CN104837904B

CN104837904B - Polypropene composition that is that tiger fur line is reduced or eliminated and retaining excellent mechanical performance

Info

Publication number: CN104837904B
Application number: CN201280077281.XA
Authority: CN
Inventors: 朱江磊; 张建东; 陈世平
Original assignee: Plastic (shanghai) Co Ltd
Current assignee: Plastic (shanghai) Co Ltd
Priority date: 2012-11-30
Filing date: 2012-11-30
Publication date: 2017-07-04
Anticipated expiration: 2032-11-30
Also published as: IN2015DN03994A; JP2015537087A; EP2925811A1; KR20150086319A; CN104837904A; KR101770487B1; EP2925811A4; WO2014082188A1; JP6143876B2

Abstract

It is used to reduce the purposes of the tiger fur line on product surface for preparing the purposes and the polypropene composition (PP) of mechanograph the present invention relates to a kind of polypropene composition (PP), the product comprising the polypropene composition (PP) and the polypropene composition (PP).

Description

Polypropylene group that is that tiger fur line is reduced or eliminated and retaining excellent mechanical performance Compound

Technical field

The present invention relates to a kind of polypropene composition (PP), the product comprising the polypropene composition (PP), Yi Jisuo State polypropene composition is used to reduce product surface for preparing the purposes and the polypropene composition (PP) of mechanograph Tiger fur line purposes.

Background technology

Now, polypropylene is for auto parts such as bumper bar, door-plate, the selected polymerization of instrument board OR gate dividing plate Thing.Particularly, when heterophasic propylene copolymers are combined good impact property with rigidity, the heterophasic propylene copolymers are suitable .Heterophasic propylene copolymers are well known in the art, and are included as polypropylene homopolymer or atactic polypropylene copolymer Matrix, be scattered here and there elastomer copolymer in the matrix.Therefore, it is not one of matrix that the polypropylene-base is scattered comprising (thin) The inclusion divided, and the inclusion includes elastomer.Term inclusion represents matrix and inclusion in heterophasic propylene copolymerization Different phases are formed in thing, the inclusion is for example visible in the following way：By high resolution microscope, such as electron microscopic Mirror or scanning force microscopy.

Although commercially available polypropylene achieves balance well between rigidity and impact, the entirety to this system is matched somebody with somebody Putting requirement becomes more to need.For example, polypropylene is generally injection molded as desired product such as automobile product and family expenses system Product.However, when product is relatively large, such as when such as car insurance bar, door-plate, instrument board OR gate dividing plate, due to polypropylene tree Flow path long needed for fat and that optics occurs often is irregular.

During injection molding, once if tiger fur line, ripple or this well-known surface defect of streamline are with perpendicular to melt flow When the low-luster bar alternate high in dynamic direction occurs, they will destroy surface aesthetic feeling.

In this respect, many trials have been done to avoid these surface defects while keeping the good of other physical properties Balance, such as DE 19754061.It has been found, however, that：This e insufficient to prevent the appearance of tiger fur line, or combination of polymers The mechanical property of thing is not satisfactory.

Therefore, the appearance of further reduction tiger fur line is stilled need in the prior art.In addition, not only need to subtract The appearance of few tiger fur line also needs to such as to impact mechanical property/and rigidity property is maintained in superelevation level.

The content of the invention

Therefore, it is an object of the invention to provide a kind of polypropene composition, the polypropene composition is being made from it Do not show tiger fur line on the surface of product completely or only show small tiger fur line.In addition, the purpose of the present invention is not only in that and carries Polypropene composition for not showing tiger fur line, also resides in the rigidity/impact property of the balance for keeping mechanical property such as excellent.

Above-mentioned and other purpose is solved by subject of the present invention (subject-matter).

Specific discovery of the invention is to provide a kind of comprising two kinds of polypropene compositions of heterophasic propylene copolymers (PP), Two kinds of heterophasic propylene copolymers are in their melt flow rate (MFR) MFR₂It is upper different and exist with specified quantitative.

According to the first aspect of the invention, there is provided a kind of polypropene composition (PP), the polypropene composition (PP) Comprising：

A) the first heterophasic propylene copolymers (HPP1), its melt flow rate (MFR) MFR₂(230 DEG C, 2.16kg) be 20.0~ 80.0g/10min, and

B) the second heterophasic propylene copolymers (HPP2), its melt flow rate (MFR) MFR₂(230 DEG C, 2.16kg) be 0.05~ 2.0g/10min,

Wherein,

I) on the basis of the gross weight of the first heterophasic propylene copolymers (HPP1) and the second heterophasic propylene copolymers (HPP2), The content of the first heterophasic propylene copolymers (HPP1) in the range of 66.6~95.2wt%, and

Ii) gross weight with the first heterophasic propylene copolymers (HPP1) and the second heterophasic propylene copolymers (HPP2) is base Standard, the content of the second heterophasic propylene copolymers (HPP2) is in the range of 4.8~33.4wt%.

It has surprisingly been found that：Polypropene composition (PP) of the invention is complete on the surface of the product being made from it Tiger fur line is not shown or small tiger fur line is only shown entirely.Additionally, compared to prior art products, Polypropylene compositions of the invention A part for thing (PP) does not show tiger fur line not only but also with important mechanical property, such as rigidity and impact property are also located In high level.

It will be appreciated that for purposes of the invention, following term has following meanings：

Term " multiphase " represents that elastocopolymer (thin) is scattered in matrix.In other words, elastomeric propylene copolymers are in matrix Middle formation inclusion.Therefore, inclusion of the matrix comprising (thin) scattered part for not being matrix, and the inclusion bag Containing elastomeric propylene copolymers.Term " inclusion " of the invention should preferably represent that matrix and inclusion are common in heterophasic propylene Different phases are formed in polymers, the inclusion is for example visible in the following way：By high resolution microscope, such as electronic display Micro mirror or scanning force microscopy.

Final composition is probably composite construction.For example, the matrix of heterophasic propylene copolymers can be formed as composition Matrix continuous phase or discontinuous phase, wherein, elastocopolymer and optional additive together or have been independently formed and have been scattered in Inclusion in matrix.

According to another aspect of the present invention, there is provided a kind of product, the product includes the polypropene composition (PP), excellent Choosing is made up of the polypropene composition (PP).Preferably, the product is mechanograph, preferably injection molded article.Further, this hair Bright another aspect further relates to the polypropene composition (PP) for preparing the purposes of mechanograph, is preferred for injection molded article Purposes.Even further aspect of the invention further relates to purposes of the polypropene composition (PP) in product is prepared, and is used for Reduce the tiger fur line on product surface.

To polypropene composition of the present invention (PP) preferred embodiment or ins and outs carry out below with reference to when, can Know these preferred embodiment or ins and outs further relate to the inventive article comprising polypropene composition (PP) and poly- third Ene compositions (PP) are used to prepare the purposes of the present invention of the purposes of the present invention and polypropene composition (PP) of mechanograph in product, For reducing the tiger fur line on product surface.

An implementation method of the invention, the first heterophasic propylene copolymers (HPP1) have：A) 20.0~75.0g/ The melt flow rate (MFR) MFR of 10min₂(230 DEG C, 2.16kg)；And/or b) with the gross weight of the first heterophasic propylene copolymers (HPP1) On the basis of amount, dimethylbenzene cold DDGS (XCS) fraction (25 DEG C) of 15.0~25.0wt%；And/or c) with the first heterophasic propylene On the basis of the gross weight of copolymer (HPP1), the ethylene contents less than 15.0wt%；And/or d) inherent viscosity (IV) be 2.0~ Amorphous (AM) phase of 3.0dl/g；And/or e) gross weight with amorphous (AM) phase of the first heterophasic propylene copolymers (HPP1) is base Standard, ethylene contents are amorphous (AM) phase of 33.0~40.0wt%.

Another implementation method of the invention, the second heterophasic propylene copolymers (HPP2) have：A) 0.1~2.0g/ The melt flow rate (MFR) MFR of 10min₂(230 DEG C, 2.16kg)；And/or b) with the gross weight of the second heterophasic propylene copolymers (HPP2) On the basis of amount, dimethylbenzene cold DDGS (XCS) fraction (25 DEG C) of 9.0~20.0wt%；C) with the second heterophasic propylene copolymers (HPP2) on the basis of gross weight, the ethylene contents of 3.0~8.0wt%；And/or d) inherent viscosity (IV) is 3.0~4.0dl/g Amorphous (AM) phase；And/or e) on the basis of the gross weight of amorphous (AM) phase of the second heterophasic propylene copolymers (HPP2), ethene Content is amorphous (AM) phase of 30.0~37.0wt%.

Another implementation method of the invention, the first heterophasic propylene copolymers (HPP1) include polypropylene homopolymer matrix And the elastomeric propylene copolymers (AM1) that are scattered in the matrix (PM1), and/or the second heterophasic propylene copolymers (PM1) (HPP2) comprising polypropylene homopolymer matrix (PM2) and the elastomeric propylene copolymers (AM2) being scattered in the matrix (PM2). Preferably, the polypropylene homopolymer matrix (PM1) of the first heterophasic propylene copolymers (HPP1) has：A) 30.0~250.0g/ The melt flow rate (MFR) MFR of 10min₂(230 DEG C, 2.16kg)；And/or b) with poly- the third of the first heterophasic propylene copolymers (HPP1) On the basis of the gross weight of polyamino alkenyl thing matrix (PM1), dimethylbenzene cold DDGS (XCS) fraction (25 DEG C) of 0.8~3.0wt%. It is further preferred that the polypropylene homopolymer matrix (PM2) of the second heterophasic propylene copolymers (HPP2) has：A) 0.1~3.0g/ The melt flow rate (MFR) MFR of 10min₂(230 DEG C, 2.16kg)；And/or b) with poly- the third of the second heterophasic propylene copolymers (HPP2) On the basis of the gross weight of polyamino alkenyl thing matrix (PM2), dimethylbenzene cold DDGS (XCS) fraction (25 DEG C) less than 2.0wt%.

An implementation method of the invention, polypropene composition (PP) is included：With the total of polypropene composition (PP) On the basis of weight, first heterophasic propylene copolymers (HPP1) of 40.0~60.0wt%；With the gross weight of polypropene composition (PP) On the basis of amount, second heterophasic propylene copolymers (HPP2) of 3.0~20.0wt%；Gross weight with polypropene composition (PP) is Benchmark, (wherein, the gross weight with elastic ethylene copolymer (EE) is as base for the elastic ethylene copolymer (EE) of 5.0~20.0wt% Standard, the elastic ethylene copolymer (EE) has the content of at least ethylene unit of 50.0wt%)；With polypropene composition (PP) On the basis of gross weight, the high density polyethylene (HDPE) (HDPE) of 5.0~10.0wt%；And, with the gross weight of polypropene composition (PP) On the basis of amount, the inorganic filler (F) of 15.0~25.0wt%.Said composition comprising EE, HDPE, F can show excellent Mechanical property, such as the rigidity/impact property of excellent balance, while not showing tiger fur line.

