molecule is compared short molecule material is hadLower flow tendency. Molecular weight increase means that MFR value reduces. Melt flow rate (MFR) (MFR) is temperature and the pressure in regulationUnder power condition by limit polymer that mouthful mould discharges in gram/10 minutes measured, and be measuring of polymer viscosity,And its viscosity is affected by its molecular weight and degree of branching mainly for every kind of polymer. 230 DEG C and 2.16kg loadUnder (ISO1133) measure melt flow rate (MFR) be expressed as MFR₂(230 DEG C). Therefore, in the present invention preferably heterogeneous thirdAlkene copolymer (HECO) has and is equal to or greater than 50 grams/10 minutes, is more preferably equal to or greater than 70.0 grams/10 minutes, still more excellentBe selected within the scope of 70.0 grams/10 minutes to 200.0 grams/10 minutes, as 75.0 grams/10 minutes to 180.0 grams/10 minutes scopesInterior MFR₂(230℃)。

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

The dimethylbenzene of elastomer (E) the formation heterophasic propylene copolymers (HECO) of heterophasic propylene copolymers (HECO) is cold solvableThe major part of thing part. Therefore, quite approx, the cold DDGS of dimethylbenzene (XCS) portion of heterophasic propylene copolymers (HECO)Divide elastomer (E) content that can be equal to heterophasic propylene copolymers (HECO). Therefore, based on heterophasic propylene copolymers(HECO), the cold DDGS 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 weightIn the scope of 35 % by weight.

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

(i) at least 1100MPa measured according to ISO527-2, more preferably 1200MPa at least, still more preferably exists1100MPa within the scope of 2500MPa, as at 1200MPa to the stretch modulus within the scope of 2200MPa,

And/or

(ii) according to ISO179 (1eA; 23 DEG C) measured at least 3.5kJ/m², more preferably 4.5kJ/m at least², still more excellentBe selected in 4.0kJ/m²To 10kJ/m²In scope, as at 4.0kJ/m²To 8.0kJ/m²Charpy breach shock resistance in scope is strongDegree,

And/or

(iii) according to ISO179 (1eA;-20 DEG C) measured at least 1.0kJ/m², more preferably 1.2kJ/m at least², still morePreferably at 1.5kJ/m²To 5.0kJ/m²Charpy breach impact strength in scope,

And/or

(iv) according to ISO6603-2 use 60 × 60 × 2mm moulding with instrument drop hammer (IFW) test determine at least6J, more preferably 12J at least, still more preferably at 8J within the scope of 28J, as at 12J to exposing energy (+23 DEG C) 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 least3J, more preferably 7J at least, still more preferably at 5J within the scope of 18J, as at 7J to exposing energy (20 DEG C) 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 elastomer(E)。

As mentioned above, matrix (M) is polypropylene (PP), and more preferably atactic propene copolymer (R-PP) or propylene are equalPolymers (H-PP), especially preferably Noblen (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 weightAmount %, still more preferably no more than 0.5 % by weight. The gross weight of above percentage by weight based on polypropylene (PP).

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

The statement Noblen using in full in the present invention relates to the polypropylene being substantially made up of propylene units,The polypropylene being formed by the propylene units that is equal to or less than 99.5 % by weight. In a preferred embodiment, NoblenIn propylene units only can be detected. Co-monomer content is determined by the FT infra-red sepectrometry 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 C₄To C₁₂Alpha-olefin, particularly ethene and/Or C₄To C₈Alpha-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 be selected from ethene, 1-butylene and 1-oneselfCan forming with the monomer of copolymerization of propylene of alkene. More specifically, atactic propene copolymer of the present invention (R-PP) is except propyleneAlso comprise the unit of derived from ethylene and/or 1-butylene. In a preferred embodiment, atactic propene copolymer (R-PP)Only comprise 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 to 2.0 % by weight modelsIn enclosing, be more preferably greater than 0.1 % by weight within the scope of 1.6 % by weight, also more preferably in 0.1 % by weight within the scope of 1.0 % by weightCo-monomer content. The gross weight of above percentage by weight based on atactic propene copolymer (R-PP).

Term " random " represents propylene copolymer (R-PP) and the first atactic propene copolymer (R-PP1), second randomComonomer random distribution in propylene copolymer of propylene 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 30.0Gram/10 minutes to 500.0 grams/10 minutes within the scope of, 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 minutes₂(230℃)。

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

In addition, polypropylene (PP) can be limited by its molecular weight. Therefore should be appreciated that, polypropylene (PP) has the gel of passing throughPermeation chromatography (GPC; ISO16014-4:2003) measured 175 kg/mol that are equal to or less than, are more preferably equal to or less than165 kg/mol, also more preferably in 75 kg/mol within the scope of 160 kg/mol, still more preferably in 80 kg/molTo the weight average molecular weight (Mw) within the scope of 150 kg/mol.

The cold DDGS of dimethylbenzene (XCS) content of polypropylene (PP) is quite moderate. Therefore, the cold DDGS 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 arrives in 0.5 % by weightIn the scope of 3.0 % by weight, as in 0.5 % by weight in the scope of 2.8 % by weight. Above percentage by weight is based on polypropylene (PP)Gross weight.

As mentioned above, polypropylene (PP) comprises at least three kinds, more preferably comprises three kinds of polypropylene parts (PP1), (PP2)(PP3), also more preferably form described three kinds of polypropylene parts by three kinds of polypropylene parts (PP1), (PP2) with (PP3)(PP1), (PP2) and (PP3) at the melt flow rate (MFR) MFR measured according to ISO1133₂(230 DEG C) aspect differs from one another.

In a preferred embodiment, the first polypropylene part (PP1) have according to ISO1133 measured 80Gram/10 minutes to 500 grams/10 minutes, more preferably 150 grams/10 minutes to 480 grams/10 minutes, also more preferably 200 grams/10 minutesBy 450 grams/10 minutes, the still more preferably melt flow rate (MFR) MFR of 250 grams/10 minutes to 450 grams/10 minutes₂(230℃)。

In addition, the second polypropylene part (PP2) preferably has according to measured 20 grams/10 minutes of ISO1133 to 300Gram/10 minutes, 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 minutes₂(230℃)。

In addition, polypropylene part (PP3) preferably has according to measured 1 gram/10 minutes of ISO1133 to 15 grams/10Minute, more preferably 2 grams/10 minutes to 15 grams/10 minutes, also more preferably 2 grams/10 minutes to 12 grams/10 minutes, still more preferably 3Gram/the melt flow rate (MFR) MFR of 10 minutes to 10 grams/10 minutes₂(230℃)。

Preferably, melt flow rate (MFR) MFR₂(230 DEG C) are from the first polypropylene part (PP1) to tripropylene part(PP3) reduce. Therefore, the melt flow rate (MFR) MFR of the first polypropylene part (PP1) and tripropylene part (PP3)₂(230DEG C) ratio [MFR (PP1)/MFR (PP3)] be preferably at least 10, more preferably at least 20, also more preferably at least 30, as 30 to 60Scope in, and/or the melt flow rate (MFR) MFR of the second polypropylene part (PP2) and tripropylene part (PP3)₂(230DEG C) ratio [MFR (PP2)/MFR (PP3)] be preferably at least 5, more preferably at least 7, also more preferably at least 10.

