CN109843999A

CN109843999A - Polypropene composition with low haze

Info

Publication number: CN109843999A
Application number: CN201780062231.7A
Authority: CN
Inventors: 周信; 朱江磊; 陈世平
Original assignee: Plastic (shanghai) Co Ltd
Current assignee: Plastic (shanghai) Co Ltd
Priority date: 2016-10-17
Filing date: 2017-10-16
Publication date: 2019-06-04
Anticipated expiration: 2037-10-16
Also published as: WO2018072049A1; CN109843999B; WO2018072666A1

Abstract

The present invention relates to a kind of polypropene composition (PC), include :-more than one polypropylene (P)；It is based on the total weight of polypropene composition (PC), more than one additives (A) of 0.05~5.0 weight %；Wherein, the melting temperature of-every kind additive (A) is measured as 100 DEG C or more by DSC；And-polypropene composition (PC) is free of additive of the melting temperature lower than 100 DEG C measured by DSC.Further relate to preparation method, the product made of the composition, and pass through DSC measurement melting temperature be 100 DEG C or more additive reduce comprising more than one polypropylene (P) polypropene composition (PC) mist degree in application.

Description

Polypropene composition with low haze

Technical field

The present invention relates to a kind of polypropene composition with low haze, manufacturing methods, by the polypropene composition system At product and special additive reduce polypropene composition mist degree in application.

Background technique

Polypropene composition has many required performances, such as light-weight, durable, low in cost etc., becomes them Construct the attractive material of many automotive interiors and external component (such as lamp housing, car door, instrument board etc.).

Polypropene composition for automobile application is characterized in that high rigidity and toughness.However, the frequent quilt of automobile component Heating.Lamp housing exposes in the sun and by lamp wherein included (although developing more and more LED information display systems, mainly Halogen lamp) caused by heat.

When automobile exposes in the sun, the surface of automobile interior decoration is also heated up significantly, such as 80 DEG C or more.

At these high temperatures, volatile chemical may volatilize and be condensate in again such as lamp housing transparent front face or On vehicle window, this, which is referred to as, is atomized.

The composition for being presently available for automobile component usually meets the requirement of rigidity and toughness, however, they haze, And it is not able to satisfy the low haze requirement for becoming stringenter in the automotive industry recently.

Therefore, it is necessary to a kind of with high rigidity and high tenacity, the polypropene composition of low haze simultaneously.

Summary of the invention

Therefore, the first modification of the invention provides a kind of polypropene composition (PC), includes:

More than one polypropylene (P)

It is based on the total weight of polypropene composition (PC), more than one additives (A) of 0.05~5.0 weight %

Wherein,

Every kind of additive (A) is 100 DEG C or more by the melting temperature that DSC is measured；And

Polypropene composition (PC) is free of additive of the melting temperature lower than 100 DEG C measured by DSC.

In the second variant, the present invention provides a kind of polypropene composition (PC), include:

Polypropylene (P)

Total weight based on polypropene composition (PC), more than one additives (A) of 0.05~5.0 weight %,

Wherein,

The haze value that polypropene composition (PC) measures at 120 DEG C is 5.0% or less.

It has surprisingly been found that (such as 50 times or more) composition can be significantly reduced using specific additive Mist degree measures the mist degree as described in experimental section.This is surprising, because the fusing point of additive is higher than automobile The usually existing temperature in.In addition, the rigidity and toughness of composition are maintained, because having no need to change or not needing significantly to change Become polymer itself, but at most the processing additives used in polypropylene manufacturing process and is compounded into combination in a usual manner Additive in object needs replacing, and is thus usually only necessary to carry out minimal adjustment even not to the technological parameter of polymer It needs to adjust.

In the first modification, the haze value that preferably polypropene composition (PC) measures at 120 DEG C is 5.0% or less.

In the polypropene composition (PC) of the second modification, preferably:

Specific embodiment

All modifications of the invention described further below.

Additive (A) can not have sharp melting point.In this case, the lower end of melting peak is considered as according to this hair Bright melting temperature.For example, available melting peak starts from 110 DEG C and terminates at 130 DEG C of melting curve.In such case Under, melting temperature is 110 DEG C.

In the present invention, term " additive " does not include pigment and filler, such as mineral filler.

Term " multimodal " or " bimodal " that the present invention uses in the whole text refer to the form of polymer, that is, its molecular weight distribution The shape of curve is figure of the molecular weight fraction as the function of its molecular weight.

It is preferably based on the total amount of polypropene composition (PC), the total amount of polypropylene (P) is at least 50 weight %, more excellent Select at least 55 weight %, even more desirably at least 60 weight %, most preferably at least 65 weight %.Polypropylene (P) typically comprises poly- At least 90 weight % of whole polymer present in propylene compositions are more preferably constituted present in polypropene composition all At least 95 weight % of polymer more preferably constitute at least 98 weight % of whole polymer present in polypropene composition. Remaining polymer generally comprises the polymer as additive carrier, is preferably made of the polymer for being used as additive carrier. This carrier comprising additive is commonly known as masterbatch.

Preferably, according to the melt of the polypropene composition (PC) measured under 230 DEG C and 2.16kg load of ISO 1133 Flow rate (MFR) is 1~50g/10min, more preferably 5~40g/10min.

Stretch modulus according to the polypropene composition (PC) of ISO 527-2 measurement is preferably 3000MPa or more, more preferably For 3500MPa or more, most preferably 3800MPa or more.Usual stretch modulus is no more than 5000MPa.

Flexural modulus according to the polypropene composition (PC) measured of ISO 178 is preferably 3000MPa or more, more preferably 3400MPa or more, most preferably 3700MPa or more.Usual stretch modulus is no more than 5000MPa.

Tensile strength according to the polypropene composition (PC) of ISO 527-2 measurement is preferably 20MPa or more, more preferably 25MPa or more, most preferably 30MPa or more.Usual stretch modulus is no more than 40MPa.

Flexural strength according to the polypropene composition (PC) measured of ISO 178 is preferably 35MPa or more, more preferably 45MPa or more, most preferably 50MPa or more.Usual stretch modulus is no more than 60MPa.

The haze value of the polypropene composition (PC) measured at 120 DEG C is preferably 5.0% hereinafter, more preferably 4.5% Hereinafter, even more preferably 3.0% hereinafter, even more preferably 1.75% hereinafter, most preferably 1.0% or less.

The haze value of the polypropene composition (PC) measured at 130 DEG C is preferably 10.0% hereinafter, more preferably 5.0% Hereinafter, even more preferably 3.0% hereinafter, most preferably 1.5% or less.

The method of measurement mist degree is described in experimental section.