Another implementation method of the invention, elastic ethylene copolymer (EE)：A) comprising ethylene unit and selected from C₄~ C₁₂The comonomer unit of alpha-olefin；And/or b) on the basis of the gross weight of elastic ethylene copolymer (EE), 50.0~ The acetate unit content of 75.0wt%；And/or c) the melt flow rate (MFR) MFR of 0.25~30.0g/10min₁(190 DEG C, 2.16kg)。

Another implementation method of the invention, high density polyethylene (HDPE) (HDPE) has the melt of 0.2~15.0g/10min Flow rate MFR₁(190 DEG C, 2.16kg) and/or at least 930kg/m³Density.

An implementation method of the invention, inorganic filler (F) is selected from group constituted by the following substances：Talcum, cloud Mother, calcium carbonate, diatomite, wollastonite, kaolin；And/or the inorganic filler (F) has 0.65~20 μm of average grain diameter d₅₀。

Another implementation method of the invention, polypropene composition (PP) has：A) the flexure mould of at least 1500MPa Amount；And/or b) it is more than 30kJ/m²Ai Zuode notch impact strengths (23 DEG C).

Another implementation method of the invention, the first heterophasic propylene copolymers (HPP1) and/or the second heterophasic propylene are total to Polymers (HPP2) is through α-nucleation, it is preferable that the first heterophasic propylene copolymers (HPP1) and the second heterophasic propylene copolymers (HPP2) Through α-nucleation.

Below, the present invention will be described in further detail.

Specific embodiment

Polypropene composition (PP) of the invention includes the first heterophasic propylene copolymers (HPP1) and the second multiphase third Alkene copolymer (HPP2).Additionally, the melt flow rate (MFR) MFR that the first heterophasic propylene copolymers (HPP1) are measured according to ISO1133₂ (230 DEG C, 2.16kg) are 20.0~80.0g/10min；And the second heterophasic propylene copolymers (HPP2) are measured according to ISO1133 Melt flow rate (MFR) MFR₂(230 DEG C, 2.16kg) are 0.05~2.0g/10min.In addition, it is common with the first heterophasic propylene On the basis of the gross weight of polymers (HPP1) and the second heterophasic propylene copolymers (HPP2), the first heterophasic propylene copolymers (HPP1) Content in the range of 66.6~95.2wt%, and the second heterophasic propylene copolymers (HPP2) content 4.8~ In the range of 33.4wt%.

In an embodiment of the invention, polypropene composition (PP) is preferably characterized in that high rigidity, that is, bend mould It is at least 1,500MPa, preferably 1 to measure, 500~2,700MPa, more preferably 1,600~2,600MPa.For example, of the invention Polypropene composition (PP) is characterized in：Flexural modulus is 1,700~2,500MPa, such as 1,720~2,500MPa.

In an embodiment of the invention, the tensile strength of polypropene composition (PP) is more than 15MPa, more preferably greatly In 17MPa, and it is most preferably more than 17MPa to 30MPa.

Additionally or alternatively, impact strength should also be at a relatively high.It is therefore preferred that polypropene composition (PP) is preferred It is characterized in：(+23 DEG C) of Ai Zuode notch impact strengths are more than 30kJ/m², more preferably equal to or greater than 40kJ/m².For example, poly- third Ene compositions (PP) are preferably characterized in that：Ai Zuode notch impact strengths (+23 DEG C) are in 40~60kJ/m²In the range of, or 45~55kJ/m²In the range of.

Preferably, the flexural modulus of polypropene composition (PP) is preferably at least 1500MPa, and/or the punching of Ai Zuode breach Hit intensity (+23 DEG C) is preferably greater than 30kJ/m².In an embodiment of the invention, the flexure of polypropene composition (PP) Modulus is at least 1500MPa, and (+23 DEG C) of its Ai Zuode notch impact strength is more than 30kJ/m²。

Polypropene composition (PP) is especially through the first heterophasic propylene copolymers (HPP1) and the second heterophasic propylene copolymers (HPP2) it is defined.

Therefore, all components are limited in more detail now.

First heterophasic propylene copolymers (HPP1) are preferably heterogeneous system, wherein, in heterogeneous system, as described herein Polypropylene homopolymer matrix (PM1) constitutes matrix, wherein, elastomeric propylene copolymers (AM1) are scattered in the matrix.

Accordingly, as polypropene composition (PP) a part the first heterophasic propylene copolymers (HPP1) except comprising third Outside alkene, also comprising comonomer.Preferably as the first heterophasic propylene copolymers of a part for polypropene composition (PP) (HPP1) in addition to comprising propylene, also comprising ethene and/or C₄~C₁₂Alpha-olefin.Therefore, term of the invention first Heterophasic propylene copolymers (HPP1) are defined as polypropylene, and the polypropylene includes the unit from following material, preferably by being derived from Constituted in the unit of following material,

(a) propylene and

(b) ethene and/or C₄~C₁₂Alpha-olefin.

Therefore, the first heterophasic propylene copolymers (HPP1) of the invention, i.e., as the one of polypropene composition (PP) Partial the first heterophasic propylene copolymers (HPP1) comprising can with the monomer of propylene copolymerization, such as comonomer, such as ethene and/ Or C₄~C₁₂Alpha-olefin, particularly ethene and/or C₄~C₈Alpha-olefin, such as 1- butylene and/or 1- alkene.Preferably, according to this First heterophasic propylene copolymers (HPP1) of invention comprising can with the monomer of propylene copolymerization, particularly by can be with the list of propylene copolymerization Body is constituted, and the monomer is selected from by ethene, 1- butylene and the 1- groups that alkene is constituted.More specifically, the first multiphase of the invention Propylene copolymer (HPP1) in addition to comprising propylene, also comprising the unit from ethene and/or 1- butylene.Preferred real Apply in mode, the first heterophasic propylene copolymers (HPP1) of the invention are only comprising the unit from propylene and ethene.Also It is highly preferred that only elastomeric propylene copolymers (AM1) include ethylene comonomer.

It is therefore preferred that the elastomeric propylene copolymers (AM1) being scattered in polypropylene homopolymer matrix (PM1) include third Alkene monomer unit and selected from ethene and/or C₄~C₁₂The comonomer unit of alpha-olefin.For example, being scattered in polypropylene homopolymer Elastomeric propylene copolymers (AM1) in matrix (PM1) include propylene monomer units and ethylene comonomer units.

Therefore, elastomeric propylene copolymers (AM1) are preferably ethylene propylene rubber (EPR), and the elastomeric propylene that is wherein scattered here and there The matrix of copolymer (AM1) is then polypropylene homopolymer matrix (PM1).

Preferably, on the basis of the gross weight of the first heterophasic propylene copolymers (HPP1), as polypropene composition (PP) A part the preferred co-monomer content of the first heterophasic propylene copolymers (HPP1), optimal ethylene content is less than 15.0wt%, preferably smaller than 12.0wt%, more preferably 3.0~10.0wt%, and most preferably 5.0~10.0wt%.

On the basis of the gross weight of the first heterophasic propylene copolymers (HPP1), as a part of polypropene composition (PP) The first heterophasic propylene copolymers (HPP1) dimethylbenzene cold DDGS (XCS) fraction (23 DEG C) be preferably 15.0~ 25.0wt%, preferably 18.0~22.0wt%, and most preferably 18.0~20wt%.

Additionally or alternatively, as polypropene composition (PP) a part the first heterophasic propylene copolymers (HPP1) Melt flow rate (MFR) MFR₂(230 DEG C, 2.16kg) be 20.0~80.0g/10min, preferably 20.0~75.0g/10min, More preferably 20.0~60.0g/10min, and most preferably 30.0~50.0g/10min.For example, as polypropene composition (PP) the melt flow rate (MFR) MFR of the first heterophasic propylene copolymers (HPP1) of a part₂(230 DEG C, 2.16kg) are 30.0 ~40.0g/10min or 35.0~40.0g/10min.

It is propylene homo as the polypropylene homopolymer matrix (PM1) of a part for the first heterophasic propylene copolymers (HPP1) Thing.In other words, the co-monomer content of polypropylene homopolymer matrix (PM1) be less than or equal to 0.5wt%, more preferably less than or Equal to 0.3wt%, and most preferably no greater than 0.1wt%.The percentage by weight is with the gross weight of polypropylene homopolymer matrix (PM1) On the basis of.

In other words, as through the term polypropylene homopolymer or polypropylene homopolymer matrix for using in full of the invention (PM1) it is related to polypropylene, the polypropylene is substantially made up of propylene units, i.e., comprising the propylene list equal to or more than 99.5wt% Unit.In a preferred embodiment, propylene units are only can detect in polypropylene homopolymer.

Moreover it is preferred that the polypropylene homopolymer matrix of the part as the first heterophasic propylene copolymers (HPP1) (PM1) dimethylbenzene cold DDGS (XCS) fraction is at a fairly low.Therefore, with the poly- of the first heterophasic propylene copolymers (HPP1) On the basis of the gross weight of propylene homopolymer matrix (PM1), the cold DDGS of the dimethylbenzene (XCS) of polypropylene homopolymer matrix (PM1) Fraction is preferably 0.8~3.0wt%, more preferably 1.0~3.0wt%, and most preferably 1.3~2.5wt%.For example, with On the basis of the gross weight of the polypropylene homopolymer matrix (PM1) of one heterophasic propylene copolymers (HPP1), polypropylene homopolymer matrix (PM1) (25 DEG C) of dimethylbenzene cold DDGS (XCS) fraction is 1.4~2.3wt%.

Additionally or alternatively, as the first heterophasic propylene copolymers (HPP1) a part polypropylene homopolymer matrix (PM1) there is at a relatively high melt flow rate (MFR).It is therefore preferred that the melt flow rate (MFR) of polypropylene homopolymer matrix (PM1) MFR₂(230 DEG C, 2.16kg) are 30.0~250.0g/10min, preferably 40.0~160.0g/10min, more preferably 80.0 ~120.0g/10min, more preferably 90.0~110.0g/10min, and most preferably 95.0~105.0g/10min.

As another key component of the first heterophasic propylene copolymers (HPP1) of a part for polypropene composition (PP) It is dispersed in the elastomeric propylene copolymers (AM1) in polypropylene homopolymer matrix (PM1).

As for the comonomer used in elastomeric propylene copolymers (AM1), it is the first heterophasic propylene copolymers that may be referred to (HPP1) information for being provided.Therefore, elastomeric propylene copolymers (AM1) are comprising can be with the monomer of propylene copolymerization, such as copolymerization list Body, such as ethene and/or C₄~C₁₂Alpha-olefin, particularly ethene and/or C₄~C₈Alpha-olefin, such as 1- butylene and/or 1- are Alkene.Preferably, elastomeric propylene copolymers (AM1) comprising can with the monomer of propylene copolymerization, particularly by can be with the list of propylene copolymerization Body is constituted, and the monomer is selected from by ethene, 1- butylene and the 1- groups that alkene is constituted.More specifically, elastomeric propylene copolymers (AM1) In addition to comprising propylene, also comprising the unit from ethene and/or 1- butylene.Therefore, in particularly preferred embodiment In, elastomeric propylene copolymers (AM1) are only comprising the unit from propylene and ethene.