In another preferred embodiment, melt flow rate (MFR) MFR₂(230 DEG C) from the first polypropylene part (PP1) toThe second polypropylene part (PP2) reduces, and reduces to tripropylene part (PP3) from the second polypropylene part (PP2). CauseThis, the second polypropylene part (PP2) preferably has than the low melt flow rate (MFR) MFR of the first polypropylene part (PP1)₂(230DEG C), 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,More preferably minimum melt flow rate (MFR) MFR in all polymer that exist in polypropylene (PP)₂(230℃)。

Preferably, polypropylene part (PP1), (PP2) and (PP3) at least one be Noblen, even more excellentSelection of land, all polypropylene parts (PP1), (PP2) and (PP3) be all Noblen.

Therefore, in a preferred embodiment, the matrix (M) of heterophasic propylene copolymers (HECO), i.e. polypropylene(PP) comprise

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

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

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

Prerequisite be at least one in three kinds of part PP1, PP2 and PP3 for Noblen, preferably at least the first poly-thirdAlkene part (PP1) is Noblen, more preferably whole three kinds of parts (PP1), (PP2) and (PP3) be all Noblen.

As mentioned above, particularly preferably, at least the first polypropylene part (PP1) is Noblen, so-calledThe first Noblen (H-PP1). Even more preferably, this first polypropylene part (PP1) has three kinds of polypropylene(PP1), (PP2) and (PP3) in the highest melt flow rate (MFR) MFR₂(230℃)。

Still more preferably, except the first polypropylene part (PP1), the second polypropylene part (PP2) or trimerization thirdAlkene part (PP3) is also Noblen. In other words, preferably, it is atactic propene copolymerization that polypropylene (PP) only comprises a kind ofThe polypropylene part of thing, is preferably only made up of a kind of polypropylene part for atactic propene copolymer. Therefore, the second polypropylenePartly (PP2) is Noblen, i.e. so-called the second Noblen (H-PP2), or tripropylene part (PP3) is thirdPolyamino alkenyl thing, i.e. so-called the 3rd Noblen (H-PP3).

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

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 propyleneHomopolymers. Under any circumstance, each co-monomer content for polypropylene part (PP1), (PP2) and (PP3) allShould be quite low. Therefore, three kinds of polypropylene parts (PP1), (PP2) and (PP3) in each co-monomer content all littleIn 1.0 % by weight, also more preferably no more than 0.8 % by weight, still more preferably no more than 0.5 % by weight. In atactic propene copolymer part(R-PP1), in (R-PP2) and situation (R-PP3), should be appreciated that, for atactic propene copolymer part (R-PP1), (R-PP2)(R-PP3) co-monomer content of each in is being greater than 0.2 % by weight in the scope of 3.0 % by weight, more preferably greatlyIn 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. Above weight hundredThe weight of proportion by subtraction 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 copolymerization listBody, as ethene and/or C₄To C₁₂Alpha-olefin, particularly ethene and/or C₄To C₈Alpha-olefin, for example 1-butylene and/or 1-oneselfAlkene. Preferably, (R-PP1), (R-PP2) and (R-PP3) comprise be independently of one another selected from ethene, 1-butylene and 1-hexene can be withThe monomer of copolymerization of propylene, especially independently of one another can be with copolymerization of propylene by what be selected from ethene, 1-butylene and 1-hexeneMonomer forms. More specifically, (R-PP1), (R-PP2) and (R-PP3) also comprise independently of one another derived from second except propyleneThe unit of alkene and/or 1-butylene. In a preferred embodiment, (R-PP1), (R-PP2) and (R-PP3) except propyleneThere is identical comonomer. Therefore, in an especially preferred embodiment, (R-PP1), (R-PP2) and (R-PP3) onlyThe unit that comprises derived from ethylene and propylene.

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

The cold DDGS of dimethylbenzene (XCS) content of the first polypropylene part (PP1) is preferably equal to or less than 4.0 % by weight, morePreferably 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 to 3.0In the scope of % by weight. The weight of above percentage by weight 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) MFR₂(230DEG C). Therefore should be appreciated that the melt flow rate (MFR) MFR measured according to ISO1133₂(230 DEG C) are equal to or greater than 80 grams/10 pointsClock, is preferably 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 morePreferably in the scope of 150 grams/10 minutes to 480 grams/10 minutes, also more preferably at 200 grams/10 minutes to 450 grams/10 minutesScope in, 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 firstPolypropylene part (PP1) has by gel permeation chromatography (GPC; ISO16014-4:2003) be measuredly equal to or less than 130Kg/mol, is more preferably equal to or less than 110 kg/mol, also more preferably in 72 kg/mol to 110 kg/mol modelsIn enclosing, 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 Noblen part (the second Noblen part (H-PP2)), preferred Noblen part (the second propyleneHomopolymers part (H-PP2)).

The cold DDGS of dimethylbenzene (XCS) content of the second polypropylene part (PP2) is preferably equal to or less than 4.0 % by weight, morePreferably 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 to 3.0In the scope of % by weight. The weight of above percentage by weight based on the second polypropylene part (PP2).

As mentioned above, the second polypropylene part (PP2) has than the high melt flow rate (MFR) of tripropylene part (PP3)MFR₂(230 DEG C). On the other hand, the melt flow rate (MFR) MFR of the first polypropylene part (PP1)₂(230 DEG C) can higher than or etc.In, preferably higher than the melt flow rate (MFR) MFR of the second polypropylene part (PP2)₂(230 DEG C). Therefore should be appreciated that the second polypropylenePartly (PP2) have according to ISO1133 measured within the scope of 20 grams/10 minutes to 300 grams/10 minutes, preferably 50 grams/Within the scope of 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, also more excellentBe selected in the melt flow rate (MFR) MFR within the scope of 100 grams/10 minutes to 200 grams/10 minutes₂(230℃)。

Tripropylene part (PP3) can be atactic propene copolymer part (the 3rd atactic propene copolymer part (R-PP3)) or Noblen part (the 3rd Noblen part (H-PP3)), preferred Noblen part (the 3rd propyleneHomopolymers part (H-PP3)).

The cold DDGS of dimethylbenzene (XCS) content of tripropylene part (PP3) is preferably equal to or less than 4.0 % by weight, morePreferably 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 to 3.0In the scope of % by weight. The weight of above percentage by weight based on tripropylene part (PP3).