1.0J/ is preferably at least according to the notched IZOD impact strength of the polypropene composition (PC) measured of EN ISO 180 m², more preferably at least 2.0J/m², most preferably at least 2.4J/m²。

It preferably, is at least 890kg/m according to the density of the polypropene composition (PC) measured of ISO 1138³, more preferably At least 900kg/m³, still more preferably 900~1200kg/m³。

Preferably, polypropylene (P) includes heterophasic propylene copolymers (HECO), and/or is selected from random copolymer of propylene (RPP) With other polypropylene of Noblen (HPP), preferably Noblen (HPP).Heterophasic propylene copolymers (HECO) include base Matter (M) and elastomeric propylene copolymer (EC).In particularly preferred modification, in addition to being used as additive carrier as described above Except optional polymer, it is copolymerized in polypropene composition (PC) there is also heterophasic propylene copolymers (HECO) and selected from propylene random Other polypropylene of object (RPP) and Noblen (HPP) (preferably Noblen (HPP)).In the particularly preferred modification In, random copolymer of propylene (RPP) and Noblen (HPP) are different from the matrix of heterophasic propylene copolymers (HECO).

Heterophasic propylene copolymers (HECO) include that polypropylene is dispersed with elastomeric propylene as matrix (M) and wherein and is copolymerized Object (EC).Therefore, polypropylene-base (M) contains the content of (thin) dispersion, which is not a part of matrix, and institute It states content and contains elastomeric propylene copolymer (EC).Term " content " indicates that matrix (M) and content are total in heterophasic propylene Different phases is formed in polymers (HECO), the content is for example, by high resolution microscope such as electron microscope or scanning forces Microscope is visible.

The matrix of heterophasic propylene copolymers (HECO) and the rubber phase of heterophasic propylene copolymers (HECO) can be only by lists One polymer composition, or can be the mixture of two or more polymer, preferably every kind of polymer is only by single polymers group At.

Heterophasic propylene copolymers (HECO) can be prepared by melt blending and/or by reactor blending.In this side Face, " reactor-blending " indicate in the presence of the product of previous stage, and each portion of polymer is produced in follow-up phase Point.For example, the matrix and dispersed phase of heterophasic polypropylene can produce in such follow-up phase.

In the entire present invention, the cold insoluble matter of dimethylbenzene (XCI) of heterophasic polypropylene (HECO) partially represents matrix (M), And the cold soluble matter of dimethylbenzene (XCS) partially represents the elastomer portion of heterophasic polypropylene (HECO), i.e. elastomeric propylene copolymer (EC)。

Further, it is also possible to the propylene of the included two or more parts of melt blending, for example, by heterophasic propylene copolymers (HECO) altogether with the melting of other propylene (such as Noblen (HPP) or random copolymer, such as random copolymer of propylene (RPP)) It is mixed.

Preferably, according to the heterophasic propylene copolymers (HECO) measured under 230 DEG C and 2.16kg load of ISO 1133 Melt flow rate (MFR) (MFR) is 0.1~150g/10min, more preferable 5~120g/10min, most preferably 10~110g/10min.

Preferably, other polypropylene measured under 230 DEG C and 2.16kg load according to ISO 1133 are (selected from propylene random Copolymer (RPP) and Noblen (HPP) (preferably Noblen (HPP))) melt flow rate (MFR) (MFR) be 0.1~ 65g/10min, more preferably 5~60g/10min.

Preferably, according to the matrix of the heterophasic polypropylene (HECO) measured under 230 DEG C and 2.16kg load of ISO 1133 (M), i.e., the MFR of part the cold insoluble matter of dimethylbenzene (XCI) in heterophasic polypropylene (HECO) be 1~400g/10min, more preferable 5 ~325g/10min, most preferably 10~250g/10min.

Preferably, according to the two of the heterophasic propylene copolymers (HECO) of ISO 1628-1 (in 135 DEG C of naphthalane) measurement The inherent viscosity (IV) of the amorphous phase (AM) of the cold soluble matter part (XCS) of toluene is 1.5dl/g or more, more preferably 1.7dl/ G or more, most preferably 1.9dl/g or more.In general, the characteristic of the amorphous phase (AM) of the cold soluble matter part (XCS) of dimethylbenzene is viscous It spends (IV) and is no more than 4.0dl/g.

Correspondingly, polypropylene-base (M) content measured according to (23 DEG C) of ISO6427, the i.e. cold insoluble matter of dimethylbenzene (XCI) Content is based on heterophasic polypropylene (HECO) preferably in the range of 70.0~95.0 weight %, more preferably in 80.0~90.0 weights In the range of amount %.

Elastomeric propylene copolymer (EC) content measured according to (23 DEG C) of ISO 6427, the i.e. cold soluble matter of dimethylbenzene (XCS) it is preferably 1.0~30.0 weight %, more preferable 5.0~25.0 weight % that content, which is based on heterophasic polypropylene (HECO), optimal Select 10.0~20.0 weight %.

Elastomeric propylene copolymer (EC) content measured according to (23 DEG C) of ISO 6427, the i.e. cold soluble matter of dimethylbenzene (XCS) it is preferably 0.5~18 weight % that content, which is based on polypropene composition (PC), more preferably 1.0~13 weight %, most preferably 2.0~8.0 weight %.

Heterophasic propylene copolymers (HECO) also include comonomer in addition to propylene.Preferably, heterophasic propylene copolymers It (HECO) also include ethylene and/or C in addition to propylene₄-C₁₂Alpha-olefin.Therefore, term " propylene copolymer " according to the present invention is answered It is interpreted as the polypropylene comprising the polypropylene derived from unit below, preferably by forming derived from unit below:

(a) propylene

With

(b) ethylene and/or C₄-C₁₂Alpha-olefin.

Therefore, the atactic propene of propylene copolymer (i.e. heterophasic propylene copolymers (HECO)) according to the present invention, matrix is total Copolymer portion and elastomeric propylene copolymer (EC) include the monomer that can be copolymerized with propylene, for example, comonomer such as ethylene and/or C₄-C₁₂Alpha-olefin, especially ethylene and/or C₄-C₈Alpha-olefin, for example, 1- butylene and/or 1- hexene.Preferably, according to this hair Bright propylene copolymer includes the monomer that can be copolymerized with propylene, especially by the monomer composition that can be copolymerized with propylene, monomer choosing From ethylene, 1- butylene and 1- hexene.More specifically, propylene copolymer of the invention include in addition to propylene can derived from ethylene And/or the unit of 1- butylene.In a preferred embodiment, propylene copolymer according to the present invention includes only to be derived from second The unit of alkene and propylene.It is more preferred still that atactic propene copolymer part and the elastomer third of matrix (if present) Alkene copolymer (EC) contains identical comonomer, such as ethylene.

Therefore, elastomeric propylene copolymer (EC) is preferably EP rubbers (EPR), and the polypropylene of matrix (M) is random Propylene copolymer or Noblen, preferably the latter.

In addition, it should be understood that the co-monomer content of heterophasic propylene copolymers (HECO) is preferably 15 weight % hereinafter, more excellent Selection of land is in the range of 0.50~12.0 weight %, more preferably in the range of 1.0~10.0 weight %, even more preferably from In the range of 3.0~8.0 weight %.