Because most elastomeric propylene copolymers (AM1) dissolve in dimethylbenzene (XCS contents at ambient temperature；I.e. two The cold solubles content of toluene), so the XCS contents of the first heterophasic polypropylene composition (HPP1) are related to elastomeric propylene copolymers (AM1) be amorphous phase amount, but be not necessarily identical.For example, elastomeric propylene copolymers (AM1) can also be very high comprising having A part for ethylene concentration, it is crystal simultaneously therefore insoluble in cold xylene.

An implementation method of the invention, is total to as the first heterophasic propylene of a part for polypropene composition (PP) Polymers (HPP1) has amorphous (AM) phase, and the inherent viscosity (IV) of amorphous (AM) phase is 2.0~3.0dl/g, and preferably 2.0 ~2.7dl/g.

Co-monomer content in elastomeric propylene copolymers (AM1), optimal ethylene content is relatively low.Therefore, exist In one implementation method, on the basis of the gross weight of amorphous (AM) phase of the first heterophasic propylene copolymers (HPP1), the first multiphase The co-monomer content of the amorphous composition of propylene copolymer (HPP1), more preferably ethylene contents are 33.0~40.0wt%, preferably It is 33.0~38.0wt%, and most preferably 34.0~38.0wt%.

Alternatively, the first heterophasic propylene copolymers (HPP1) are Noblen or atactic propene copolymer or block propylene Copolymer, its melt flow rate (MFR) MFR₂(230 DEG C, 2.16kg) are 20.0~80.0g/10min.

Such as the first heterophasic propylene copolymers (HPP1), the second heterophasic propylene copolymers (HPP2) are also heterogeneous system, should In heterogeneous system, polypropylene homopolymer matrix (PM2) as described herein constitutes matrix, wherein, elastomeric propylene copolymers (AM2) It is scattered in the matrix.

Accordingly, as polypropene composition (PP) a part the second heterophasic propylene copolymers (HPP2) except comprising third Outside alkene, also comprising comonomer.Preferably as the second heterophasic propylene copolymers of a part for polypropene composition (PP) (HPP2) in addition to comprising propylene, also comprising ethene and/or C₄~C₁₂Alpha-olefin.Therefore, term of the invention second Heterophasic propylene copolymers (HPP2) are defined as polypropylene, and the polypropylene includes the unit from following material, preferably by being derived from Constituted in the unit of following material,

(a) propylene and

(b) ethene and/or C₄~C₁₂Alpha-olefin.

Therefore, the second heterophasic propylene copolymers (HPP2) of the invention, i.e., as the one of polypropene composition (PP) Partial the second heterophasic propylene copolymers (HPP2) comprising can with the monomer of propylene copolymerization, such as comonomer, such as ethene and/ Or C₄~C₁₂Alpha-olefin, particularly ethene and/or C₄~C₈Alpha-olefin, such as 1- butylene and/or 1- alkene.Preferably, according to this Second heterophasic propylene copolymers (HPP2) of invention comprising can with the monomer of propylene copolymerization, particularly by can be with the list of propylene copolymerization Body is constituted, and the monomer is selected from by ethene, 1- butylene and the 1- groups that alkene is constituted.More specifically, the second multiphase third of the invention Alkene copolymer (HPP2) in addition to comprising propylene, also comprising the unit from ethene and/or 1- butylene.Preferably implementing In mode, the second heterophasic propylene copolymers (HPP2) of the invention are only comprising the unit from ethene and propylene.Also more Preferably, only elastomeric propylene copolymers (AM2) include ethylene comonomer.

It is therefore preferred that the elastomeric propylene copolymers (AM2) being scattered in polypropylene homopolymer matrix (PM2) include third Alkene monomer unit and selected from ethene and/or C₄~C₁₂The comonomer unit of alpha-olefin.For example, being scattered in polypropylene homopolymer Elastomeric propylene copolymers (AM2) in matrix (PM2) include propylene monomer units and ethylene comonomer units.

Therefore, elastomeric propylene copolymers (AM2) are preferably ethylene propylene copolymers, and the elastomeric propylene copolymerization that is wherein scattered here and there The matrix of thing (AM2) is then polypropylene homopolymer matrix (PM2).

Preferably, on the basis of the gross weight of the second heterophasic propylene copolymers (HPP2), as polypropene composition (PP) A part the preferred co-monomer content of the second heterophasic propylene copolymers (HPP2), optimal ethylene content is 3.0~ 8.0wt%, preferably 3.0~7.0wt%, more preferably 4.0~6.0wt%, and most preferably 4.1~5.1wt%.

In an embodiment of the invention, on the basis of the gross weight of the second heterophasic propylene copolymers (HPP2), the (25 DEG C) of dimethylbenzene cold DDGS (XCS) fraction of two heterophasic propylene copolymers (HPP2) is 9.0~20.0wt%, preferably 10.0~15.0wt%, and most preferably 12.0~14.0wt%.

Additionally or alternatively, as polypropene composition (PP) a part the second heterophasic propylene copolymers (HPP2) Melt flow rate (MFR) MFR₂(230 DEG C, 2.16kg) be 0.05~2.0g/10min, preferably 0.1~2.0g/10min, it is more excellent Elect 0.2~1.0g/10min, and most preferably 0.2~0.5g/10min as.For example, as one of polypropene composition (PP) The melt flow rate (MFR) MFR of the second heterophasic propylene copolymers (HPP2) for dividing₂(230 DEG C, 2.16kg) are 0.2~0.3g/ 10min。

Therefore, a particular requirement of the invention is, the melt flow rate (MFR) of the first heterophasic propylene copolymers (HPP1) MFR₂Different from the melt flow rate (MFR) MFR of the second heterophasic propylene copolymers (HPP2)₂(230 DEG C, 2.16kg).Of the invention In one implementation method, the melt flow rate (MFR) MFR of first heterophasic propylene copolymers (HPP1) of polypropene composition (PP)₂ (230 DEG C, 2.16kg) be 20.0~80.0g/10min, and polypropene composition (PP) the second heterophasic propylene copolymers (HPP2) melt flow rate (MFR) MFR₂(230 DEG C, 2.16kg) are 0.05~2.0g/10min.For example, polypropene composition (PP) the melt flow rate (MFR) MFR of the first heterophasic propylene copolymers (HPP1)₂(230 DEG C, 2.16kg) are 20.0~75.0g/ 10min, and second heterophasic propylene copolymers (HPP2) of polypropene composition (PP) melt flow rate (MFR) MFR₂(230 DEG C, 2.16kg) it is 0.2~0.5g/10min.

It is propylene homo as the polypropylene homopolymer matrix (PM2) of a part for the second heterophasic propylene copolymers (HPP2) Thing.In other words, the co-monomer content of polypropylene homopolymer matrix (PM2) be less than or equal to 0.5wt%, more preferably less than or Equal to 0.3wt%, and most preferably no greater than 0.1wt%.The percentage by weight is with the gross weight of polypropylene homopolymer matrix (PM2) On the basis of.

In other words, as through the term polypropylene homopolymer or polypropylene homopolymer matrix for using in full of the invention (PM2) it is related to polypropylene, the polypropylene is substantially made up of propylene units, i.e., comprising the propylene list equal to or more than 99.5wt% Unit.In a preferred embodiment, propylene units are only can detect in polypropylene homopolymer.

Moreover it is preferred that the polypropylene homopolymer matrix of the part as the second heterophasic propylene copolymers (HPP2) (PM2) dimethylbenzene cold DDGS (XCS) fraction is at a fairly low.Therefore, with the poly- of the second heterophasic propylene copolymers (HPP2) On the basis of the gross weight of propylene homopolymer matrix (PM2), the cold DDGS of the dimethylbenzene (XCS) of polypropylene homopolymer matrix (PM2) (25 DEG C) of fraction is less than 2.0wt%, preferably 0.1~2.0wt, and more preferably 0.5~2.0wt%.For example, with the second multiphase On the basis of the gross weight of the polypropylene homopolymer matrix (PM2) of propylene copolymer (HPP2), polypropylene homopolymer matrix (PM2) (25 DEG C) of dimethylbenzene cold DDGS (XCS) fraction is 1.0~2.0wt%.

Additionally or alternatively, as the second heterophasic propylene copolymers (HPP2) a part polypropylene homopolymer matrix (PM2) also there is at a fairly low melt flow rate (MFR).It is therefore preferred that the melt flows speed of polypropylene homopolymer matrix (PM2) Rate MFR₂(230 DEG C, 2.16kg) be 0.1~3.0g/10min, preferably 0.1~2.0g/10min, more preferably 0.1~ 1.0g/10min, and most preferably 0.1~0.5g/10min.

As another key component of the second heterophasic propylene copolymers (HPP2) of a part for polypropene composition (PP) It is dispersed in the elastomeric propylene copolymers (AM2) in polypropylene homopolymer matrix (PM2).

As for the comonomer used in elastomeric propylene copolymers (AM2), it is the second heterophasic propylene copolymers that may be referred to (HPP2) information for being provided.Therefore, elastomeric propylene copolymers (AM2) are comprising can be with the monomer of propylene copolymerization, such as copolymerization list Body, such as ethene and/or C₄~C₁₂Alpha-olefin, particularly ethene and/or C₄~C₈Alpha-olefin, such as 1- butylene and/or 1- are Alkene.Preferably, elastomeric propylene copolymers (AM2) comprising can with the monomer of propylene copolymerization, particularly by can be with the list of propylene copolymerization Body is constituted, and the monomer is selected from by ethene, 1- butylene and the 1- groups that alkene is constituted.More specifically, elastomeric propylene copolymers (AM2) In addition to comprising propylene, also comprising the unit from ethene and/or 1- butylene.Therefore in particularly preferred embodiment In, elastomeric propylene copolymers (AM2) are only comprising the unit from propylene and ethene.

An implementation method of the invention, is total to as the second heterophasic propylene of a part for polypropene composition (PP) Polymers (HPP2) includes amorphous (AM) phase, and the inherent viscosity (IV) of amorphous (AM) phase is 3.0~4.0dl/g, and preferably 3.5 ~4.0dl/g.

In an embodiment of the invention, with the gross weight of amorphous (AM) phase of the second heterophasic propylene copolymers (HPP2) On the basis of amount, the co-monomer content of amorphous (AM) phase of the second heterophasic propylene copolymers (HPP2), more preferably ethylene contents are 30.0~37.0wt%, and preferably 30.0~35.0wt.

As described above, a requirement of the invention is, as the first multiphase third of a part for polypropene composition (PP) Alkene copolymer (HPP1) and the second heterophasic propylene copolymers (HPP2) are provided with specified quantitative.

Preferably, it is with the gross weight of the first heterophasic propylene copolymers (HPP1) and the second heterophasic propylene copolymers (HPP2) Benchmark, polypropene composition (PP) of the invention is common comprising first heterophasic propylene of the content in the range of 66.6~95.2wt% Polymers (HPP1), and second heterophasic propylene copolymers (HPP2) of the content in the range of 4.8~33.4wt%.