As mentioned above, tripropylene (PP3) preferably have three kinds of polypropylene parts (PP1), (PP2) and (PP3) inMinimum melt flow rate (MFR) MFR₂(230 DEG C), more preferably have in the polymer moieties existing in polypropylene (PP) minimumMelt flow rate (MFR) MFR₂(230 DEG C). Therefore should be appreciated that, tripropylene (PP3) have according to ISO1133 measuredWithin 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, stillMore preferably within the scope of 2.0 grams/10 minutes to 12.0 grams/10 minutes, as the melt flows of 3 grams/10 minutes to 10 grams/10 minutesSpeed MFR₂(230℃)。

If various piece, specifically to measure and to exist, can obtain fabulous result so. Therefore preferably, according toThe melt flow rate (MFR) MFR that ISO1133 is measured₂(230 DEG C) are (excellent within the scope of 1.0 grams/10 minutes to 15.0 grams/10 minutesBe selected within the scope of 2.0 grams/10 minutes to 15.0 grams/10 minutes, still more preferably at 2.0 grams/10 minutes to 12.0 grams/10 minutes modelsEnclose in) melt flow rate (MFR) MFR₂The amount of (230 DEG C) polypropylene part, preferably the amount of tripropylene part (PP3) is 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 to 25In the scope of % 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 ISO1133₂(230 DEG C) were at 80.0 grams/10 minutesTo the amount of the polypropylene part within the scope of 500.0 grams/10 minutes, preferably the amount of the first polypropylene part (PP1) arrives in 20 % by weightIn the scope of 55 % by weight, preferably in 25 % by weight in the scope of 45 % by weight, the more preferably scope to 45 % by weight in 30 % by weightIn, 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 remainder, preferably the second polypropylene portionPoint (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 30% by weight is in the scope of 45 % by weight, and still more preferably 35 % by weight exist to the amount of 45 % by weight. Above numerical value is based on matrix (M),Be 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 ISO1133₂(230DEG C) polypropylene part within the scope of 1.0 grams/10 minutes to 15.0 grams/10 minutes, preferably tripropylene part (PP3)With the melt flow rate (MFR) MFR measured according to ISO1133₂(230 DEG C) were at 80.0 grams/10 minutes to 500.0 grams/10 minutes modelsPolypropylene part in enclosing, preferably the weight ratio [PP3/PP1] of the first polypropylene part (PP1) is at 10/45 to 25/30 modelIn enclosing, more preferably in 1/3 to 5/7 scope.

Can obtain extraordinary result, prerequisite is based on the first polypropylene part (PP1), the second polypropylene part(PP2) and the total amount of tripropylene part (PP3), 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 retouched in detail belowState. Therefore, three kinds of polypropylene parts (PP1), (PP2) and (PP3) be homogeneous mixture, this is to obtain by mechanical blendingArrive. In another embodiment, polypropylene (PP) by by polypropylene part (PP1), (PP2) and (PP3) blend obtain.

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

As mentioned above, the diformazan of the final heterophasic propylene copolymers of performance major effect (HECO) of elastomer (E)The cold DDGS of benzene (XCS). In other words, the performance limiting for elastomer (E) below is equally applicable to heterophasic propylene copolymerizationThe cold DDGS of dimethylbenzene (XCS) part of thing (HECO).

Described elastomer can be any elastomer. But, in a preferred embodiment of the invention, elastomer(E) Toughening Effect of Ethylene Copolymer Elastomer for comprising ethylene monomer unit and comonomer unit, wherein said comonomer is selected from C₃To C₂₀Alpha-olefin, preferably propylene, 1-butylene, 1-hexene and 1-octene; Or C₅To C₂₀α, ω-alkadienes, preferably 1,7-is pungentDiene. In a preferred embodiment, comonomer is selected from propylene, 1-butylene, 1-hexene and 1-octene, especially preferred1-octene.

In one embodiment, elastomer (E) has according to measured 10 grams/10 minutes of ISO1133 to 80 grams/10Minute melt flow rate (MFR) MFR₂(190 DEG C). More preferably, elastomer (E) has 15 grams/10 minutes to 70 grams/10 minutes,Still more preferably 20 grams/10 minutes to 60 grams/10 minutes, the also more preferably melt flows speed of 20 grams/10 minutes to 50 grams/10 minutesRate MFR₂(190℃)。

In another preferred embodiment, elastomer (E) has 0.7dl/g to 2.5dl/g, and preferably 0.8dl/g arrives2.0dl/g, more preferably 0.8dl/g is to the intrinsic viscosity of 1.5dl/g. Intrinsic viscosity is according to DINISO1628/1, in October, 1999(at 135 DEG C in naphthalane) are measured.

In addition, elastomer (E) preferably has lower than 940kg/m³, more preferably 920kg/m³Or lower, still more preferably exist850kg/m³To 920kg/m³In scope, also more preferably at 860kg/m³To 910kg/m³Density 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 elastomer 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), preferably based on matrix (M) be polypropylene (PP) andElastomer (E) weight together, elastomer (E) is to be equal to or greater than the amount of 20.0 % by weight, more preferably to be equal to or greater than20.0 % by weight, to the amount of 50.0 % by weight, are also more preferably present in heterophasic propylene altogether with 25.0 % by weight to the amount of 40.0 % by weightIn polymers (HECO).

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

Therefore, preferably, based on heterophasic propylene copolymers (HECO), preferably based on polypropylene (PP) and elastomer (E)Total amount, 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 75.0 weightsThe matrix (M) of amount %, 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, and still more preferably 25.0 % by weight arriveThe elastomer (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 "Represent that polyethylene (PE) is different from elastomer (E). Polyethylene (PE) be crystallization and be insoluble to cold xylene, and elastomer(E) be mainly amorphous and be dissolved in thus cold xylene. In a preferred embodiment, polyethylene (PE) is highDensity polyethylene (HDPE). 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, preferably 20 grams/10 minutesBy 40 grams/10 minutes, the melt flow rate (MFR) MFR of more preferably 25 grams/10 minutes to 35 grams/10 minutes₂(190℃)。

High density polyethylene (HDPE) (HDPE) generally has at least 940kg/m³, preferably 945kg/m at least³, more preferably at least955kg/m³, still more preferably at 945kg/m³To 970kg/m³In scope, also more preferably at 950kg/m³To 965kg/m³In scopeDensity.

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 arrive 0Within the scope of 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 heterophasic propylene copolymers (HECO)Matrix (M), in polypropylene (PP). More properly, polyethylene (PE), high density polyethylene (HDPE) (HDPE) is abundant with elastomerMix, thereby form the inclusion of heterophasic propylene copolymers (HECO) together with elastomer (E).

Inorganic filler

Except polymers compositions discussed above, based on the gross weight of heterophasic propylene copolymers (HECO), heterogeneousPropylene copolymer (HECO) can also optionally comprise maximum 25 % by weight, and preferably maximum 22 % by weight, more preferably arrive in 4 % by weightWithin the scope of 25 % by weight, still more preferably 5 % by weight to the inorganic filler (F) of the amount of 20 % by weight. Preferably, inorganic filler (F) is pageSilicate, mica or wollastonite. Even more preferably, inorganic filler (F) is selected from mica, wollastonite, kaolinite, smectite, illiteracyDe-stone and talcum. Most preferably, inorganic 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, as2.5 μ m are to the cut-off particle diameter d95[mass percent within the scope of 8.0 μ m].