Therefore, the co-monomer content of polypropylene-base (M) is 1.0 weight % hereinafter, more preferably no more than 0.8 weight % is measured, even more preferably from 0.5 weight % is no more than, is such as no more than 0.2 weight %.

It is being equal to from the unit content of propylene in the cold soluble matter of dimethylbenzene (XCS) derived from elastomeric propylene copolymer (EC) Detectable propylene content in part.Therefore, the range of detectable propylene is in the part the cold soluble matter of dimethylbenzene (XCS) 50.0~75.0 weight %, more preferable 55.0~70.0 weight %.Therefore, in a specific embodiment, elastomeric propylene Copolymer (EC) (i.e. part the cold soluble matter of dimethylbenzene (XCS)) includes 25.0~50.0 weight %, more preferable 30.0~45.0 weight Measure the derived from ethylene and/or C of %₄~C₁₂The unit of alpha-olefin.

The statement " Noblen " used throughout the present invention is related to substantially by (that is, 99.9 weight % or more) third The polypropylene of alkene unit composition.In preferred embodiments, propylene units only can be detected in Noblen.

In the case that more than one polypropylene for including in matrix (M) are atactic propene copolymers, it will be understood that random Propylene copolymer includes the monomer that can be copolymerized with propylene, such as comonomer such as ethylene and/or C₄~C₁₂Alpha-olefin, especially second Alkene and/or C₄~C₈Alpha-olefin, such as 1- butylene and/or 1- hexene.Preferably, atactic propene copolymer packet according to the present invention Containing the monomer that can be copolymerized with propylene, especially by the monomer composition that can be copolymerized with propylene, which is selected from ethylene, 1- butylene and 1- Hexene.More specifically, atactic propene copolymer of the invention include in addition to propylene can derived from ethylene and/or 1- butylene list Member.In a preferred embodiment, atactic propene copolymer includes the unit of only derived from ethylene and propylene.

Additionally, it is appreciated that the co-monomer content of atactic propene copolymer is preferably greater than 0.1~2.0 weight %'s In range, more preferably in the range of being greater than 0.1 to 1.6 weight %, even more preferably from the range of 0.1~1.0 weight %.

" random " comonomer for indicating propylene copolymer of term is randomly distributed in propylene copolymer.It is (poly- according to IUPAC Close the basic terms table in object science；1996) IUPAC recommendation understands term " random ".

As described above, heterophasic polypropylene can be prepared by or mixtures thereof reactor blending, melt blending.These methods are It is known in the art.

In a preferred modification, heterophasic polypropylene (HECO) and Noblen (HPP) or random copolymer (such as Random copolymer of propylene (RPP)), preferably Noblen (HPP) be blended.

Heterophasic polypropylene (HECO) and Noblen (HPP) or random copolymer are (for example, random copolymer of propylene (RPP)) the weight ratio preferred 1:10 to 10:1, more preferable 1:5 to 2:1, most preferably 1 between (preferably Noblen (HPP)): 3 to 1:1.

Heterophasic polypropylene (HECO) according to the present invention is preferably with multistage process known in the art production, mesostroma It is produced at least one slurry-phase reactor, subsequent elastomer copolymer produces at least one gas-phase reactor.

Therefore, polymerization system may include more than one convention stir slurry-phase reactor and/or more than one gas-phase reactor. It is preferable to use reactor be selected from loop reactor and gas-phase reactor, especially this method use at least one loop reactor With at least one gas-phase reactor.Several reactors can also be used with each type, for example, using a loop in a series arrangement Reactor and two or three gas-phase reactor or two loop reactors and one or two gas-phase reactor.

Preferably, this method further includes the catalyst system prepolymerization with selection, as described in detail later, including neat lattice Le-Natta procatalyst, external donor and co-catalyst.

In a preferred embodiment, in liquid propene, (i.e. liquid phase mainly includes propylene, wherein dissolved with few for prepolymerization Measure other reactants and optional inert component) it is middle as bulk slurry polymerizations progress.

Prepolymerization is usually at 0~50 DEG C, carries out at a temperature of preferably 10~45 DEG C, more preferable 15~40 DEG C.

Pressure in pre-polymerization reactor is not important, but must be high enough that reaction mixture keeps liquid phase.Therefore, Pressure can be 20~100 bars, such as 30~70 bars.

It is preferred that catalytic component is fully incorporated prepolymerization step.However, in ingredient of solid catalyst (i) and co-catalyst (ii) in the case where can feeding respectively, a part of co-catalyst only can be introduced into prepolymerisation stage and introduces remainder Subsequent polymerization stage.Similarly, in such a case it is necessary to which enough co-catalysts are introduced prepolymerisation stage, thus Enough polymerization reactions are obtained wherein.

Other components can also be added to prepolymerisation stage.Therefore, as known in the art, pre-polymerization can be added in hydrogen The conjunction stage is to control the molecular weight of prepolymer.In addition, antisatic additive can be used for that particle is prevented to be adhering to each other or adhere to instead It answers on the wall of device.

Prepolymerization conditions and response parameter are accurately controlled in the technical scope of this field.

Slurry-phase reactor indicates any reactor, such as with the continuous of ontology or slurry operations or simply stirs batch still Formula reactor or loop reactor, polymer form particle form wherein." ontology " refers to comprising at least 60wt% monomer Reaction media in polymerization.According to preferred embodiment, slurry-phase reactor includes ontology loop reactor.

" gas-phase reactor " refers to any mechanical mixture or fluidized-bed reactor.Preferably, gas-phase reactor includes machinery The fluidized-bed reactor of stirring, gas velocity are at least 0.2 meter per second.

The particularly preferred embodiment for being used to prepare heterophasic polypropylene of the invention (HECO) includes: including a ring The combination of road reactor and one or two gas-phase reactor or two loop reactors and one or two gas-phase reactor In combined method, it is polymerize.

Preferred multistage process is slurry-gas phase technique, such as is developed and be referred to as by BorealisSkill The slurry-gas phase technique of art.In this respect, with reference to 0 887 379A1, WO 92/12182 of EP, WO 2004/000899, WO 2004/111095, WO 99/24478, WO 99/24479 and WO 00/68315.They are incorporated herein by reference.

Another suitable slurry-gas phase technique is BasellTechnique.

Preferably, as described in detail later, by using specific Ziegler-Natta procatalyst and specific outside Donor combination preferably exists to prepare heterophasic polypropylene of the invention (HECO)OrIt is made in technique It is standby.

Therefore, a preferred multistage process may comprise steps of:

In the first slurry-phase reactor and optional second slurry-phase reactor, in the presence of selected catalyst system Prepare polypropylene-base, such as be described below in detail, catalyst system include specific Ziegler-Natta procatalyst (i), External donor (iii) and co-catalyst (ii), two slurry-phase reactors use identical polymerizing condition,

Slurry-phase reactor product is transferred at least one first gas-phase reactor, such as a gas-phase reactor or string Join the first gas-phase reactor and the second gas-phase reactor of connection,

In at least first gas-phase reactor, in the presence of polypropylene-base and in the presence of a catalyst system, system Standby elastomer copolymer,

Recycling polymer product is for being further processed.