For example, with the gross weight of the first heterophasic propylene copolymers (HPP1) and the second heterophasic propylene copolymers (HPP2) be base Standard, polypropene composition (PP) comprising 70.0~95.0wt% content the first heterophasic propylene copolymers (HPP1) and 5.0~ Second heterophasic propylene copolymers (HPP2) of the content of 30.0wt%.Alternatively, with the first heterophasic propylene copolymers (HPP1) and On the basis of the gross weight of the second heterophasic propylene copolymers (HPP2), polypropene composition (PP) includes containing for 80.0~95.0wt% Second heterophasic propylene copolymers (HPP2) of first heterophasic propylene copolymers (HPP1) of amount and the content of 5.0~20.0wt%. In an embodiment of the invention, with the first heterophasic propylene copolymers (HPP1) and the second heterophasic propylene copolymers (HPP2) Gross weight on the basis of, the of content of the polypropene composition (PP) comprising 85.0~95.0wt% such as 90.0~95.0wt% Second heterophasic propylene of the content of one heterophasic propylene copolymers (HPP1) and 5.0~15.0wt% such as 5.0~10.0wt% is total to Polymers (HPP2).

Additionally or alternatively, between the first heterophasic propylene copolymers (HPP1) and the second heterophasic propylene copolymers (HPP2) Weight ratio [(HPP1)/(HPP2)] in the range of 20/1~2/1, more preferably in the range of 15/1~3/1, and most preferably In the range of 12/1~3/1.

Preferably, polypropene composition (PP) of the invention can also include general additive, such as plumper, antioxygen Agent, nucleator, light stabilizer, slipping agent, and/or pigment.Preferably, the gross weight with polypropene composition (PP) is as base Standard, the content of the additive in addition to inorganic filler should be not more than 7.0wt%, should more preferably be not more than 5.0wt%.

In an embodiment of the invention, on the basis of the weight of polypropene composition (PP), polypropene composition (PP) content of first heterophasic propylene copolymers (HPP1) of the content comprising 40.0~60.0wt% and 3.0~20.0wt% Second heterophasic propylene copolymers (HPP2).For example, on the basis of the weight of polypropene composition (PP), polypropene composition (PP) The second of first heterophasic propylene copolymers (HPP1) of the content comprising 45.0~55.0wt% and the content of 3.0~15.0wt% Heterophasic propylene copolymers (HPP2).

Preferably, polypropene composition (PP) of the invention is except comprising the first heterophasic propylene copolymers (HPP1) and second Outside heterophasic propylene copolymers (HPP2), can also elastic ethylene copolymer (EE) be included to improve impact property.It is noted that bullet Sex ethylene copolymer (EE) (chemically) is different from the first heterophasic propylene copolymerization as a part for polypropene composition (PP) Second heterophasic propylene copolymerization of the elastomeric propylene copolymers (AM1) of thing (HPP1) and the part as polypropene composition (PP) The elastomeric propylene copolymers (AM2) of thing (HPP2).

Elastic ethylene copolymer (EE) is comprising ethylene unit and selected from C₄~C₁₂The comonomer unit of alpha-olefin, especially It is ethylene unit and selected from C₄~C₈The comonomer unit of alpha-olefin, such as 1- butylene and/or 1- alkene and/or 1- octenes. Preferably, elastic ethylene copolymer (EE) includes ethylene unit and the comonomer selected from 1- butylene, 1- alkene and 1- octenes Unit, is constituted particularly by ethylene unit and selected from the comonomer unit of 1- butylene, 1- alkene and 1- octenes.More specifically Ground, elastic ethylene copolymer (EE) in addition to comprising ethene, also comprising the unit from 1- butylene and/or 1- octenes.Cause This, in particularly preferred embodiments, elastic ethylene copolymer (EE) is only comprising the unit from ethene and 1- octenes.

Ethylene contents in elastic ethylene copolymer (EE) are of a relatively high.Therefore, in a preferred embodiment, with On the basis of the gross weight of elastic ethylene copolymer (EE), as the elastic ethylene copolymer of a part for polypropene composition (PP) (EE) ethylene contents are at least 50.0wt%, preferably 50.0~75.0wt%.For example, with elastic ethylene copolymer (EE) It is 60.0 as the ethylene contents of the elastic ethylene copolymer (EE) of a part for polypropene composition (PP) on the basis of gross weight ~70.0wt%, such as 65.0~70.0wt%.

Additionally or alternatively, as polypropene composition (PP) a part elastic ethylene copolymer (EE) melt Flow rate MFR₁(190 DEG C, 2.16kg) be 0.25~30.0g/10min, preferably 0.25~20.0g/10min, more preferably It is 0.25~15.0g/10min, and most preferably 0.25~10.0g/10min.

It is therefore preferred that being preferably bullet as the elastic ethylene copolymer (EE) of a part for polypropene composition (PP) Sex ethylene -1- octene copolymers, wherein, on the basis of the gross weight of elastic ethylene copolymer (EE), rubbery ethylene -1- octenes are total to The ethylene contents of polymers are at least 50.0wt%；The melt flow rate (MFR) MFR of rubbery ethylene -1- octene copolymers₁(190 DEG C, 2.16kg) it is 0.25~30.0g/10min.For example, the elastic ethylene copolymer of the part as polypropene composition (PP) (EE) it is rubbery ethylene -1- octene copolymers, wherein, on the basis of the gross weight of elastic ethylene copolymer (EE), rubbery ethylene - The ethylene contents of 1- octene copolymers are 65.0~70.0wt%；The melt flow rate (MFR) MFR of elastic ethylene copolymer (EE)₁ (190 DEG C, 2.16kg) are 0.25~10.0g/10min.

In an embodiment of the invention, on the basis of the gross weight of polypropene composition (PP), Polypropylene compositions The elastic ethylene copolymer (EE) of content of the thing (PP) comprising 5.0~20.0wt%.For example, with the total of polypropene composition (PP) On the basis of weight, the rubbery ethylene of content of the polypropene composition (PP) comprising 5.0~15.0wt% or 5.0~10.0wt% is total to Polymers (EE).

Polypropene composition (PP) of the invention is removed comprising the first heterophasic propylene copolymers (HPP1) and the second heterophasic propylene Outside copolymer (HPP2) and optional elastic ethylene copolymer (EE), can also high density polyethylene (HDPE) (HDPE) be included to change The anti-scratch performance on the surface of the kind product being molded by polypropene composition of the invention (PP).High density polyethylene (HDPE) (HDPE) (chemically) it is different from as the first heterophasic propylene copolymers (HPP1) of a part for polypropene composition (PP) Elastomeric propylene copolymers (AM2) of elastomeric propylene copolymers (AM1) and the second heterophasic propylene copolymers (HPP2) and optional Elastic ethylene copolymer (EE).

It is well known in the art and commercially available according to high density polyethylene (HDPE) used in the present invention (HDPE).

The preferred melt flow rate (MFR) MFR of high density polyethylene (HDPE) (HDPE)₁(190 DEG C, 2.16kg) are 0.2~15.0g/ 10min, preferably 0.5~10.0g/10min, more preferably 1.0~10.0g/10min, and most preferably 5.0~10.0g/ 10min。

Normally, the density of high density polyethylene (HDPE) (HDPE) is at least 930kg/m³, preferably 930~970kg/m³, and more Preferably 930~950kg/m³。

In an embodiment of the invention, on the basis of the gross weight of polypropene composition (PP), Polypropylene compositions The high density polyethylene (HDPE) (HDPE) of content of the thing (PP) comprising 5.0~10.0wt%.For example, with the total of polypropene composition (PP) On the basis of weight, the high density polyethylene (HDPE) (HDPE) of content of the polypropene composition (PP) comprising 5~8wt%.

In order to reach the expected level of rigidity, polypropene composition (PP) of the invention preferably comprises a selected amount of inorganic fill out Material (F).Therefore, on the basis of the gross weight of polypropene composition (PP), polypropene composition (PP) of the invention is preferably The inorganic filler (F) of the content comprising 15.0~25.0wt%.In an embodiment of the invention, with polypropene composition (PP) on the basis of gross weight, polypropene composition (PP) of the invention preferably comprises the content of 15.0~20.0wt% Inorganic filler.

An implementation method of the invention, inorganic filler (F) is selected from group constituted by the following substances：Talcum, cloud Mother, calcium carbonate, diatomite, wollastonite and kaolin.For example, inorganic filler (F) is talcum.

In an embodiment of the invention, the average grain diameter d of inorganic filler (F)₅₀It is 0.65~20 μm.

For example, polypropene composition (PP) includes talcum as inorganic filler (F).An embodiment party of the invention Formula, the inorganic filler for polypropene composition (PP) is with 0.65~20 μm of average grain diameter d₅₀Talcum.

Therefore, polypropene composition (PP) of the invention preferably comprises：

A) on the basis of the gross weight of polypropene composition (PP), first heterophasic propylene copolymers of 40.0~60.0wt% (HPP1),

B) on the basis of the gross weight of polypropene composition (PP), second heterophasic propylene copolymers of 3.0~20.0wt% (HPP2),

C) on the basis of the gross weight of polypropene composition (PP), the elastic ethylene copolymer (EE) of 5.0~20.0wt%, Wherein, on the basis of the gross weight of elastic ethylene copolymer (EE), the content of the ethylene unit of the elastic ethylene copolymer (EE) It is at least 50.0wt%,

D) on the basis of the gross weight of polypropene composition (PP), the high density polyethylene (HDPE) (HDPE) of 5.0~10.0wt%, And

E) on the basis of the gross weight of polypropene composition (PP), the inorganic filler (F) of 15.0~25.0wt%.

For example, polypropene composition (PP) of the invention preferably comprises：

A) on the basis of the gross weight of polypropene composition (PP), first heterophasic propylene copolymers of 45.0~55.0wt% (HPP1),

B) on the basis of the gross weight of polypropene composition (PP), second heterophasic propylene copolymers of 3.0~15.0wt% (HPP2),

C) on the basis of the gross weight of polypropene composition (PP), the elastic ethylene copolymer (EE) of 5.0~15.0wt%, Wherein, on the basis of the gross weight of elastic ethylene copolymer (EE), the content of the ethylene unit of the elastic ethylene copolymer (EE) It is at least 50.0wt%,

D) on the basis of the gross weight of polypropene composition (PP), the high density polyethylene (HDPE) (HDPE) of 5.0~8.0wt%, And

E) on the basis of the gross weight of polypropene composition (PP), the inorganic filler (F) of 15.0~20.0wt%.

Preferably, polypropene composition (PP) of the invention can also include at least one general selected from by following thing Texture into group additive：Plumper, antioxidant, nucleator, light stabilizer, ultra-violet stabilizer, slipping agent, damage resistant Agent (such as organosilicon), dispersant and coloring agent.For example, polypropene composition (PP) also includes additive, such as it is anti-oxidant Agent, ultra-violet stabilizer, damage resistant agent (for example, organosilicon), dispersant and coloring agent.Preferably, polypropylene of the invention In composition (PP), on the basis of the gross weight of polypropene composition (PP), these additives in addition to inorganic filler (F) Content should be not more than 14.0wt%, such as no more than 11.0wt%.In an embodiment of the invention, polypropene composition (PP) comprising antioxidant, ultra-violet stabilizer, damage resistant agent (such as organosilicon), dispersant and coloring agent as addition Agent, on the basis of the gross weight of polypropene composition (PP), the content of the additive is 3.0~11.0wt%, and preferably 3.0 ~8.0wt%.