Usually, inorganic filler (F) has according to known BET method and utilizes N₂Gas is measured as analyzing adsorbateBe less than 22m²/ g, is more preferably less than 20m²/ g, is also more preferably less than 18m²The surface area of/g. Meet the nothing of these requirementsMachine filler (F) 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 plumper (AS), anti-oxidantAgent (AO), nucleator (NA), hindered amine as light stabilizer (HALS), slipping agent (SA) and pigment. Preferably, of the present invention heterogeneousIn propylene copolymer (HECO), the amount of getting rid of the additive of inorganic filler (F) should be no more than 7 % by weight, more preferably should be no more than5 % 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 65.0 weightsThe matrix (M) of amount %, 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, and still more preferably 25.0 % by weight arriveThe elastomer (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, still more preferably 0 to 6Polyethylene (PE) within the scope of % by weight, preferably high density polyethylene (HDPE) (HDPE),

(d) maximum 25 % by weight, more preferably 4 % by weight are to 25 % by weight, and still more preferably 5 % by weight are filled out to the inorganic of 20 % by weightMaterial (F), 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 molding systemProduct, preferably motor vehicle injection-molded item. Even be more preferably used in and produce automotive interior and external articles, as bumper, return moldings part,Foot-operated servicing unit, body panel, spoiler, instrument board, inner gadget etc., especially bumper.

The present invention also provides (motor vehicle) goods, and as injection-molded item, it comprises at least 60 % by weight, and 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 by of the present invention heterogeneous thirdAlkene copolymer (HECO) forms. Therefore, the invention particularly relates to motor vehicle goods, relate in particular to automotive interior and external articles,As bumper, return moldings part, foot-operated servicing unit, body panel, spoiler, instrument board, inner gadget etc., particularly bumper,It comprises at least 60 % by weight, more preferably at least 70 % by weight, the also more preferably heterophasic propylene copolymerization of the present invention of at least 75 % by weightThing (HECO), 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. At oneIn preferred embodiment, heterophasic propylene copolymers (HECO) uses in 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 by comprising elastomer (E) and matrix (M) blend according to heterophasic propylene copolymers of the present invention (HECO)The method of step prepare. Term " blend " refers to according to the present invention provides at least two kinds of different materials that existedThe action of blend. On the other hand, term " mixing " comprises blend, but is also included under a kind of material existence by making another kindSubstance reaction carrys out original position and forms blend.

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

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

(a1) in the first reactor (R1), make propylene and optionally at least one ethene and/or C₄To C₁₂Alpha-olefines polymerizationClose, 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 propyleneOptionally at least one ethene and/or C₄To C₁₂Alpha-olefine polymerizing, thereby obtain the second polypropylene part (PP2), described inThe 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 in step (c1)Optionally at least one ethene and/or C₄To C₁₂Alpha-olefine polymerizing, thereby obtain tripropylene part (PP3), whereinDescribed the first polypropylene part (PP1), described the second polypropylene part (PP2) and described tripropylene part (PP3) are thoseThis mixing and form polypropylene (PP);

Or

(a2) in the first reactor (R1), make propylene and optionally at least one ethene and/or C₄To C₁₂Alpha-olefines polymerizationClose, 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 propyleneOptionally at least one ethene and/or C₄To C₁₂Alpha-olefine polymerizing, thereby obtain tripropylene part (PP3), described inThe 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 in step (c2)Optionally at least one ethene and/or C₄To C₁₂Alpha-olefine polymerizing, thereby obtain the second polypropylene part (PP2), whereinDescribed the first polypropylene part (PP1), described the second polypropylene part (PP2) and described tripropylene part (PP3) are thoseThis mixing and form polypropylene (PP);

Or

(a3) in the first reactor (R1), make propylene and optionally at least one ethene and/or C₄To C₁₂Alpha-olefines polymerizationClose, 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 propyleneOptionally at least one ethene and/or C₄To C₁₂Alpha-olefine polymerizing, thereby obtain tripropylene part (PP3), described inThe 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 in step (c3)Optionally at least one ethene and/or C₄To C₁₂Alpha-olefine polymerizing, thereby obtain the first polypropylene part (PP1), whereinDescribed the first polypropylene part (PP1), described the second polypropylene part (PP2) and described tripropylene part (PP3) are thoseThis mixing and form polypropylene (PP);

Or

(a4) in the first reactor (R1), make propylene and optionally at least one ethene and/or C₄To C₁₂Alpha-olefines polymerizationClose, 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 propyleneOptionally at least one ethene and/or C₄To C₁₂Alpha-olefine polymerizing, thereby obtain the first polypropylene part (PP1), described inThe 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 in step (c4)Optionally at least one ethene and/or C₄To C₁₂Alpha-olefine polymerizing, thereby obtain tripropylene part (PP3), whereinDescribed the first polypropylene part (PP1), described the second polypropylene part (PP2) and described tripropylene part (PP3) are thoseThis mixing and form polypropylene (PP);

Or

(a5) in the first reactor (R1), make propylene and optionally at least one ethene and/or C₄To C₁₂Alpha-olefines polymerizationClose, 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 propyleneOptionally at least one ethene and/or C₄To C₁₂Alpha-olefine polymerizing, thereby obtain the first polypropylene part (PP1), described inTripropylene 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 in step (c5)Optionally at least one ethene and/or C₄To C₁₂Alpha-olefine polymerizing, thereby obtain the second polypropylene part (PP2), whereinDescribed the first polypropylene part (PP1), described the second polypropylene part (PP2) and described tripropylene part (PP3) are thoseThis mixing and form polypropylene (PP);

Or

(a6) in the first reactor (R1), make propylene and optionally at least one ethene and/or C₄To C₁₂Alpha-olefines polymerizationClose, 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 propyleneOptionally at least one ethene and/or C₄To C₁₂Alpha-olefine polymerizing, thereby obtain the second polypropylene part (PP2), described inTripropylene 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 in step (c6)Optionally at least one ethene and/or C₄To C₁₂Alpha-olefine polymerizing, thereby obtain the first polypropylene part (PP1), whereinDescribed the first polypropylene part (PP1), described the second polypropylene part (PP2) and described tripropylene part (PP3) are thoseThis mixing and form polypropylene (PP).

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

For polypropylene (PP), the first polypropylene part (PP1), the second polypropylene part (PP2) and tripropylene portionDivide the preferred embodiment of (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. CauseThis, this method at least comprises the first reactor (R1), the second reactor (R2) and the 3rd reactor (R3). Term " polymerisationDevice " should represent to occur main polymerization part. Therefore,, if method is made up of four polymer reactors, this definition is not got rid ofWhole method comprises the selection of the prepolymerization step in pre-polymerization reactor for example. Term " by ... form " anti-in main polymerizationAnswering device aspect is only closing form.

The first reactor (R1) is preferably slurry reactor (SR), and can be the arbitrary continuation with body or slurry operationOr the tank reactor or loop reactor at intermittence of simple agitation. Ontology representation is in the reaction that comprises at least 60% (w/w) monomerPolymerization in medium. 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 havingAt least mechanical agitation fluidized-bed reactor of the gas velocity of 0.2m/ second. Therefore should be appreciated that, Gas-phase reactor is for preferably havingThe fluid bed-type of reactor of mechanical agitator.