About above-mentioned preferred slurry-gas phase technique, the following general information about process conditions can be provided.

Temperature is preferably 40~110 DEG C, preferably 50~100 DEG C, especially 60~90 DEG C, and pressure limit is 20~80 bars, It is preferred that 30~60 bars, it may be optionally added hydrogen to control molecular weight in a way known.

The reaction product of slurry polymerization (carrying out preferably in loop reactor) is then transferred to subsequent gas phase reaction In device, wherein temperature is preferably in the range of 50~130 DEG C, and more preferable 60~100 DEG C, pressure limit is 5~50 bars, and preferably 8 ~35 bars, and can choose addition hydrogen to control molecular weight in a way known.

Mean residence time in the reactor area being determined above can change.In one embodiment, slurry Mean residence time in reactor (such as loop reactor) is 0.5~5 hour, such as 0.5~2 hour, and gas phase reaction Mean residence time in device is usually 1~8 hour.

If desired, can at supercritical conditions in a known way in slurry-phase reactor (preferably loop reactor) into Row polymerization, and/or polymerize in gas-phase reactor with condensation mode.

, according to the invention it is preferred to be obtained in the presence of catalyst system by multistage polymerization technique as described above Heterophasic polypropylene, the catalyst system include Ziegler-Natta procatalyst as component (i), containing lower alcohol with The transesterification product of phthalic acid ester.

Major catalyst used according to the invention is prepared as follows:

A) by MgCl₂And C₁-C₂Spray crystallization or lotion the solidification adduct and TiCl of alcohol₄Reaction,

B) in the C₁-C₂Transesterification occurs for the bialkyl ortho phthalate of the pure and mild formula (I) to form internal donor Under conditions of, the product of stage a) and the bialkyl ortho phthalate of formula (I) are reacted,

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

C) product of washing stage b), or

D) optionally, make the product and other TiCl of stage c)₄Reaction.

For example, major catalyst such as patent application WO 87/07620, WO 92/19653, WO 92/19658 and EP 0491 Production as defined in 566.The content of these documents is incorporated herein by reference herein.

Firstly, forming MgCl₂And C₁-C₂Adduct (the formula MgCl of alcohol₂* nROH), wherein R be methyl or ethyl, n be 1~ 6.Preferably, ethyl alcohol is used as alcohol.

By adduct fusing, then spray crystallization or lotion solidify first, are used as catalyst carrier.

In next step, formula MgCl₂* nROH (wherein R be methyl or ethyl (preferably ethyl), n be 1~6) spray crystallization or Lotion solidifies adduct and TiCl₄Contact, to form titanised carrier, following step is as follows:

Following substances are added to the titanised carrier, to form the first product:

(i) bialkyl ortho phthalate of 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 more preferably

(iii) bialkyl ortho phthalate of formula (I), selected from the own ester of phthalic acid propyl (PrHP), adjacent benzene two Formic acid dioctyl ester (DOP), diisooctyl phthalate (DIDP) and phthalic acid double tridecyl ester (DTDP), it is also more excellent The bialkyl ortho phthalate for selecting formula (I) is dioctyl phthalate (DOP), such as diisooctyl phthalate or neighbour Phthalic acid ethylhexyl, especially di (2-ethylhexyl) phthalate,

First product is set to undergo suitable transesterification conditions, that is, temperature is higher than 100 DEG C, and preferably 100~150 DEG C, More preferable 130~150 DEG C, so that the ester group of the methanol or ethyl alcohol and the bialkyl ortho phthalate of the formula (I) Transesterification is carried out, to form preferably at least 80 moles of %, the adjacent benzene of the formula (II) of more preferable 90 moles of %, most preferably 95 moles % Diformazan acid dialkyl ester:

Wherein R¹And R²It is methyl or ethyl, preferably ethyl,

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

The transesterification product is recycled, as major catalyst composition (component (i)).

In a preferred embodiment, formula MgCl₂* the adduct of nROH (wherein R is methyl or ethyl, and n is 1~6) Be melted, then in gas of the melt preferably by gas injection cooling solvent or cooling, thus by adduct crystallization at Advantageous form in form, as described in such as WO 87/07620.

The adduct of the crystallization is preferably used as catalyst carrier, and with described in WO 92/19658 and WO 92/19653 Major catalyst reaction for use in the present invention.

Relict catalyst is removed by extraction, obtains the adduct of titanised carrier and internal donor, wherein being derived from ester The group of alcohol has changed.

When retaining enough titaniums on carrier, it is by the active element as major catalyst.

Otherwise, repeat titanizing, after being like this to ensure enough titanium concentration so that it is guaranteed that activity.

Preferably, the titanium contained by major catalyst that the present invention uses at most 2.5 weight %, preferably up to 2.2 weight %, More preferably up to 2.0 weight %.Its donor content is preferably 4~12 weight %, more preferably 6~10 weight %.

It is highly preferred that the adjacent benzene by using ethyl alcohol as pure and mild dioctyl phthalate (DOP) as formula (I) Diformazan acid dialkyl ester generates diethyl phthalate (DEP) as internal donor compound and is made what the present invention used Major catalyst.

In another preferred embodiment, Ziegler-Natta procatalyst can be by existing in catalyst system Lower vinyl compounds are modified, which includes specific Ziegler-Natta procatalyst, external donor And co-catalyst, the vinyl compound have following formula:

CH₂=CH-CHR³R⁴

Wherein, R³And R⁴It is formed together 5- or 6-membered saturation, insatiable hunger and/or aromatic ring or independently indicates comprising 1~4 The alkyl of carbon atom, and modified catalyst is used to prepare heterophasic polypropylene composition of the invention.The vinyl chemical combination of polymerization Object can be used as α-nucleating agent.The modification is used in particular for preparing heterophasic polypropylene (H-PP1).

About the modification of catalyst, with reference to international application WO 99/24478, WO 99/24479, and especially WO 00/ 68315, about catalyst modification and the reaction condition of polymerization reaction, these documents are incorporated herein by reference.

It is used other than specific Ziegler-Natta procatalyst in order to prepare heterophasic polypropylene of the invention Catalyst system preferably comprises organic metal co-catalyst as component (ii).

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

The component (iii) of used catalyst system is the external donor indicated by formula (IIIa) or (IIIb).Formula (IIIa) By defined below:

Si(OCH₃)₂R₂ ⁵ (IIIa)

Wherein R⁵The branched alkyl with 3~12 carbon atoms is indicated, preferably with the branched alkyl of 3~6 carbon atoms Or the naphthenic base with 4~12 carbon atoms, preferably with the naphthenic base of 5~8 carbon atoms.

It is particularly preferred that R⁵Selected from isopropyl, isobutyl group, isopentyl, tert-butyl, tertiary pentyl, neopentyl, cyclopenta, ring Hexyl, methylcyclopentyl and suberyl.