Preferred damage resistant agent is organosilicon.For example, on the basis of the gross weight of polypropene composition (PP), polypropylene group The content of the damage resistant agent such as organosilicon that compound (PP) is included be less than or equal to 3.0wt%, preferably 1.0~2.0wt%, And more preferably about 1.0wt%.

Polypropene composition (PP) of the invention preferably comprises α-nucleator.It is further preferred that the present invention is without beta-nucleated Agent.According to the present invention, nucleator is defined as being different from the nucleator of inorganic filler (F).Therefore, nucleator be preferably chosen from by The group that following material is constituted：

(i) unary carboxylation and polycarboxylate, such as Sodium Benzoate or p t butylbenzoic acid aluminium；And

(ii) dibenzyl sorbitol (such as 1,3: 2,4 dibenzyl sorbitols) and C₁-C₈- alkyl-substituted two benzal Base glucitol derivative, such as methyldibenzylidene sorbierite, ethyl dibenzyl sorbitol or dimethyldibenzylidenesorbitol (such as 1,3: 2,4 two (methylbenzilidene) sorbierite) or substituted promise Buddhist nun's 01 derivatives, such as 1,2,3- tri- deoxy -4,6 : 5,7- double-O- [(4- propyl group phenyl) methylene]-Nuo Ni alcohol；And

(iii) di-phosphate ester salt, such as 2,2 '-di-2-ethylhexylphosphine oxide (4,6- di-tert-butyl-phenyl) sodium phosphate or hydroxyl-bis- [2, 2 '-methylene-bis- (4,6- di-tert-butyl-phenyl) phosphoric acid] aluminium；And

(iv) vinyl cycloalkane polymer and vinyl alkane polymers (as described above)；And

(v) its mixture.

This kind of additive generally can commercially be bought, and for example such as " the plastic additive hand of Hans Zweifel Volume (Plastic Additives Handbook) ", the 5th edition：Described in 2001.

Most preferably, α-nucleator is the first heterophasic propylene copolymers (HPP1) and/or the second heterophasic propylene copolymers (HPP2) part of (namely polypropene composition (PP)).Therefore, heterophasic propylene copolymers (HPP1) and/or heterophasic propylene α-nucleation agent content preferably up to the 5.0wt% of copolymer (HPP2) (namely polypropene composition (PP)).Preferred real In applying mode, heterophasic propylene copolymers (HPP1) and/or heterophasic propylene copolymers (HPP2) (namely polypropene composition (PP)) α-nucleator comprising no more than 3000ppm, more preferably 1~2000ppm, the α-nucleator is in particular selected from by following The group that material is constituted：Dibenzyl sorbitol (such as 1,3: 2,4 dibenzyl sorbitols), Dibenzalsorbierite derivatives, It is preferred that dimethyldibenzylidenesorbitol (such as 1,3: 2,4 two (methylbenzilidene) sorbierite) or substituted promise Buddhist nun's alcohol spread out Biology, such as 1,2,3- tri- deoxy -4, double-O- [(4- propyl group phenyl) the methylene]-Nuo Ni alcohol of 6: 5,7-, vinyl cycloalkane gather Compound, vinyl alkane polymers and its mixture.

In a preferred embodiment, heterophasic propylene copolymers (HPP1) and/or heterophasic propylene copolymers (HPP2) are (also It is polypropene composition (PP)) include vinyl cycloalkane polymer such as vinyl cyclohexane (VCH) polymer, and/or second Alkenyl alkane polymer is used as α-nucleator.Preferably, in the c implementation methods, heterophasic propylene copolymers (HPP1) and multiphase Propylene copolymer (HPP2) is poly- comprising vinyl cycloalkane such as vinyl cyclohexane (VCH) polymer and/or vinyl alkane Compound, optimal ethylene butylcyclohexane (VCH).Preferably, vinyl cycloalkane is vinyl cyclohexane (VCH) polymer, and it leads to Cross among BNT technologies are introduced in heterophasic propylene copolymers (HPP1) and/or heterophasic propylene copolymers (HPP2) and (namely drawn Enter among polypropene composition (PP)).It is highly preferred that this preferred embodiment in, heterophasic propylene copolymers (HPP1) In vinyl cycloalkane such as vinyl cyclohexane (VCH) polymer and/or vinyl alkane polymers content, more preferably The content of vinyl cyclohexane (VCH) polymer be not more than 500ppm, more preferably 1~200ppm, most preferably 5~ 100ppm；Also, heterophasic propylene copolymers (HPP2) medium vinyl cycloalkane such as vinyl cyclohexane (VCH) polymer and/ Or the content of vinyl alkane polymers, the content of more preferably vinyl cyclohexane (VCH) polymer is not more than 500ppm, more excellent Elect 1~200ppm, most preferably 5~100ppm as.It is therefore preferred that its amount in polypropene composition (PP) is not more than 500ppm, more preferably 1~200ppm, most preferably 5~100ppm.

On BNT- technologies, with reference to international application WO 99/24478, WO 99/24479, particularly WO 00/68315.Root According to this technology, the preferred Ziegler-Natta procatalyst of catalyst system in the presence of a catalyst system can be by polymerising ethylene Based compound is modified, and the catalyst system especially comprising specific Ziegler-Natta procatalyst, external donor and is helped Catalyst, wherein, vinyl compound has formula：

CH₂=CH-CHR³R⁴

Wherein, R³And R⁴Formed together 5 yuan or 6 yuan of saturated rings, unsaturation ring or aromatic rings or independently represent comprising 1~ 4 alkyl of carbon atom.Also, the catalyst being modified is used to prepare heterophasic polypropylene composition of the invention, i.e., many Phase propylene copolymer (HPP1) and/or heterophasic propylene copolymers (HPP2), most preferably heterophasic propylene copolymers (HPP1) and multiphase Propylene copolymer (HPP2).Vinyl compound after polymerization is used as α-nucleator.In the modification procedure of catalyst, vinyl The weight of compound and solid catalyst component is than preferably up to 5 (5: 1), preferably up to 3 (3: 1), most preferably 0.5 (1: 2) ~2 (2: 1).Most preferred vinyl compound is vinyl cyclohexane (VCH).

According to another aspect of the present invention, polypropene composition (PP) is prepared by following steps：In an extruder, will Second heterophasic propylene copolymers (HPP2), optional elastic ethylene copolymer (EE), optional high density polyethylene (HDPE) (HDPE), can The inorganic filler (F) of choosing and another optional additive are blended with the first heterophasic propylene copolymers (HPP1)；And, In an extruder, the first heterophasic propylene copolymers (HPP1) for will being obtained, the second heterophasic propylene copolymers (HPP2) and optional Elastic ethylene copolymer (EE), high density polyethylene (HDPE) (HDPE), the mixture of inorganic filler (F) and other additives squeeze Go out.Term " blending " of the invention refers to the behavior of the mixture for providing at least two different pre-existing materials, First heterophasic propylene copolymers (HPP1), the second heterophasic propylene copolymers (HPP2) and optional elastic ethylene copolymer are provided (EE), the behavior of the mixture of high density polyethylene (HDPE) (HDPE), inorganic filler (F) and other additives.

Can using conventional mixing apparatus or blending equipment, for example using Banbury mixer, double roller rubber grinding machine, Buss co-kneader (Buss-co-Kenader) or double screw extruder, for being by the single component of composition of the invention First heterophasic propylene copolymers (HPP1) and the second heterophasic propylene copolymers (HPP2) and optional elastic ethylene copolymer (EE), High density polyethylene (HDPE) (HDPE), inorganic filler (F) and other additives are blended.From the polymeric material that extruder is reclaimed It is common to exist in the form of granules.Then, these particles are preferably further processed, i.e., this is produced by injection molding The product and product of the composition of invention.

The screw speed of residence time or extruder in blending equipment must be selected, sufficiently high such that it is able to realize Homogenizing degree.

All components for preparing polypropene composition of the invention (PP) are it is known that and commercially commercially available. Therefore, their preparation is also known.For example, it is preferably in continuous polymerization technique, i.e., known in the art multistage In section operation, the first heterophasic propylene copolymers (HPP1) of the invention and the second heterophasic propylene copolymerization are prepared independently of one another Thing (HPP2), wherein, prepare corresponding matrix (polypropylene homopolymer matrix independently of one another at least one slurry reactor (PM1) and polypropylene homopolymer matrix (PM2)), and then, at least one i.e. one or two Gas-phase reactor each other Independently prepare elastocopolymer (elastomeric propylene copolymers (AM1) and elastomeric propylene copolymers (AM2)).

More accurately, the first heterophasic propylene copolymers (HPP1) are obtained by following steps：In at least one reactor Polypropylene homopolymer matrix (PM1) is prepared in system, the system includes at least one reactor；By the polypropylene homopolymer Matrix (PM1) is transferred in subsequent reactor system, and the system includes at least one reactor, wherein, it is equal in polypropylene In the presence of copolymer matrix (PM1), elastomeric propylene copolymers (AM1) are prepared.

Additionally or alternatively, the second heterophasic propylene copolymers (HPP2) are obtained by following steps：At least one Polypropylene homopolymer matrix (PM2) is prepared in reactor system, the system includes at least one reactor；By the polypropylene Homopolymers matrix (PM2) is transferred in subsequent reactor system, and the system includes at least one reactor, wherein, poly- In the presence of propylene homopolymer matrix (PM2), elastomeric propylene copolymers (AM2) are prepared.

Therefore, each polymerization system can include one or more conventional stirrings slurry reactor and/or one or many Individual Gas-phase reactor.Preferably, the reactor for using is selected from the group of loop reactor and Gas-phase reactor, and especially, should Technique uses at least one loop reactor and at least one Gas-phase reactor.The several various types of of series connection can also be used Reactor, such as one loop reactor and two or three Gas-phase reactor or two loop reactors and one or two Individual Gas-phase reactor.

Preferably, for the first heterophasic propylene copolymers (HPP1) and/or the system of the second heterophasic propylene copolymers (HPP2) Standby technique also comprising the prepolymerization using selected catalyst system as detailed below, the catalyst system comprising Ziegler-receive Tower major catalyst, external donor and co-catalyst.

In a preferred embodiment, prepolymerization is to carry out bulk slurry polymerizations, i.e. liquid phase in liquid propene mainly to wrap Containing propylene and a small amount of other reactants and optional dissolving inert component in the inner.

Prepolymerization normal open is carried out at a temperature of 0~50 DEG C, preferably 10~45 DEG C and more preferably 15~40 DEG C.

Pressure in pre-polymerization reactor is not crucial, but must be sufficiently high, to keep reactant mixture as liquid Phase.Therefore, pressure can be 20~100bar, such as 30~70bar.