Therefore, in a preferred embodiment, the first reactor (R1) is slurry reactor (SR), as ring type reactionDevice (LR), and the second reactor (R2) and the 3rd reactor (R3) they are Gas-phase reactor (GPR). Therefore,, for this method, useBe connected in series at least three, preferably three polymer reactors, slurry reactor (SR), as loop reactor (LR), firstGas-phase reactor (GPR-1), and the second Gas-phase reactor (GPR-2). As required, place before in advance at slurry reactor (SR)Polymer reactor.

A kind of preferred multi-stage method is " ring type-gas phase " method, for example, developed by the BorealisA/S of Denmark(be called asTechnology), for example, in patent documentation, as EP0887379, WO92/12182WO2004/000899, described in WO2004/111095, WO99/24478, WO99/24479 or WO00/68315.

Another suitable slurry-gas phase process is BasellMethod.

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

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

-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 molal weight.

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

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

-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 molal weight.

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

In three reactor area, the time of staying can change.

In the embodiment for the preparation of polyacrylic method, bulk reaction device, for example, in loop reactorThe time of staying in the scope of 0.1 hour to 2.5 hours, for example 0.15 hour to 1.5 hours, when stop in Gas-phase reactorBetween 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), i.e. slurry reactor (SR), as surpassed in loop reactor (LR)Under critical condition, carry out polymerization with condensation mode in known manner and/or in Gas-phase reactor (GPR).

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

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

Prepolymerization, generally at 10 DEG C to 60 DEG C, preferably 15 DEG C to 50 DEG C, more preferably enters at the temperature of 20 DEG C to 45 DEG COK.

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

Preferably catalytic component is all incorporated into prepolymerization step. But, when ingredient of solid catalyst (i) with help and urgeWhen agent (ii) can be distinguished charging, can only a part of co-catalyst be incorporated in prepolymerisation stage, remainder is introducedIn follow-up polymerization stage. In addition, in this case, so many co-catalyst must be incorporated in prepolymerisation stageTo make wherein to obtain enough polymerisations.

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

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

According to the present invention, polypropylene (PP) preferably passes through the multistage as above under the existence of catalyst systemPolymerization obtains, and described catalyst system comprises Z-N major catalyst as component (i), described Ziegler-NaThe ester exchange offspring that tower major catalyst contains lower alcohol and phthalic acid ester.

Prepare by following steps according to major catalyst used in the present invention

A) make through spray crystallization or the curing MgCl of emulsion₂And C₁To C₂Adduct and the TiCl of alcohol₄Reaction

B) at described C₁To C₂Alcohol and the condition of the bialkyl ortho phthalate generation ester exchange of formula (I) under make the stageA) product reacts to form internal donor with the bialkyl ortho phthalate of described formula (I)

Wherein R^1’And R^2’Be C at least independently₅Alkyl

C) wash phase product b), or

D) optionally make step product c) and other TiCl₄Reaction.

Major catalyst is as for example in patent application WO87/07620, WO92/19653, WO92/19658 and EP0491566Limit to prepare. The content of these files is included in herein by reference.

First form formula MgCl₂* the MgCl of nROH₂And C₁To C₂The adduct of alcohol, wherein R is that methyl or ethyl and n are1 to 6. Ethanol is preferably as alcohol.

First melting then spray crystallization or the curing adduct of emulsion as catalyst carrier.

In next step, formula MgCl₂* nROH through spray crystallization or curing adduct and the TiCl of emulsion₄Contact is to formTitanizing carrier, wherein R is methyl or ethyl, 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 R¹' and R²' be C at least independently₅Alkyl, as C at least₈Alkyl,

Or preferably

(ii) bialkyl ortho phthalate of formula (I), wherein R^1’And R^2’For identical, and be C at least₅Alkyl, asAt least C₈Alkyl,

Or more preferably

(iii) bialkyl ortho phthalate of formula (I), it is selected from phthalic acid propyl group hexyl ester (PrHP), adjacent benzeneDioctyl phthalate dioctyl ester (DOP), diisooctyl phthalate (DIDP) and phthalic acid two (tridecyl) ester (DTDP), alsoMore preferably the bialkyl ortho phthalate of formula (I) is that dioctyl phthalate (DOP) is as diisooctyl phthalateOr 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 DEG C, preferably at 100 DEG C to 150Between DEG C, the more preferably temperature between 130 DEG C to 150 DEG C, so that the phthalic acid of described methyl alcohol or ethanol and described formula (I)The described ester group of dialkyl carries out ester exchange, to form preferably at least 80 % by mole, and more preferably at least 90 % by mole, most preferablyThe bialkyl ortho phthalate of the formula (II) of at least 95 % by mole

Wherein R¹And R²For methyl or ethyl, preferably ethyl,

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

Reclaim described ester exchange offspring as major catalyst composition (component (i)).

Formula MgCl₂* the adduct of nROH (wherein R is that methyl or ethyl and n are 1 to 6) in a preferred embodimentMelting, then melt preferably by gas inject in cooling solvent or cooling gas, thereby described adduct crystallizationFor the favourable form of form, as for example described in the WO87/07620.

Described at WO92/19658 and WO92/19653, the adduct of this crystallization preferably carries as catalystBody reaction are for can be used for the major catalyst in the present invention.

In the time removing catalyst residue by extraction, obtain the adduct of titanizing carrier and internal donor, wherein sourceGroup in ester alcohol changes.

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

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 major catalyst used in the present invention, preferably 2.2 % by weight at the most, moreThe preferred titanium of 2.0 % by weight at the most. Its donor content preferably in 4 % by weight between 12 % by weight, more preferably arrive in 6 % by weightBetween 10 % by weight.

More preferably, passed through to use ethanol as alcohol and phthalic acid according to major catalyst used in the present inventionDioctyl ester (DOP) is prepared as the bialkyl ortho phthalate of formula (I), generates diethyl phthalate (DEP) conductInternal donor compound.

Still more preferably, the BCF20P catalyst that is Borealis according to catalyst used in the present invention is (as at WO99/Disclosed prepared according to WO92/19653 in 24479; Especially use dioctyl phthalate according to WO92/19658As the bialkyl ortho phthalate of formula (I)) 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 is except specific Ziegler-NaOutside tower major catalyst, preferably also comprise organic metal promoters as component (ii).

Therefore, co-catalyst is preferably selected from trialkylaluminium as triethyl aluminum (TEA), dialkylaluminum chloride and alkyl sesquialterAluminium chloride.

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

Si(OCH₃)₂R₂ ⁵(IIIa)

Wherein R⁵Represent to have the alkyl of branching of 3 to 12 carbon atoms, preferably there is the branching of 3 to 6 carbon atomsAlkyl, or there is the cycloalkyl of 4 to 12 carbon atoms, preferably there is the cycloalkyl of 5 to 8 carbon atoms.

Particularly preferably, R⁵Be selected from isopropyl, isobutyl group, isopentyl, the tert-butyl group, tertiary pentyl, neopentyl, cyclopenta, ringHexyl, methylcyclopentyl and suberyl.