Formula (IIIb) is by defined below:

Si(OCH₂CH₃)₃(NR^xR^y) (IIIb)

Wherein, R^xAnd R^yCan be identical or different, represent the alkyl with 1~12 carbon atom.

R^xAnd R^yIndependently selected from the linear aliphatic hydrocarbon group with 1~12 carbon atom, the branch with 1~12 carbon atom Chain aliphatic hydrocarbyl and cyclic aliphatic hydrocarbon group with 1~12 carbon atom.Particularly preferred R^xAnd R^yIndependently selected from methyl, ethyl, N-propyl, normal-butyl, octyl, decyl, isopropyl, isobutyl group, isopentyl, tert-butyl, tertiary pentyl, neopentyl, cyclopenta, hexamethylene Base, methylcyclopentyl and suberyl.

More preferable R^xAnd R^yIt is identical, even more preferably from R^xAnd R^yIt is all ethyl.

Most preferably external donor is such as dicyclopentyl dimethoxyl silane [Si (OCH shown in formula (IIIa)₃)₂(ring penta Base)₂], diisopropyl dimethoxy silane [Si (OCH₃)₂(CH(CH₃)₂)₂]。

Other polypropylene

As described above, polypropylene (P) preferably comprises heterophasic propylene copolymers (HECO), and/or it is copolymerized selected from propylene random Other polypropylene of object (RPP) and Noblen (HPP), preferably Noblen (HPP).

Hereinafter, these polymer are described in detail.

Random copolymer of propylene (RPP)

The melt flow rate (MFR) MFR that random copolymer of propylene (RPP) is measured according to ISO 1133₂(230 DEG C, 2.16kg) no More than 50g/10min, preferably in the range of 1~30g/10min, more preferably in the range of 2~20g/10min, such as 4~ In the range of 15g/10min.

In another preferred modification, random copolymer of propylene (RPP) is fast according to the melt flows that ISO 1133 is measured Rate MFR₂(230 DEG C, 2.16kg) are no more than 75g/10min, preferably in the range of 1~70g/10min, more preferably 5~ In the range of 65g/10min.

The melting temperature T of random copolymer of propylene (RPP)_mIt is preferred that in the range of 150~170 DEG C, preferably 155~ In the range of 170 DEG C, more preferably in the range of 160~170 DEG C, such as in the range of 164~170 DEG C.

According to molecular weight, random copolymer of propylene (RPP) can be it is unimodal or multimodal or bimodal, preferably propylene without It is multimodal or bimodal for advising copolymer (RPP), and more preferable random copolymer of propylene (RPP) is bimodal.

It is preferred that random copolymer of propylene (RPP) is isotactic.It is, therefore, to be understood that random copolymer of propylene (RPP) With quite high five-tuple concentration, that is, it is higher than 80%, more preferably higher than 85%, even more preferably greater than 90%, even more preferably from height In 92%, even more preferably greater than 93%, such as it is higher than 95%.

Preferably, random copolymer of propylene (RPP) is at least 870kg/m according to the density that ISO 1138 is measured³, more preferably At least 890kg/m³, even more desirably at least 900kg/m³, even more preferably from 900~915kg/m³。

It is preferably based on the total weight of random copolymer of propylene (RPP), random copolymer of propylene (RPP) includes less than 1 weight Measure the comonomer selected from alpha-olefin (such as ethylene, butylene, hexene, optimal ethylene) of %.

Based on the total weight of random copolymer of propylene (RPP), random copolymer of propylene (RPP) preferably has less than 3.0 weights Measure %, part the cold soluble matter of dimethylbenzene (XCS) of preferably 1.5~2.5 weight %.

Noblen (HPP)

The melt flow rate (MFR) MFR that Noblen (HPP) is measured according to ISO 1133₂(230 DEG C, 2.16kg) are no more than 50g/10min, preferably in the range of 1~30g/10min, more preferably in the range of 2~20g/10min, such as in 4~15g/ In the range of 10min.

In another preferred modification, melt flow rate (MFR) that Noblen (HPP) is measured according to ISO 1133 MFR₂(230 DEG C, 2.16kg) are no more than 75g/10min, preferably in the range of 1~70g/10min, more preferably in 5~65g/ In the range of 10min.

The melting temperature T of Noblen (HPP)_mIt is preferred that in the range of 150~170 DEG C, preferably at 155~170 DEG C In the range of, more preferably in the range of 160~170 DEG C, such as in the range of 164~170 DEG C.

As described above, statement " Noblen " used in the present invention is related to substantially being made of propylene units (that is, 99 The propylene units of weight % or more, the preferably propylene units of 99.9 weight % or more) polypropylene.In preferred embodiment In, propylene units only can be detected in Noblen.

According to molecular weight, Noblen (HPP) can be unimodal or multimodal or bimodal, preferred Noblen It (HPP) is multimodal or bimodal, more preferable Noblen (HPP) is bimodal.

It is preferred that Noblen (HPP) is isotactic.It is, therefore, to be understood that Noblen (HPP) has quite High five-tuple concentration is higher than 80%, more preferably higher than 85%, even more preferably greater than 90%, even more preferably greater than 92%, also More preferably higher than 93%, such as it is higher than 95%.

Preferably, Noblen (HPP) is at least 870kg/m according to the density that ISO 1138 is measured³, more preferably at least 890kg/m³, even more desirably at least 900kg/m³, even more preferably from 900~915kg/m³。

Random copolymer of propylene (RPP) according to the present invention and Noblen (HPP) can in slurry-phase reactor and/or It is produced in gas-phase reactor.

It is excellent in the case where random copolymer of propylene (RPP) or preferred Noblen (HPP) are multimodals or are bimodal Choosing with multistage process known in the art production, the multistage process include at least one slurry-phase reactor and then at least One gas-phase reactor.

As described above, random copolymer of propylene (RPP) and/or preferred Noblen (HPP) be preferably it is bimodal.? In this case, it is preferably produced with multistage process, which includes that two slurry-phase reactors or a slurry are anti- Device, and a subsequent gas-phase reactor are answered, more preferably in a slurry-phase reactor and a subsequent gas-phase reactor.

Preferred slurries reactor is loop reactor.

Another suitable slurry-gas phase technique is BasellTechnique.

Suitable catalyst system is described in EP 591224, is incorporated herein by reference.

CH₂=CH-CHR³R⁴

As described above, comprising heterophasic propylene copolymers (HECO) and being selected from random copolymer of propylene (RPP) at polypropylene (P) In other polyacrylic situations of Noblen (HPP) (preferably Noblen (HPP)), other polypropylene (preferably should Preferred Noblen (HPP)) it is different from the matrix of heterophasic propylene copolymers (HECO).In general, Noblen (HPP) is extremely Few matrix for being different from heterophasic propylene copolymers (HECO) in terms of melt flow rate (MFR) (MFR).

Mineral filler (F)

In addition to polymers compositions, it is based on the total amount of polypropene composition (PC), polymer composition of the invention (PC) packet Containing at most 45 weight %, preferably up to 40 weight %, the more preferably up to mineral filler (F) of 30 weight %.