Catalytic component is preferably fully incorporated prepolymerization step.However, in ingredient of solid catalyst (i) and co-catalyst (ii) part can be respectively fed, the co-catalyst of a part only can be incorporated into prepolymerisation stage, and by remainder It is incorporated into subsequent polymerization stage.Equally need to be introduced in the prepolymerization stage in this case and be enough to be filled wherein Divide the co-catalyst of polymerisation.

Prepolymerisation stage can also add other components.Therefore, it is such as known in the art, hydrogen can be added to pre-polymerization The conjunction stage is controlling the molecular weight of prepolymer.Additionally, antisatic additive can be used to prevent particle adhered to one another or be bonded in On the wall of reactor.

The precise control of prepolymerization conditions and response parameter is techniques well known.

Slurry reactor specifies any reactor, such as the continuous or single batch stirred tank operated on body or slurry Reactor or loop reactor, wherein polymer form the shape of particle." body " means in reaction medium comprising at least The polymerization of 60wt% monomers.According to preferred embodiment, slurry reactor includes body loop reactor.

" Gas-phase reactor " means any mechanical mixture reactor or fluidized-bed reactor.Preferably, Gas-phase reactor Comprising the mechanical agitation fluidized-bed reactor with least 0.2m/sec gas velocities.

For the first heterophasic propylene copolymers (HPP1) of the invention and/or the system of the second heterophasic propylene copolymers (HPP2) Standby particularly preferred embodiment includes a loop reactor and one or two comprising polymerization, the technique is implemented in process The combination of individual Gas-phase reactor or the combination comprising two loop reactors and one or two Gas-phase reactor.

Preferred multistage process is slurry-gas phase process, and what such as Borealis was developed is referred to asTechnology Slurry-gas phase process.In this respect, with reference to following patent document：EP 0 887 379 A1、WO 92/12182、WO 2004/ 000899th, WO 2004/111095, WO 99/24478, WO 99/24479 and WO 00/68315.They are wrapped by quoting Containing in this article.

Another suitable slurry-gas phase process is BasellTechnique.

Preferably, as detailed below, preferably such asOrDescribed in technique, made by combination The first heterophasic propylene copolymerization of the invention is prepared with specific Ziegler-Natta procatalyst and specific external donor Thing (HPP1) and/or the second heterophasic propylene copolymers (HPP2).

Therefore, a preferred multistage process can be comprised the steps of：

- in the first slurry reactor and the second optional slurry reactor, in selected catalysis for example as detailed below Polypropylene-base is prepared in the presence of agent system, the selected catalyst system includes specific Ziegler-Natta procatalyst I (), external donor (iii) and co-catalyst (ii), the two slurry reactors use identical polymerizing condition；

- the slurry reactor product is transferred at least one first Gas-phase reactor, such as one Gas-phase reactor, Or in the first Gas-phase reactor and the second Gas-phase reactor being connected in series；

- at least first Gas-phase reactor, elasticity is prepared in the presence of polypropylene-base and catalyst system Copolymer；

- polymer product is reclaimed for further technique.

On above-mentioned preferred slurry-gas phase process, the following general information provided by process conditions is may be referred to.

Temperature is preferably 40~110 DEG C, and preferably between 50~100 DEG C, particularly between 60~90 DEG C, its pressure exists 20~80bar, preferably in the range of 30~60bar, alternatively add hydrogen controlling molecular weight by the second in a known way.

Then, the product of the slurry polymerisation carried out preferably in loop reactor is transferred to subsequent gas phase reaction In device, wherein, temperature preferably in the range of 50~130 DEG C, more preferably 60~100 DEG C, pressure in the range of 5~50bar, It is preferred that 8~35bar, alternatively is added hydrogen to control molecular weight by the second in a known way again.

Mean residence time in reactor area as described above can change.In one embodiment, in slurry In material reactor, such as the mean residence time in loop reactor is in the range of 0.5~5 hour such as 0.5~2 Hour, and the mean residence time in Gas-phase reactor generally can be 1~8 hour.

Optionally, in slurry reactor, preferably in loop reactor, can be in a known manner under super critical condition It is polymerized, and/or is polymerized with condensation mode in Gas-phase reactor.

According to the present invention, as described above, heterophasic polypropylene preferably passes through multistage polymerization in the presence of catalyst system Technique is obtained.The catalyst system includes Ziegler-Natta procatalyst as component (i), the Ziegler-Natta procatalyst Ester exchange offspring comprising lower alcohol and phthalic acid ester.

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

A) by MgCl₂And C₁-C₂The spray crystallization of alcohol or the adduct and TiCl of emulsification solidification₄Reaction,

B) bialkyl ortho phthalate of the product of step a) and formula (I) is reacted

Wherein, R^1′And R^2′It independently is at least C₅Alkyl

The reaction is in the C₁-C₂There is ester exchange to form inside in the bialkyl ortho phthalate of alcohol and the formula (I) Carried out under conditions of donor,

C) product of washing step b) or

D) alternatively by the product of step c) and extra TiCl₄Reaction.

Major catalyst is for example such as patent application WO 87/07620, WO 92/19653, WO 92/19658 and EP 0 491 Preparing defined in 566.The content of these documents is incorporated herein by reference herein.

It is initially formed MgCl₂And C₁-C₂The adduct of alcohol, its formula is MgCl₂* nROH, wherein R are methyl or ethyl, with And n is 1~6.Preferred alcohol is used as alcohol.

The adduct for being melted and then being atomized crystallization or emulsification solidification first is used as catalyst carrier.

In the following step, it is MgCl by the formula of spray crystallization or emulsification solidification₂* (wherein R is methyl or second to nROH Base, preferably ethyl, and n be 1~adduct and TiCl 6)₄Contact, so as to form titanised carrier, is then walked as follows Suddenly：

Following material is added to the titanised carrier to form the first product：

The bialkyl ortho phthalate of (i) formula (I), wherein R^1′And R^2′It independently is at least C₅- alkyl, such as at least C₈- alkyl；

Or preferably,

(ii) bialkyl ortho phthalate of formula (I), wherein R^1′And R^2′It is identical, and be at least C₅- alkyl, such as extremely Few C₈- alkyl；

Or it is highly preferred that

(iii) it is selected from by phthalic acid propyl group hexyl ester (PrHP), phthalic acid dioctyl ester (DOP), adjacent benzene The adjacent benzene of the logical formula (I) of the group that two-isodecyl of dioctyl phthalate base ester (DIDP) and two-tridecane of phthalic acid base ester (DTDP) are constituted Diformazan acid dialkyl ester, the bialkyl ortho phthalate even more preferably from formula (I) is phthalic acid dioctyl ester (DOP), than Such as two-isooctyl acrylate of phthalic acid or phthalic acid diethylhexyl ester, particularly phthalic acid diethylhexyl ester；

First product is undergone suitable transesterification conditions, that is, be subjected to higher than 100 DEG C, preferably at 100~150 DEG C Between, more preferably in 130~150 DEG C of temperature, to cause the phthalic acid of the methyl alcohol or ethanol and the formula (I) There is ester exchange in the ester group of dialkyl ester, with formation preferably at least 80mol%, more preferably at least 90mol%, most preferably extremely The bialkyl ortho phthalate of the formula (II) of few 95mol%；

Wherein, R¹And R²It is methyl or ethyl, preferably ethyl,

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

The ester exchange offspring is reclaimed as major catalyst composition (component (i)).

In a preferred embodiment, formula MgCl is made₂* nROH (wherein, R is methyl or ethyl, and n be 1~6) Adduct is melted, and then the fused mass is expelled in the gas of the solvent of cooling or cooling by gas preferably, thus makes to add Compound crystallizes into form favourable in form, such as described in WO 87/07620.

The adduct of the crystallization is preferably used as catalyst carrier, and is reacted with can be used for major catalyst of the invention, such as Described in WO 92/19658 and WO 92/19653.

When by extracting removal relict catalyst, the adduct of titanised carrier and internal donor is obtained, derived from it Change from the group of ester alcohol.

If the titanium of q.s is maintained on carrier, its active element that can serve as major catalyst.

Otherwise, titanizing is repeated after being processed more than, to ensure enough titanium concentration and activity thus.

Preferably, at most 2.5wt%, preferably up to 2.2wt% and more is included according to major catalyst used in the present invention The preferably up to titanium of 2.0wt%.Its donor content preferably between 4~12wt%, and more preferably in 6~10wt%.

It is highly preferred that according to major catalyst used in the present invention by using ethanol as alcohol and phthalic acid two Octyl group ester (DOP) is as bialkyl ortho phthalate, generation diethyl phthalate (DEP) of formula (I) as internal confession It is prepared by body compound.

It is more preferred still that being such as the catalyst described in embodiment part, spy according to catalyst used in the present invention It is not that phthalic acid dioctyl ester is used as the bialkyl ortho phthalate of formula (I) according to WO 92/19658.

In another embodiment, Ziegler-Natta procatalyst can in the presence of a catalyst system pass through polymerising ethylene Based compound is modified, and the catalyst system includes specific Ziegler-Natta procatalyst, external donor and co-catalysis Agent, wherein, vinyl compound has formula：

CH₂=CH-CHR³R⁴

Wherein, R³And R⁴Formed together 5 yuan or 6 yuan of saturated rings, unsaturation ring or aromatic rings or independently represent comprising 1~ 4 alkyl of carbon atom.Also, the catalyst being modified is used to prepare heterophasic polypropylene composition of the invention.Polymerization Vinyl compound afterwards can be used as α-nucleator.This is modified and is particularly useful for making heterophasic polypropylene (H-PP1).

As for the modified of catalyst, with reference to international application WO 99/24478, WO 99/24479, with particular reference to WO 00/ 68315, will be related to modified reaction condition on catalyst in them and be related to the content bag of polymerisation by quoting Containing in this article.

In order to prepare the heterophasic polypropylene according to invention, the catalyst system for being used, preferably except comprising specific neat Outside Ge Le-Natta procatalyst, also comprising organic metal promoters as component (ii).

It is therefore preferable that selecting co-catalyst in the group constituted from following material：Trialkylaluminium such as triethyl aluminum (TEA), Dialkylaluminum chloride and alkyl sesquichloride.

The component (iii) of the catalyst system for being used is the external donor as shown in formula (IIIa) or (IIIb).Formula (IIIa) it is defined as：

Si(OCH₃)₂R₂ ⁵ (IIIa)

Wherein, R⁵Represent that there is the branched alkyl of 3~12 carbon atoms, preferably with 3~6 branched alkanes of carbon atom Base, or with 4~12 cycloalkyl of carbon atom, preferably with 5~8 cycloalkyl of carbon atom.

It is particularly preferred that R⁵Selected from group constituted by the following substances：Isopropyl, isobutyl group, isopentyl, the tert-butyl group, uncle Amyl group, neopentyl, cyclopenta, cyclohexyl, methylcyclopentyl and suberyl.

Formula (IIIb) is defined as：

Si(OCH₂CH₃)₃(NR^xR^y) (IIIb)

Wherein, R^xAnd R^yWith identical or difference, and the alkyl with 1~12 carbon atom can be represented.