Formula (IIIb) is defined by following formula

Si(OCH₂CH₃)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 1 to 12 carbon atomBranching aliphatic alkyl and the annular aliphatic alkyl with 1 to 12 carbon atom. Particularly preferably, R^xAnd R^yIndependently selected fromMethyl, ethyl, n-pro-pyl, normal-butyl, octyl group, decyl, isopropyl, isobutyl group, isopentyl, the tert-butyl group, tertiary pentyl, neopentyl,Cyclopenta, 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 lignocaine triethoxysilane.

More preferably, external donor is selected from lignocaine triethoxysilane [Si (OCH₂CH₃)₃(N(CH₂CH₃)₂)], twoCyclopenta dimethoxy silane [Si (OCH₃)₂(cyclopenta)₂], diisopropyl dimethoxy silane [Si (OCH₃)₂(CH(CH₃)₂)₂] and composition thereof.

In another embodiment, Z-N major catalyst can be by making second under the existence of catalyst systemAlkenyl compound polymerization carrys out modification, and described catalyst system comprises specific Z-N major catalyst (component (i)), outerPortion's donor (component (iii)) and optionally co-catalyst (component (iii)), described vinyl compound has following formula:

CH₂=CH-CHR³R⁴

Wherein R³And R⁴Form together 5 yuan or 6 yuan of saturated, undersaturated or aromatic rings, or represent independently to comprise 1 to 4The alkyl of individual carbon atom, through the catalyst of modification for the preparation of heterophasic propylene copolymers according to the present invention. Through the ethene of polymerizationBased compound can be used as α-nucleator.

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

Then, by obtained polypropylene (PP) and elastomer (E) and optional additive blend. General use extrudedMachine, if single screw extrusion machine and double screw extruder are for blend. Other suitable devices comprise planetary extruder and single spiral shellBar is kneader altogether. Especially preferred is the double screw extruder that comprises high strength mixing section and kneading block. For the preparation of heterogeneous thirdThe suitable melt temperature of alkene copolymer (HECO) is in the scope of 170 DEG C to 300 DEG C, preferably the scope of 200 DEG C to 260 DEG CIn. Normally pill form of the heterophasic propylene copolymers (HECO) reclaiming from extruder. Then preferably further process thisA little pills, for example by injection moulding to obtain goods, as the goods that above limit more in detail.

To further illustrate the present invention by embodiment below.

Embodiment

A. measuring method

Unless otherwise defined, otherwise the definition of following term and assay method be applicable to above general description of the present invention withAnd 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 of prepared polymer in the second reactor (R2)Mark,

C (PP1) is the first polypropylene part (PP1), and the co-monomer content of the product of the first reactor (R1) is [heavyAmount %],

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

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

Calculate the cold DDGS 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 of prepared polymer in the second reactor (R2)Mark,

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

The product of XS (R2) for obtaining in the second reactor (R2), the first polypropylene part (PP1) and second is gatheredThe cold DDGS of dimethylbenzene (XCS) content [% by weight] of the mixture of propylene part (PP2),

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

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 of prepared polymer in the second reactor (R2)Mark,

MFR (PP1) is the first polypropylene part (PP1), the i.e. melt flow rate (MFR) of the product of the first reactor (R1)MFR₂(230 DEG C) [gram/10 minutes],

The product of MFR (R2) for obtaining in the second reactor (R2), the first polypropylene part (PP1) and second is gatheredThe melt flow rate (MFR) MFR of the mixture of propylene part (PP2)₂(230 DEG C) [gram/10 minutes],

The melt flow rate (MFR) MFR that MFR (PP2) is the second polypropylene part (PP2) of calculating₂(230 DEG C) [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 first polypropylene part (PP1) and the second polypropylene part(PP2) weight fraction of mixture,

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

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

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

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

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

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

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

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 first polypropylene part (PP1) and the second polypropylene part(PP2) weight fraction of mixture,

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

MFR (R2) is the product of the second reactor (R2), i.e. the first polypropylene part (PP1) and the second polypropylene part(PP2) the melt flow rate (MFR) MFR of mixture₂(230 DEG C) [gram/10 minutes],

The product of MFR (R3) for obtaining in the 3rd reactor (R3), the first polypropylene part (PP1), second is gatheredThe melt flow rate (MFR) MFR of the mixture of propylene part (PP2) and tripropylene part (PP3)₂(230 DEG C) [gram/10 pointsClock],

The melt flow rate (MFR) MFR that MFR (PP3) is the tripropylene part (PP3) that calculates₂(230 DEG C) [gram/10 minutes].

Number-average molecular weight (M_n), weight average molecular weight (M_w) and molecular weight distribution (MWD) pass through gel infiltration according to following methodsChromatogram (GPC) is determined:

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 refractive index detector andThe WatersAllianceGPCV2000 of line viscosimeter adopts the 3xTSK-gel column (GMHXL-HT) and 1,2 of TosoHaas,4-trichloro-benzenes (TCB, with 200mg/L2,6-di-t-butyl-4-methyl-phenol is stable) as solvent at 145 DEG C with steady flowSpeed is used for 1mL/ minute. Each analysis injected 216.5 μ L sample solutions. Post group is with having in 0.5 kg/mol to 11,500 thousand19 narrow MWD polystyrene (PS) reference materials within the scope of gram/mol and one group of wide polypropylene reference material fully characterizingRelative scale is calibrated. By by 5mg to 10mg polymer dissolution to 10mL (at 160 DEG C) through stable TCB (with mobile phaseIdentical) in and before in GPC instrument, under shake, keeping preparing for 3 hours all samples at sample introduction continuously.

Density is measured according to ISO1183-1-method A (2004). Sample preparation is passed through according to ISO1872-2:2007Compression molding complete.

MFR₂(230 DEG C) are measured according to ISO1133 (230 DEG C, 2.16kg load).

MFR₂(190 DEG C) are measured according to ISO1133 (190 DEG C, 2.16kg load).

The co-monomer content of being undertaken by FTIR spectroscopic methodology quantizes

In mode well-known in the art, via quantitatively¹³The basic ownership of C nuclear magnetic resonance (NMR) spectral method calibrationAfter, determine co-monomer content by quantitative fourier transform infrared spectroscopy (FTIR). Film is pressed at 100 μ mTo the thickness between 500 μ m, and with transmission mode spectra re-recorded.

Particularly, use at 720cm^-1To 722cm^-1And 730cm^-1To 733cm^-1Place find quantitative band through baseline schoolPositive peak area is determined the ethylene contents of propylene-ethylene copolymers. Particularly, use at 1377cm^-1To 1379cm^-1Place is sent outThe peak area through baseline correction of existing quantitative band is determined butylene or the hexene content of polyethylene and ethylene copolymers. Based on reference to thicknessDegree obtains quantitative result.

The cold DDGS of dimethylbenzene (XCS, % by weight): the content of the cold DDGS of dimethylbenzene (XCS) is according to ISO16152: firstVersion; 2005-07-01 determines at 25 DEG C.