Generally, based on the total amount of polypropene composition (PC), the content of mineral filler (F) is 1.0 weight % or more, more excellent Select 5.0 weight % or more, most preferably 10 weight % or more.

Preferably, mineral filler (F) is selected from glass fibre, carbon fiber, phyllosilicate, mica, or mixtures thereof wollastonite. Even further preferably, mineral filler (F) is selected from mica, wollastonite, kaolinite, montmorillonite, montmorillonite and talcum.Most preferred mine Object filler (F) is talcum.

Usually and preferably, it other than mineral filler defined above (F), is not present in polypropene composition (PC) Other mineral filler.Accordingly, there exist mineral filler be preferably made of mineral filler (F).

The average grain diameter d50 [mass percent] of mineral filler (F) preferably in the range of 1~20 μm, more preferably 1~ In the range of 10 μm, even more preferably from the range of 1~5 μm.

In general, the cut-off partial size d95 [mass percent] of mineral filler (F) is 20 μm hereinafter, more preferably 2.5~10 In the range of μm.

In general, mineral filler (F) is according to commonly known BET method N₂Surface of the gas as analysis adsorbent measurement Product is less than 22m²/ g, more preferably less than 20m²/ g, even more preferably less than 18m²/g。

The representative instance of commercially available talc product is Luzenac A7C, Steamic T1CA, Jetfine T1CA and HAR (height Aspect ratio) talcum.

Pigment

Optionally, polypropene composition includes pigment.Suitable pigment is known in the art.

It is preferable to use black pigments.

Total weight based on polypropene composition is present in the total amount of the pigment in polypropene composition of the invention (PC) Preferably 0.10~5.0 weight %, more preferable 0.25~3.5 weight %, most preferably 0.25~2.5 weight %.

Additive (A)

Preferably, additive (A) includes antioxidant, processing aid, acid scavenger, lubricant.

The total amount of additive (A) is preferably in the range of 0.05~5.0 weight %, more preferable 0.10~3.5 weight %, most It is preferred that 0.25~2.5 weight %.

As described above, various additives (A) are 100 DEG C or more by the melting temperature that DSC is measured.

Suitable additive is, for example, following compound:

Antioxidant

1,3,5- tri- (3 ', 5 '-di-t-butyls -4 '-hydroxybenzyl) isocyanuric acid, No. CAS: 27676-62-6, T_m 218 ℃；

Phosphorous acid three (2,4- di-tert-butyl-phenyl) ester, No. CAS: 31570-04-4, T_m182℃；

Poly- ((6- morpholino-guanamine, 4- diyl) (1,2,2,6,6- pentamethyl -4- piperidyl) imino group) six methylenes Base (1,2,2,6,6- pentamethyl -4- piperidyl) imino group)), No. CAS: 193098-40-7, it can be used as Cyasorb UV-3529 It is obtained from Cytec, Tm:110 DEG C；

1,3,5- trimethyl -2,4,6- tri- (3,5- di-tert-butyl-hydroxy phenyl) benzene, No. CAS: 1709-70-2, Tm: 240℃；

Double-(3,3- bis--(4'- hydroxyl -3'- tert-butyl-phenyl) butyric acid)-glycol ester, No. CAS: 32509-66-3, Tm: 167℃；

1,3,5- tri- (4- tert-butyl -3- hydroxyl -2,6- dimethyl benzyl) -1,3,5- triazine -2,4,6- (1H, 3H, 5H) - Triketone, No. CAS: 40601-76-1, Tm:159 DEG C；

Processing aid:

Talcum, Tm:800 DEG C,

Acid scavenger:

Calcium stearate, Tm:145 DEG C

Method

The invention further relates to a kind of methods for being used to prepare polypropene composition of the invention (PC), comprising the following steps:

(i) more than one polypropylene (P) are provided；

(ii) more than one additives (A) are provided, wherein every kind of additive (A) is 100 by the melting temperature that DSC is measured DEG C or more；

(iii) melting mixing polypropylene (P) and additive (A)；

Wherein,

There is no the additives that the melting temperature measured by DSC is lower than 100 DEG C in polypropylene (P)；And

Additive of the melting temperature lower than 100 DEG C by DSC measurement is not added in method.

The melting mixing of polypropylene and additive is well known in the art, such as uses static mixer or extrusion Machine.It is preferable to use extruders, such as counter rotating twin screW extruder.

Other components can reside in step (iii), such as mineral filler (F) and/or pigment defined in the present invention.

Additive and optional pigment and mineral filler (F) (if present) can be added simultaneously or then be added. In the case where method of the invention carries out in an extruder, additive and optional pigment and mineral filler (if there is Words) usually it is added by one or more side feeders of extruder.

Usually and preferably, added before additive (A) and pigment (if present) mineral filler (F) (if In the presence of if).

Usually and preferably, added after additive (A) and mineral filler (F) (if present) pigment (if In the presence of if).

In the case where method of the invention carries out in an extruder, usually and preferably, individual side feeder is used for Mineral filler (F) (if present), additive (A) and pigment (if present).

It, can be pre- by additive and polypropylene powder (carrier as additive) before being added in polypropylene (P) Mixing.Usually and preferably, it is based on the total weight of polypropene composition (PC), the amount of the polypropylene powder is not more than 2.0 weights Measure %, more preferably no more than 1.0 weight %.

Temperature during melting mixing is preferably in the range of 190~260 DEG C.

The invention further relates to a kind of products, comprising polypropene composition (PC) of the invention, preferably by of the invention poly- third Ene compositions (PC) composition.

Article according to the invention is preferably injection-molded item, such as automotive interior and external component.

The additive (A) for being 100 DEG C or more the invention further relates to the melting temperature measured by DSC is being reduced comprising one kind Application in the mist degree of the polypropene composition (PC) of the above polypropylene (P).

The preferred embodiment of polypropene composition (PC) of the invention is also the excellent of method of the invention, product and application Embodiment is selected, vice versa.

Experimental section

Melt flow rate (MFR) (MFR) is according to ISO 1133 (230 DEG C, 2.16kg load) measurement.

(dog-bone shapes, 4mm are thick using injection-molded test specimens described in EN ISO 1873-2 for stretch modulus and tensile strength Degree), according to ISO 527-2 (crosshead speed=50mm/min；23 DEG C) it measures.

Bending modulus and bending strength are in 80 × 10 × 4mm according to EN ISO 1873-2 injection molding³On test bar, It is measured according to ISO 178 at 23 DEG C with 3 points of bendings.

Density is measured according to ISO 1183.

The cut-off partial size d95 and average grain diameter d50 of mineral filler are surveyed according to ISO 13320-1 by laser particle size analyzer It is fixed.

The surface area of mineral filler is measured according to ISO 9277.

Notched IZOD impact strength (23 DEG C) is measured according to EN ISO 180.