R^xAnd R^yIndependently selected from group constituted by the following substances：With 1~12 linear aliphatic race alkyl of carbon atom, Branched aliphatic alkyl with 1~12 carbon atom and with 1~12 cyclic aliphatic hydrocarbon group of carbon atom.Especially Preferably, R^xAnd R^yIndependently selected from group constituted by the following substances：It is methyl, ethyl, n-propyl, normal-butyl, octyl group, decyl, different Propyl group, isobutyl group, isopentyl, the tert-butyl group, tertiary pentyl, neopentyl, cyclopenta, cyclohexyl, methylcyclopentyl and suberyl.

It is highly preferred that R^xAnd R^yThe two is identical, even more preferably from R^xAnd R^yIt is ethyl.

It is highly preferred that the external donor of formula (IIIb) is diethylamino triethoxysilane.

Most preferably, external donor is formula (IIIa), such as dicyclopentyl dimethoxyl silane [Si (OCH₃)₂(cyclopenta) 2] or diisopropyl dimethoxy silane [Si (OCH₃)₂(CH(CH₃)₂)₂]。

Polypropene composition of the invention is applied to extensive purposes.It is particularly preferred that polypropene composition of the invention Maintain mechanical property, such as well balanced rigidity/impact property, while not showing tiger fur line also.

In view of the good result obtained on polypropene composition of the invention (PP), the polypropene composition (PP) it is particularly useful for making mechanograph.Therefore, another aspect of the present invention is related to comprising polypropene composition as described above (PP) product.

For example, on the basis of the gross weight of the product, the product comprising at least 60.0wt%, more preferably at least The polypropene composition (PP) of the content of 80.0wt%, most preferably at least 95.0wt%.In an embodiment of the invention, The product is made up of polypropene composition of the invention (PP).

Preferably, the product is mechanograph, preferably injection molded article.The preferred example of this injection molded article is in automobile The large parts of the application in industry or household industry.For example, the present invention relates to a kind of automobile product, more particularly in automobile Portion and outside, such as bumper bar, body panel, spoiler, instrument board and/or door-plate.

Therefore, the present invention be more particularly directed to a kind of automobile product, more particularly to automotive interior and outside, such as bumper bar, car Body panelling, spoiler, instrument board, door-plate etc., particularly bumper bar and/or door-plate, the product include at least 60.0wt%, more excellent The polypropene composition of the invention (PP) of at least 80.0wt%, still more preferably at least 95.0wt% is selected, such as by of the invention Polypropene composition (PP) is constituted.

Therefore, another aspect of the present invention is related to the purposes of polypropene composition as described above (PP), for preparing mould Product.Preferably, polypropene composition (PP) as described above is used to prepare injection molded article.

Additionally, another aspect of the present invention is the purposes of polypropene composition as described above (PP), for reducing product Tiger fur line on surface, the product includes polypropene composition of the invention (PP), preferably by polypropene composition of the invention (PP) constitute.

Now, the present invention will further be explained by examples provided below.

Embodiment

Unless otherwise indicated, the definition of following term and assay method be applied to above-mentioned general description of the invention and with Lower embodiment.

A. definition/measuring method

Density is measured according to ISO 1183-1- methods A (2004).By according to ISO 1872-2：2007 pressing mold Complete sample preparation.

Average grain diameter d₅₀(laser diffraction) when according to ISO 13320-1 pass through laser diffraction (laser particle analyzer (Mastersizer) when) determining, calculated by particle diameter distribution [mass percent] and obtained.

MFR₂(230 DEG C) are measured according to ISO 1133 (230 DEG C of temperature loads 2.16kg).

MFR₁(190 DEG C) are measured according to ISO 1133 (190 DEG C of temperature loads 2.16kg).

The cold DDGS of dimethylbenzene (XCS, wt%)：The content of the cold DDGS of dimethylbenzene (XCS) is according to ISO 6427 at 23 DEG C Under be measured.

Content of amorphous (AM) is by separating the cold DDGS fraction (XCS) of above-mentioned dimethylbenzene and using acetone precipitation amorphous portion Divide to measure.Filter and the sediment is dried in 90 DEG C of vacuum drying oven.

AM%=(100 × m₁×v₀)/(m₀×v₁)

Wherein,

" AM% " is amorphous composition.

“m₀" it is initial polymer content (g)

“m₁" be sediment weight (g)

“v₀" it is initial volume (mL)

“v₁" it is the volume (mL) for analyzing sample

Inherent viscosity is measured according to DIN ISO in October, 1628/1,1999 (in naphthalane, at 135 DEG C).

Tensile strength, break-draw strain (or elongation at break) are according to ISO 527-2 (crosshead speed=50mm/ min；23 DEG C) measured using the injection-molded test sample (dog bone shape, 4mm is thick) described in EN ISO 1873-2.

Flexural modulus is according to ISO 294-1：1996 80 × 10 × 4mm for preparing³Injection-molded test sample on, according to ISO 178 determine 3 points of bendings.

Ai Zuode notch impact strengths according to ISO 180/1A, by using as described in EN ISO 1873-2 at 23 DEG C Injection-molded test sample (80 × 10 × 4mm) be measured.

Co-monomer content, particularly ethylene contents use use¹³The Fourier transform infrared spectroscopy that C-NMR is calibrated (FTIR) measure.When the ethylene contents in measuring polypropylene, by hot pressing for the sample thin film (μ of thickness about 250 m).The absworption peak 720cm of propylene-ethylene copolymers^-1And 733cm^-1Area use Perkin Elmer FTIR1600 spectrum Instrument is measured.In 767cm^-1Place's assessment propene-1-butene copolymer.By by¹³The ethylene contents data school of C-NMR measurements Quasi- the method.Additionally referring to " IR-Spektroskopie f ü r Anwender "；WILEY-VCH, 1997, and " Validierung in der Analytik ", WILEY-VCH, 1997.

Tiger fur line：Visual valuation shows in the black foil that size is 356 (length) × 70 (width) × 2 (thickness) mm The tendency of tiger fur line, the black foil will be extruded compound injection molding to make by using injection molding machine with the injection speed of 30mm/s .Tiger fur line on black foil surface is measured below the light source of the fluorescent lamp of 40W by naked eyes." elimination " refer to There is no the thin slice of any tiger fur line under the test condition on whole sheet surface." obvious " then means real in this test condition Test on sheet surface and occur in that tiger fur line." unobvious " mean to test in this test condition occurred in that on sheet surface it is slight Tiger fur line but unobvious.

B. embodiment

Polymer (HPP1a), (HPP1b), (HPP1c), (HPP1d) and (HPP2) with pre-polymerization reactor, one It is prepared in slurry loop reactor and two Borstar experimental rigs of Gas-phase reactor.In loop reactor and first Matrix is prepared in Gas-phase reactor, and elastomer phase is prepared in the second Gas-phase reactor.

The catalyst used in polymerization technique is prepared as follows：First, under atmospheric pressure, in the reactor By the MgCl of 0.1mol₂× 3EtOH is suspended in the decane of 250mL under inert conditions.The solution is cooled to -15 DEG C of temperature Degree, adds the cold TiCl of 300mL while the temperature is maintained at into the level₄.Then, it is the temperature of the slurry is slow Rise to 20 DEG C.At such a temperature, phthalic acid dioctyl ester (DOP) of 0.02mol is added into the slurry.In addition After phthalic acid ester, the temperature is risen to 135 DEG C in 90 minutes, and slurry is stood 60 minutes.Then, add The TiCl of another 300mL₄, and 120 minutes at keeping the temperature at 135 DEG C.Hereafter, catalyst is filtered out from liquid Come, and 300mL heptane wash is used 6 times at 80 DEG C.Then, filtering and drying solid catalytic component.Catalyst and its preparation Principle, be typically for example described in patent discloses EP 491566, EP591224 and EP 586390.Use triethyl aluminum (TEAL) as co-catalyst and dicyclopentyl dimethoxyl silane (D- donors) is used as donor.The ratio of aluminium and donor is such as Shown in table 1.

Before polymerization, prepolymerization is carried out to catalyst using a certain amount of vinyl cyclohexane, obtained with final polymer Obtain poly- (vinyl cyclohexane) (PVCH) of 200ppm concentration.Institute in respective technique such as EP 1 028 984 and EP 1 183 307 State.

Table 1：The performance of polymer (HPP1a), (HPP1b), (HPP1c), (HPP1d) and (HPP2)

Parameter	Unit	HPP1a	HPP1b	HPP1c	HPP1d	HPP2
							Donor type		D	D	D	D	D
TEAL/ donor ratios	[mol/mo1]	15	15	15	15	15
							Matrix
	[g/10min]	100	40	240	160	0.3
							XCS	[wt%]	2	1.4	2	1.0	1.5
Final performance
								[g/10min]	38	20	50	70	0.25
AM	[wt%]	18	16.5	21	18	12
							XCS	[wt%]	19	17.5	23	20	13
The IV of AM	[dl/g]	2.3	2.6	2.7	2.2	3.5
							Total C2	[wt%]	8.0	7.5	10	8.5	4.6
The C2 of AM	[wt%]	35	34	33	36	33

Based on the formula described in table 2, implementation of the present invention is prepared by using Coperion STS-35 double screw extruders The composition of example 1~10.

EE：It is the commodity " POE 8150 " of Dow Chemical (Shanghai, China).It is the elastomeric copolymer of ethene and octene Thing, wherein, ethylene contents are 61wt%, MFR₁(190 DEG C, 2.16kg) are 0.5g/10min, and density is 0.868g/cm³。

HDPE：It is commercially available polyethylene product of the purchase from Panjin petrochemical corporation (complex) (Panjin, Liaoning, China) " HD5070EA ", wherein, density is 0.95g/cm³, and MFR₁(190 DEG C, 2.16kg) are 7.5g/10min.

F：It is the commodity talc " HTP Ultra 5 " of Yi meter Fa ratios (IMI Fabi) China, wherein, d₅₀It is 0.65 μm.

P：It is the commercial pigments " CMB899- of Shanghai Yu Cheng Can Xing plastic materials Co., Ltd (Shanghai, China) Black9557”。

AC：It is the commercial polypropylene powder " HC001A-B1 " of Borealis AG, wherein, MFR₂(230 DEG C, 2.16kg) It is 2.5g/10min.

Using Coperion STS-35 double screw extruders (purchase is Chinese from (Nanjing) company grand again of section) for preparing The embodiment of the present invention comprising polypropene composition of the invention, the double screw extruder has the diameter of 35mm.The twin-screw Extruder is run with the mean speed of 400rpm, wherein, the Temperature Distribution in region is 190~235 DEG C.Its draw ratio (L/D) is 44.Temperature, flow and screw speed for preparing each region of the extruder of the composition of the embodiment of the present invention are listed in table 3。

The temperature in each region of extruder, flow and screw speed are active parameter (initiative Parameters), and on the control panel of extruder it is configured.Melt temperature (the fused mass in mould of extruder Temperature) and torque be passive parameter (passive parameters), on the control panel of extruder show.Vavuum pump is located at Region 9, and the vacuum of -0.01MPa is produced inside extruder.