Intrinsic viscosity is according to DINISO1628/1, and measure in October, 1999 (at 135 DEG C in naphthalane).

Melt temperature T_m, crystallization temperature T_cUtilize MettlerTA820 differential scanning calorimeter (DSC) 5mg to 10mg sampleProduct are measured. Crystallization curve and melting curve be the cooling and heating scanning process of 10 DEG C/min between 30 DEG C and 225 DEG C bothMiddle acquisition. Melt temperature and crystallization temperature are taken as endothermic peak and exothermic peak.

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

Stretch modulus be according to ISO527-1 (crosshead speed=1mm/ minute) 23 DEG C of uses according to ENISO1873-2That manufactures measures according to the injection moulding sample of ISO527-2 (1B) (dog bone shape 10, thickness is 4mm).

Charpy otch impact strength according to ISO179/1eA 23 DEG C and at-20 DEG C by use as ENInjection moulding sample (80 × 10 × 4mm) described in ISO1873-2 is determined.

Expose energy and use the moulding of 60 × 60 × 2mm and the test speed instrument of 4.4m/s according to ISO6603-2(IFW) test of dropping hammer is determined. Report expose energy by the integrations at+23 DEG C and-20 DEG C of measured failure energy curvesObtain.

At the injection moulding disk of trumpet assembly, (diameter 180mm, thickness 3mm have cutting of the flow angle of 355 ° and 5 ° to shrinkage factorThe angle of rupture) upper definite. Apply two samples of two different maintenance pressure times (being respectively 10s and 20s) molding. Melting of cast gate placeTemperature is 260 DEG C, and average flow forward position speed in mould is 100mm/s. Tool temperature: 40 DEG C, back-pressure: 600 bar.

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

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

BET measures according to ISO9277.

B. embodiment

All polymer have pre-polymerization reactor, a slurry loop reactor and two Gas-phase reactorIn Borstar pilot-plant, prepare. The catalyst P olytrack8502 being purchased from Grace (US) with as two of external donorEthylamino triethoxysilane [Si (OCH₂CH₃)₃(N(CH₂CH₃)₂)] (U donor) and as the triethyl group of activator and scavengerAluminium (TEAL) is used in combination with the ratio shown in table 1. Catalyst by making vinyl chemical combination under the existence of catalyst systemThing polymerization carrys out modification.

Table 1: the preparation of polypropylene (PP)

Parameter	Unit	H-PP
			Donor type		U
Al/ donor ratio	[moles/mole]	9
			Ring type
MFR2(230℃)	[gram/10 minutes]	343 19 -->
			XCS	[% by weight]	2.1
GPR1
			MFR2(230℃)	[gram/10 minutes]	218
XCS	[% by weight]	2.0
			MFR2*	[gram/10 minutes]	134
XCS*	[% by weight]	1.8
			GPR2
MFR2(230℃)	[gram/10 minutes]	125
			XCS	[% by weight]	1.8
MFR2**	[gram/10 minutes]	6.5
			XCS**	[% by weight]	1.5
MWD	[-]	6.5
			Distribute ring type/GPR1/GPR2	[% by weight]	42/42/16

* the polymer of preparing in GPR1

The polymer of preparing in * GPR2

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

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

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

HK060AE is the commodity of BorealisAG, and it is to have the MFR of 125 grams/10 minutes₂(230 DEG C/2.16kg) and905kg/m³The polypropylene homopolymer of density.

Engage8400 is the commodity of DowElastomers, and it is to have the MFR of 30 grams/10 minutes₂(190℃，2.16kg) and 870kg/m³The ethylene-octene copolymer of density.

HDPE is the commercial high density polyethylene (HDPE) (HDPE) " MG9601 " of Borealis, and it has 30 grams/10 minutesMFR (190 DEG C/2.16kg) and 960kg/m³Density.

Talcum is the commercial talcum " SteamicT1CA " that can obtain from Luzenac, and it has 1.8 μ m'sD50, the cut-off particle diameter (d of 6.2 μ m₉₅) and 8.0m²The 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
							MFR2(230℃)	[gram/10 minutes]	92	100	80	86	75 20 -->
Stretch modulus	[MPa]	1330	1450	1860	1060	1680
							Impact strength+23 DEG C	[kJ/m2]	5.2	4.1	4.0	4.1	4.5
Impact strength-20 DEG C	[kJ/m2]	2.0	1.6	2.0	2.0	2.0
							Expose energy+23 DEG C	[J]	19	18	12	6	12
Expose energy-20 DEG C	[J]	10	9	4	1.3	4
							Radial shrinkage ratio	[%]	1.0	1.3	0.9	1.1	0.9
Tangential shrinkage factor	[%]	1.1	1.4	0.9	1.1	1.0

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

Claims (18)

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

(a) be the matrix (M) of polypropylene (PP), described polypropylene (PP) comprise at least three kinds of polypropylene part PP1, PP2 andPP3, described three kinds of polypropylene part PP1, PP2 and PP3 under 230 DEG C and 2.16kg load according to measured molten of ISO1133Body flow rate MFR₂Aspect differs from one another, wherein the first polypropylene part PP1 taking the gross weight based on described matrix (M) as20.0 % by weight exist to the amount of 55 % by weight, and have under 230 DEG C and 2.16kg load measured according to ISO1133The melt flow rate (MFR) MFR of 80 grams/10 minutes to 500 grams/10 minutes₂, the second polypropylene part PP2 is with based on described matrix(M) to be 20 % by weight exist to the amount of 55 % by weight gross weight, and have under 230 DEG C and 2.16kg load according to ISOThe 1133 measured melt flow rate (MFR) MFR of 20 grams/10 minutes to 300 grams/10 minutes₂, PP3 is with base for tripropylene partBe that 10 % by weight exist to the amount of 30 % by weight in the gross weight of described matrix (M), and have 230 DEG C and 2.16kg loadThe lower melt flow rate (MFR) MFR of 1 gram/10 minute to 15 gram/10 minute measured according to ISO1133₂, and

(b) be dispersed in the elastomer (E) in described matrix (M), the wherein weight based on described heterophasic propylene copolymers (HECO)The described elastomer (E) of the amount that comprises 25 to 40 % by weight, and described elastomer (E) has at 135 DEG C according to DINISO1628/1 0.8dl/g measuring is to the intrinsic viscosity of 1.5dl/g.

2. heterophasic propylene copolymers according to claim 1 (HECO), wherein said heterophasic propylene copolymers (HECO) toolThere is the melt flow rate (MFR) MFR of at least 50 gram/10 minute measured according to ISO1133 under 230 DEG C and 2.16kg load₂。

3. heterophasic propylene copolymers according to claim 1 and 2 (HECO), wherein said polypropylene part PP1, PP2 andAt least one in PP3 is Noblen.

4. heterophasic propylene copolymers according to claim 3 (HECO), wherein said polypropylene part PP1, PP2 and PP3In at least two kinds be Noblen.

5. heterophasic propylene copolymers according to claim 4 (HECO), wherein said polypropylene part PP1, PP2 and PP3Be Noblen.