Polymer and additive are measured using Mettler TA820 differential scanning calorimetry (DSC) 5~10mg sample Melting temperature T_m.Between 30 DEG C to 225 DEG C, scanning is cooled and heated with 10 DEG C/min, obtains crystallization curve and melting curve.It is molten Melt temperature to obtain as endothermic peak and exothermic peak.Melting temperature (the T of additive_m) can also be obtained from document.However, in this hair In bright, the value as above obtained is used.

Mist degree

Polymer and combinations thereof

Using the mist degree equipment " Haze-gard dual 4727 " of German BYK-Gardner, according to Koito The mist degree test method of Manufacturing Co., Ltd. (Japan), the mist degree of test polymer or combinations thereof object.

Testing procedure:

A. the plate of polymer samples (diameter 80mm, thickness 3mm) is put into glass container and is atomized, use sealing ring cap Glass plate, is then fixed on sealing ring by the firmly opening of glass container.Finally, cooling device is fixed on a glass；

B. glass container is put into 120 DEG C or 130 DEG C of hot tank (" FT-F1 " of Shandong Province of China Labthink company) and is added Heat 24 hours, sample generate escaping gas rise and condense in be cooled to by cooling device 25 DEG C glass plate following table Face；

C. after heating and condensing 24 hours, glass plate is taken out from container, and glass plate is then put at room temperature dry In dry utensil, until glass plate reaches room temperature.Use the mist degree of mist degree machine " Haze-gard dual 4727 " measurement glass plate.

Haze value is calculated by following equation:

Mist degree rate (%)=((T4/T2)-T3 (T2/T1)) × 100%

T1: the light quantity being incident on glass plate

T2: through the light summation of glass plate

T3: the light quantity of instrument scattering

T4: the light quantity of instrument and test specimen scattering

Wherein, T1, T2, T3 and T4 are tested by BYK-Gardner " Haze-gard dual 4727 " mist degree equipment With the value of acquisition.

Additive itself

The above method can also be used for the mist degree of or mixtures thereof test additive.In this case, the above method is repeated, Wherein the pure additive in powder replaces circular slab to be used as sample, in an amount equivalent to the Polypropylene compositions of diameter 80mm, thickness 3mm It is measured present in the circular slab of object, which is made of the polypropene composition comprising these additives.

The cold soluble matter part (XCS, wt%) of dimethylbenzene is according to the 16152 (first edition of ISO；2005-07-01) at 25 DEG C Measurement.

By separating the cold soluble matter part (XCS) of above-mentioned dimethylbenzene and using acetone precipitation pars amorpha, to measure without calmly Shape content (AM).Filtering precipitate is simultaneously dry in 90 DEG C of vacuum drying oven.

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

Number-average molecular weight (M_n), weight average molecular weight (M_w) and molecular weight distribution (MWD) pass through gel permeation chromatography (GPC) It is measured according to following methods:

Weight average molecular weight M_wWith molecular weight distribution (MWD=M_w/M_n, wherein M_nIt is number-average molecular weight, M_wIt is weight average molecular weight) It is measured by the method based on ISO 16014-1:2003 and ISO 16014-4:2003.In 145 DEG C and the steady flow of 1mL/min Under speed, using 2000 instrument of Waters Alliance GPCV equipped with refractive index detector and in-line viscometer, use 3 × TSK- gel column (GMHXL-HT) and 1 from TosoHaas, 2,4- trichloro-benzenes (TCB, with the tertiary fourth of 2,6- bis- of 200mg/L Base -4- methylphenol is stablized) it is used as solvent.216.5 μ L sample solution of analysis injection every time.Use 19 narrow MWD polystyrene (PS) the wide polypropylene mark that relative calibration and one group of the reference substance within the scope of 0.5kg/mol~11,500kg/mol sufficiently characterize Quasi- object calibrates column group.By the way that it is steady that 5~10mg polymer is dissolved in 10mL (at 160 DEG C) before sampling into GPC instrument In fixed TCB (identical as mobile phase) and continuous shake 3 hours is kept, to prepare all samples.

Microstructure is quantified by NMR spectra

Quantitative nuclear magnetic resonance (NMR) spectrum is further used for the co-monomer content of quantifying polymers.For¹H and¹³C, The Bruker Advance III 400NMR spectrometer recording solution run at 400.15MHz and 100.62MHz is used respectively State quantifies¹³C{¹H } NMR spectra.By using¹³The optimal 10mm elongating temperature probe of C, under conditions of 125 DEG C, for All atmosphere use nitrogen, to record all spectrum.By the material of about 200mg and chromium acetylacetonate (III) (Cr (levulinic Ketone)₃) it is dissolved in the 7,2- tetrachloroethanes-d of 3ml together₂(TCE-d₂) in, obtain 65mM relaxation agent solution in a solvent (Singh,G.,Kothari,A.,Gupta,V.,Polymer Testing 28 5(2009),475).In order to ensure uniformly molten Liquid after carrying out initial sample preparation in hot-zone, NMR pipe is further heated in revolving burner 1 hour few.In insertion magnetic After body, which is rotated at 10Hz.This set is selected primarily to high-resolution and accurate quantification ethylene contents are quantitative It is required.In the case where not utilizing NOE, come using best pinnacle angle, 1s recycling delay and double horizontal WALTZ16 decoupled systems Using standard pulse excitation (Zhou, Z., Kuemmerle, R., Qiu, X., Redwine, D., Cong, R., Taha, A., Baugh,D.,Winniford,B.,J.Mag.Reson.187(2007)225；Busico,V.,Carbonniere,P., Cipullo,R.,Pellecchia,R.,Severn,J.,Talarico,G.,Macromol.Rapid Commun.2007,28, 1128).6144 (6k) a transient state in total is obtained to each spectrum.

To quantitative¹³C{¹H } H NMR spectroscopy is handled, is integrated, and determines phase by integrating using proprietary computer program The quantization property of pass.It is displaced using solution chemical, ethylene block of all equal indirect references of chemical shift at 30.00ppm (EEE) central methylene.Even if this method also allows than reference in the case where this structural unit is not present.It sees It observes and the corresponding characteristic signal (Cheng, H.N., Macromolecules 17 (1984), 1950) of the combination of ethylene.

By running through¹³C{¹H } whole SPECTRAL REGIONs in spectrum multiple signal integral, use (Wang, the W- such as Wang J., method Zhu, S., Macromolecules 33 (2000), 1157), to be quantified to comonomer score.Select this To the computing capability of existing area defects when the reason of kind method, is its robustness (robust nature) and needs. Integral domain is finely adjusted, to increase the applicability to the co-monomer content encountered in entire scope.

For wherein only observing the system of the isolated ethylene in PPEPP sequence, the method for modification Wang et al., to reduce The influence of the non-zero integral in the known site being not present.This approach reduces the mistakes of the ethylene contents to this system to over-evaluate It calculates, and is realized by reducing the quantity for determining the site of absolute ethylene contents:

E=0.5 (S β β+S β γ+S β δ+0.5 (S α β+S α γ))

By using this group of site, corresponding integral equation becomes:

E=0.5 (I_H+I_G+0.5(I_C+I_D))

Use institute in the article (Wang, W-J., Zhu, S., Macromolecules 33 (2000), 1157) of Wang et al. The same symbol.Equation for absolute propylene content is not modified.