AC is used as carrier and dispersion for other additives (damage resistant agent, antioxidant and UV light stabilizing agent) Agent.AC and other additives are premixed, it is then, mixed by what is obtained by the feeding machine 1 positioned at the region 1 of extruder Compound is enriched among extruder together with HPP1a/HPP1b/HPP1c/HPP1d, HPP2, EE, HDPE and P.By positioned at extrusion The side feeding machine in the region 3 of machine enriches F among extruder.Heated by the region 1-11 of extruder and in mixing extruder Material, and die head by extruder is made into particle.

Using the injection molding machine Victory 120 purchased from En Geer machineries (Shanghai) Co., Ltd., for preparing for measuring The conventional molded sample of mechanical property such as tensile property, flexural property and impact property (such as, Ai Zuode breach, 23 DEG C) and Molded sheet for measuring " tiger fur line ".The injection molding machine includes single screw rod plasticising portion and injection part.Single screw rod plasticising portion includes 3 Individual heating zone.Injection part includes nozzle and mould.In order to prepare the conventional examples for measuring mechanical property, test described above In method it is represented and require mould is conventional mould, its have dog-bone or it is rectangular have in a lateral edges it is small The internal cavities of " V " breach.

The particle of each composition of the IE1~IE10 for being obtained by extruder as described above is fed among injection molding machine.Should Particle is heated in 3 heating zones, melted and mixes, and then injects mould to form " the dog bone with " V " breach by nozzle Head " shape or rectangular sample, for measuring mechanical property.Above-mentioned injection molding machine is also commonly used for preparing for measuring " tiger fur line " Molding print, but it is 356 (length) mm × 70 (width) mm × 2 (thickness) mm's that the mould is replaced by suitable for preparing size The mould of rectangular sheet.The size and dimension mirror image of the internal cavities of mould corresponds to the thin slice for testing " tiger fur line ".

The particle of the composition of each embodiment that will be obtained in an extruder as described above feeds among injection molding machine.This Grain is heated in 3 heating zones, melts and mixed, and the cavity of mould is then injected by nozzle, to obtain for testing " tiger fur The thin slice of line ".

It is listed in measuring the technological parameter of the mechanical property of each embodiment of the invention for molded sample to be carried out into injection molding Table 4.

The mechanical property of molded sample and " the tiger fur line " of molded sheet are measured according to method as described above, and such as Shown in table 6.The mechanical property and optical property (tiger fur line) of prior art formula comparative example 1 (CE1) and comparative example 2 (CE2) are general Condition is also summarized in table 6 (6a-6b).The mechanical property and optical property of existing product (CE1 and CE2) are real always according to such as present invention The identical method used in example 1~10 is applied to be tested.

Table 6a：The performance of the embodiment of the present invention

Table 6b：The performance of the embodiment of the present invention and comparative example

E：Eliminate

C：Substantially

UC：It is unobvious

CE1：It is that the heterophasic propylene copolymers comprising 67wt%, the talcum of HDPE, 20wt% of 8wt% and residue are flat The commodity of the additive of weighing apparatus, the heterophasic propylene copolymers have：The MFR of 18g/10min₂(230 DEG C, 2.16kg), 20wt%'s Ethylene contents, the XCS of 30wt%, the AM of 29wt%, wherein, the ethylene contents of the AM of heterophasic propylene copolymers are 69wt%.

CE2：It is the commodity " C3322T-2 " of Puli's spy's composite limited company (Shanghai, China), it is included：Tool There is the MFR more than 60g/10min₂Polypropylene, the C of (230 DEG C, 2.16kg)₂-C₈Elastomer copolymer, HDPE, talcum and surplus The additive of remaining balance.

From table 6a and table 6b, compared to comparative example CE1 and CE2, the embodiment of the present invention has eliminated the appearance of tiger fur line. Additionally, the embodiment of the present invention with EE, HDPE and F shows mechanical property such as notch impact strength, rigidity and stretching Intensity goes out colour balance, and compared to comparative example CE1 and CE2 comprising similar components, these performances are retained or more preferably.

Claims

1. polypropene composition (PP), it is included：

A) on the basis of the gross weight of polypropene composition (PP), first heterophasic propylene copolymers of 40.0~60.0wt% (HPP1), wherein, the melt flow rate (MFR) MFR that the first heterophasic propylene copolymers (HPP1) are measured according to ISO 1133₂(230 DEG C, 2.16kg) it is 20.0~75.0g/10min, and

B) on the basis of the gross weight of polypropene composition (PP), second heterophasic propylene copolymers of 3.0~20.0wt% (HPP2), wherein, the melt flow rate (MFR) MFR that the second heterophasic propylene copolymers (HPP2) are measured according to ISO 1133₂(230 DEG C, 2.16kg) it is 0.2~0.3g/10min,

C) on the basis of the gross weight of polypropene composition (PP), the elastic ethylene copolymer (EE) of 5.0~20.0wt%, its In, on the basis of the gross weight of elastic ethylene copolymer (EE), the content of the ethylene unit of the elastic ethylene copolymer (EE) It is at least 50.0wt%,

E) on the basis of the gross weight of polypropene composition (PP), the inorganic filler (F) of 15.0~25.0wt%,

Wherein,

I) on the basis of the gross weight of the first heterophasic propylene copolymers (HPP1) and the second heterophasic propylene copolymers (HPP2), first The content of heterophasic propylene copolymers (HPP1) in the range of 66.6~95.2wt%, and

Ii) on the basis of the gross weight of the first heterophasic propylene copolymers (HPP1) and the second heterophasic propylene copolymers (HPP2), the The content of two heterophasic propylene copolymers (HPP2) in the range of 4.8~33.4wt%,

Wherein, the first heterophasic propylene copolymers (HPP1) have：

On the basis of the gross weight of the first heterophasic propylene copolymers (HPP1), according to (25 DEG C) dimethylbenzene of measurement of ISO 16152 Cold DDGS (XCS) level is divided into 15.0~25.0wt%；

On the basis of the gross weight of the first heterophasic propylene copolymers (HPP1), ethylene contents are less than 15.0wt%；

Inherent viscosity (IV) is amorphous (AM) phase of 2.0~3.0dl/g, wherein, with the first heterophasic propylene copolymers (HPP1) On the basis of the gross weight of amorphous (AM) phase, the ethylene contents of amorphous (AM) phase are 33.0~40.0wt%, wherein, the second multiphase third Alkene copolymer (HPP2) has：

On the basis of the gross weight of the second heterophasic propylene copolymers (HPP2), according to (25 DEG C) dimethylbenzene of measurement of ISO 16152 Cold DDGS (XCS) level is divided into 9.0~20.0wt%；

On the basis of the gross weight of the second heterophasic propylene copolymers (HPP2), ethylene contents are 3.0~8.0wt%；

Inherent viscosity (IV) is amorphous (AM) phase of 3.0~4.0dl/g, wherein, with the second heterophasic propylene copolymers (HPP2) On the basis of the gross weight of amorphous (AM) phase component, the ethylene contents of amorphous (AM) phase are 30.0~37.0wt%, and

Wherein, the first heterophasic propylene copolymers (HPP1) are by polypropylene homopolymer matrix (PM1) and are scattered in the matrix (PM1) In elastomeric propylene copolymers (AM1) constitute, the second heterophasic propylene copolymers (HPP2) by polypropylene homopolymer matrix (PM2) and The elastomeric propylene copolymers (AM2) being scattered in the matrix (PM2) are constituted.

2. polypropene composition (PP) according to claim 1, wherein, poly- the third of the first heterophasic propylene copolymers (HPP1) Polyamino alkenyl thing matrix (PM1) has：

A) the melt flow rate (MFR) MFR measured according to ISO 1133₂(230 DEG C, 2.16kg) are 30.0~250.0g/10min, and/ Or

B) on the basis of the gross weight of the polypropylene homopolymer matrix (PM1) of the first heterophasic propylene copolymers (HPP1), according to ISO Dimethylbenzene cold DDGS (XCS) level of 16152 (25 DEG C) measurements is divided into 0.8~3.0wt%.

3. polypropene composition (PP) according to claim 1, wherein, poly- the third of the second heterophasic propylene copolymers (HPP2) Polyamino alkenyl thing matrix (PM2) has：

A) the melt flow rate (MFR) MFR measured according to ISO 1133₂(230 DEG C, 2.16kg) are 0.1~3.0g/10min, and/or

B) on the basis of the gross weight of the polypropylene homopolymer matrix (PM2) of the second heterophasic propylene copolymers (HPP2), according to ISO Dimethylbenzene cold DDGS (XCS) fraction of 16152 (25 DEG C) measurements is less than 2.0wt%.

4. polypropene composition (PP) according to claim 1, wherein, the elastic ethylene copolymer (EE)：

A) comprising ethylene unit and selected from C₄~C₁₂The comonomer unit of alpha-olefin, and/or

B) on the basis of the gross weight of the elastic ethylene copolymer (EE), ethylene unit with 50.0~75.0wt% contains Amount, and/or

C) the melt flow rate (MFR) MFR measured according to ISO 1133₁(190 DEG C, 2.16kg) are 0.25~30.0g/10min.

5. polypropene composition (PP) according to claim 1, wherein, the high density polyethylene (HDPE) (HDPE) has：

A) the melt flow rate (MFR) MFR measured according to ISO 1133₁(190 DEG C, 2.16kg) are 0.2~15.0g/10min, and/or

B) density is at least 930kg/m³。

6. polypropene composition (PP) according to claim 1, wherein, the inorganic filler (F)：

A) it is selected from group constituted by the following substances：Talcum, mica, calcium carbonate, diatomite, wollastonite and kaolin, and/or

B) average grain diameter d₅₀It is 0.65~20 μm.

7. polypropene composition (PP) according to claim 1, wherein, the polypropene composition (PP) has：

A) flexural modulus measured according to ISO 178 is at least 1500MPa, and/or

B) according to ISO180 (1A；+ 23 DEG C) measurement Ai Zuode notch impact strengths be more than 30kJ/m²。

8. polypropene composition (PP) according to claim 1, wherein, the first heterophasic propylene copolymers (HPP1) and/or Second heterophasic propylene copolymers (HPP2) are through α-nucleation.

9. polypropene composition (PP) according to claim 8, wherein, the first heterophasic propylene copolymers (HPP1) and second Heterophasic propylene copolymers (HPP2) are through α-nucleation.

10. product, comprising the polypropene composition (PP) according to any one of claim 1~9.

11. products according to claim 10, the polypropene composition as any one of according to claim 1~9 (PP) constitute.

12. product according to claim 10 or 11, wherein, the product is mechanograph.

13. products according to claim 12, wherein, the product is injection molded article.

The purposes of 14. polypropene composition (PP) according to any one of claim 1~9, for preparing mechanograph.

15. purposes according to claim 14, for preparing injection molded article.

Purposes of 16. polypropene compositions (PP) in the product according to any one of claim 10~13 is prepared, uses Tiger fur line on the reduction product surface.