6. heterophasic propylene copolymers according to claim 1 and 2 (HECO), wherein said elastomer (E)

(a) have under 190 DEG C and 2.16kg load according to measured 10 grams/10 minutes to 80 grams/10 minutes of ISO1133Melt flow rate (MFR) MFR₂, and/or

(b) gross weight based on described heterophasic propylene copolymers (HECO), is included in institute with 25 % by weight to the amount of 35 % by weightState in heterophasic propylene copolymers (HECO), and/or

(c) have lower than 940kg/m³Density.

7. heterophasic propylene copolymers according to claim 1 and 2 (HECO), wherein said elastomer (E) is for comprising etheneThe Toughening Effect of Ethylene Copolymer Elastomer of monomeric unit and comonomer unit, wherein said comonomer is selected from C₃To C₂₀Alpha-olefin;Or C₅To C₂₀α, ω-alkadienes.

8. heterophasic propylene copolymers according to claim 7 (HECO), wherein said C₃To C₂₀Alpha-olefin be selected from propylene,1-butylene, 1-hexene and 1-octene.

9. heterophasic propylene copolymers according to claim 7 (HECO), wherein said comonomer is selected from propylene, 1-fourthAlkene, 1-hexene, 1-octene and 1,7-octadiene.

10. heterophasic propylene copolymers according to claim 1 and 2 (HECO), wherein said polypropylene (PP) has 25The cold DDGS of the dimethylbenzene that is equal to or less than 3.5 % by weight (XCS) part of measuring according to ISO16152 at DEG C.

11. heterophasic propylene copolymers according to claim 1 and 2 (HECO), wherein said three kinds of polypropylene part PP1,Each in PP2 and PP3 all has the diformazan that is equal to or less than 4.0 % by weight of measuring according to ISO16152 at 25 DEG CThe cold DDGS of benzene (XCS) content.

12. heterophasic propylene copolymers according to claim 1 and 2 (HECO), wherein said heterophasic propylene copolymers(HECO) also comprise

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

And/or

(b) inorganic filler (F).

13. 1 kinds for the preparation of according to the method for heterophasic propylene copolymers in any one of the preceding claims wherein (HECO),It comprises the following steps:

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

14. methods for the preparation of heterophasic propylene copolymers (HECO) according to claim 13, it also comprises following stepRapid:

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

15. according to the method for the preparation of heterophasic propylene copolymers (HECO) described in claim 13 or 14, its also comprise withLower step:

(a) different from the another kind that is selected from PP1, PP2 and PP3 a kind of polypropylene part that is selected from PP1, PP2 and PP3 are gathered to thirdThe blend of alkene part, then adds the remaining part of PP1, PP2 and PP3, or

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

16. methods for the preparation of heterophasic propylene copolymers (HECO) according to claim 14, it also comprises following stepRapid:

(a1) in the first reactor (R1), make propylene and optionally at least one ethene and/or C₄To C₁₂Alpha-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 optionalAt least one ethene of ground and/or C₄To C₁₂Alpha-olefine polymerizing, thereby obtain the second polypropylene part PP2, described first poly-thirdAlkene part PP1 mixes 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 in step (c1), make propylene and appointAt least one ethene of selection of land and/or C₄To C₁₂Alpha-olefine polymerizing, thereby obtain tripropylene part PP3, wherein said theOne polypropylene part PP1, described the second polypropylene part PP2 and described tripropylene part PP3 are the also shapes being mixed with each otherBecome polypropylene (PP);

Or

(a2) in the first reactor (R1), make propylene and optionally at least one ethene and/or C₄To C₁₂Alpha-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 optionalAt least one ethene of ground and/or C₄To C₁₂Alpha-olefine polymerizing, thereby obtain tripropylene part PP3, described first poly-thirdAlkene part PP1 mixes 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 in step (c2), make propylene and appointAt least one ethene of selection of land and/or C₄To C₁₂Alpha-olefine polymerizing, thereby obtain the second polypropylene part PP2, wherein said theOne polypropylene part PP1, described the second polypropylene part PP2 and described tripropylene part PP3 are the also shapes being mixed with each otherBecome polypropylene (PP);

Or

(a3) in the first reactor (R1), make propylene and optionally at least one ethene and/or C₄To C₁₂Alpha-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 optionalAt least one ethene of ground and/or C₄To C₁₂Alpha-olefine polymerizing, thereby obtain tripropylene part PP3, described second poly-thirdAlkene part PP2 mixes 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 in step (c3), make propylene and appointAt least one ethene of selection of land and/or C₄To C₁₂Alpha-olefine polymerizing, thereby obtain the first polypropylene part PP1, wherein said theOne polypropylene part PP1, described the second polypropylene part PP2 and described tripropylene part PP3 are the also shapes being mixed with each otherBecome polypropylene (PP);

Or

(a4) in the first reactor (R1), make propylene and optionally at least one ethene and/or C₄To C₁₂Alpha-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 optionalAt least one ethene of ground and/or C₄To C₁₂Alpha-olefine polymerizing, thereby obtain the first polypropylene part PP1, described second poly-thirdAlkene part PP2 mixes 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 in step (c4), make propylene and appointAt least one ethene of selection of land and/or C₄To C₁₂Alpha-olefine polymerizing, thereby obtain tripropylene part PP3, wherein said theOne polypropylene part PP1, described the second polypropylene part PP2 and described tripropylene part PP3 are the also shapes being mixed with each otherBecome polypropylene (PP);

Or

(a5) in the first reactor (R1), make propylene and optionally at least one ethene and/or C₄To C₁₂Alpha-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 optionalAt least one ethene of ground and/or C₄To C₁₂Alpha-olefine polymerizing, thereby obtain the first polypropylene part PP1, described trimerization thirdAlkene part PP3 mixes 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 in step (c5), make propylene and appointAt least one ethene of selection of land and/or C₄To C₁₂Alpha-olefine polymerizing, thereby obtain the second polypropylene part PP2, wherein said theOne polypropylene part PP1, described the second polypropylene part PP2 and described tripropylene part PP3 are the also shapes being mixed with each otherBecome polypropylene (PP);

Or

(a6) in the first reactor (R1), make propylene and optionally at least one ethene and/or C₄To C₁₂Alpha-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 optionalAt least one ethene of ground and/or C₄To C₁₂Alpha-olefine polymerizing, thereby obtain the second polypropylene part PP2, described trimerization thirdAlkene part PP3 mixes 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 in step (c6), make propylene and appointAt least one ethene of selection of land and/or C₄To C₁₂Alpha-olefine polymerizing, thereby obtain the first polypropylene part PP1, wherein said theOne polypropylene part PP1, described the second polypropylene part PP2 and described tripropylene part PP3 are the also shapes being mixed with each otherBecome polypropylene (PP).

17. 1 kinds of goods, it comprises according to the heterophasic propylene copolymers described in any one in claim 1 to 12 (HECO).

18. according to the heterophasic propylene copolymers described in any one in claim 1 to 12 (HECO) use in road vehicle applicationOn the way.