The molar percentage of comonomer incorporation is calculated by molar fraction:

E [mole %]=100 × fE

The weight percent of comonomer incorporation is calculated by molar fraction:

[weight %]=100 × (fE × 28.06) E/((fE × 28.06)+((1-fE) × 42.08))

Using Kakugo et al. analysis method (Kakugo, M., Naito, Y., Mizunuma, K., Miyatake, T., Macromolecules 15 (1982) 1150), to measure the distribution of the comonomer sequence under triple level.Select this side The reason of method, is its robustness and integral domain fine tuning to increase being applicable in the co-monomer content of wider range Property.

The compound used

(3 ', the 5 '-di-t-butyls -4 '-hydroxybenzyl) isocyanide of 1,3,5- tri- urine that Irganox 3114 is obtained by BASF Acid, No. CAS: 27676-62-6, T_m218℃；

Phosphorous acid three (2,4- di-tert-butyl-phenyl) ester that Irgafos 168 is obtained by BASF, No. CAS: 31570-04-4, T_m182℃；

Poly- ((6- morpholino-guanamine, 4- diyl) (1,2,2,6,6- that Cyasorb UV-3529 is obtained by Cytec Pentamethyl -4- piperidyl) imino group) hexa-methylene (1,2,2,6,6- pentamethyl -4- piperidyl) imino group)), No. CAS: 193098-40-7, T_m: 110 DEG C；

Octadecyl 3- (3 ', 5 '-di-tert-butyl-hydroxy phenyl) propionic ester that Irganox 1076 is obtained by BASF, No. CAS: 2082-79-3, T_m: 50 DEG C；

Two-the stearyl-thios that Irganox PS-802FL is obtained by BASF, CAS:211-750-5, T_m: 64℃；

Cyasorb UV3808, is obtained by Cytec, T_m: 28, be the mixture of following substance:

- 3,5- di-tert-butyl-4-hydroxybenzoic acid hexadecane base ester, CAS:67845-93-6；And

The ester admixture of -2,2,6,6- tetramethyl -4- piperidine alcohols and higher fatty acids (mainly stearic acid), CAS: 86403-32-9；

Jetfine T1CA talcum, is obtained, T by Imerys France_m: 800 DEG C；

Yuch black-1906 pigment is obtained, T by Cabot (U.S.)_m: 125 DEG C；

PP-H, GD, 225 Noblen powder, T_m: 160 DEG C；

Include glycerin monostearate (T_mBe 65 DEG C) Borealis's commercial resin: BD950MO, BD265MO, BE961MO, BF970MO, BH975MO, BJ368MO, HG385MO and HJ311MO.

Without glycerin monostearate (T_mBe 65 DEG C), also be free of melting temperature T_mAny other additive lower than 100 DEG C Borealis's commercial resin: HJ311A1, HD915CF, BJ356A1.

HD915CF is the Noblen prepared by Borealis Borstar at nuclear technology (BNT), MFR (ISO 1133,230 DEG C/2.16kg) it is 8g/10min, glycerin monostearate is free of, T is also free of_mAny other less than 100 DEG C adds Add agent.

BJ356A1 is the heterophasic polypropylene prepared by Borealis Borstar at nuclear technology (BNT), MFR (ISO 1133,230 DEG C/2.16kg) it is 95g/10min, glycerin monostearate is free of, T is also free of_mIt is any other less than 100 DEG C Additive.

The mist degree for having determined that base polymer, is as a result given in Table 1 below.

Table 1	Polypropylene	Mist degree [%] at 120 DEG C
			RE1	BD950MO	13.8
RE2	BD265MO	15.7
			RE3	BE961MO	58.5
RE4	BF970MO	12.3
			RE5	BH975MO	13
RE6	BJ368MO	6.84
			RE7	HG385MO	10.9
RE8	HJ311MO	6.18
			IE9	HJ311A1	1.81
IE10	HD915CF	0.12
			IE11	BJ356A1	0.06

RE: comparative example

IE: example

In addition, determining the mist degree of each additive as described above.As a result and dosage is listed in Table 2 below.

Table 2	Additive	T_m[℃]	It measures [mg]	Mist degree [%] at 120 DEG C
					RE11	Irganox 1076	50	0.5g	13.6
RE12	Irganox PS-802FL	64	0.5g	12.6
					RE13	Cyasorb UV3808	28	0.5g	24.4
IE14	Irganox 3114	218	0.5g	1.05
					IE15	Irgafos 168	182	0.5g	6.57
IE16	Cyasorb UV-3529	110	0.5g	3.39

RE: comparative example

IE: example

In addition, using having the counter rotating twin screW extruder of main feed device and three side feeders to prepare following combination Object.

Component shown in following table is fed by main feed device, and filler (talcum) is fed by the first side feeder, addition Agent is fed by second side feeder, and pigment is fed by third side feeder.By additive and gathering as additive carrier Propylene powder mixing.Amount is provided with weight percent.

The physical property of the composition of preparation is also shown in the following table 3.

It can be clearly seen that polypropene composition of the invention has much lower mist degree from table 3, contains and be free of The base resin (i.e. HD915CF and BJ356AI) and T of GMS_mAdditive (i.e. AO 3114 and UV-3529) greater than 100 DEG C, this The mist degree of the polypropene composition of invention reduces 50 times than current material, which contains the base resin containing GMS (HJ311MO, HG385MO and BD950MO) and T_mLess than 100 DEG C additive (i.e. AO1076, Irganox PS-802FL and UV-3808)。

Other than reduced mist degree, composition of the invention remains the mechanical performance similar with current material, expires The requirement of sufficient mechanical performance.

Therefore, composition of the invention has much lower mist degree, while meeting the requirement to mist degree and mechanical performance.

Claims

1. a kind of polypropene composition (PC), includes:

More than one polypropylene (P),

Total weight based on the polypropene composition (PC), more than one additives (A) of 0.05~5.0 weight %,

Wherein,

The polypropene composition (PC) is free of additive of the melting temperature lower than 100 DEG C measured by DSC.

2. a kind of polypropene composition (PC), includes:

Polypropylene (P),

Wherein,

The haze value that the polypropene composition measures at 120 DEG C is 5.0% or less.

3. polypropene composition (PC) according to claim 1, wherein the polypropene composition measures at 120 DEG C Haze value be 5.0% or less.

4. polypropene composition (PC) according to claim 2, wherein

5. the polypropene composition (PC) according to any one of preceding claims 1~4, wherein be based on the polypropylene The total amount of composition (PC), the total amount of the polypropylene (P) are at least 50 weight %.

6. the polypropene composition (PC) according to any one of preceding claims 1~5, wherein polypropylene (P) packet Containing heterophasic polypropylene (HECO), and/or selected from random copolymer of propylene (RPP) and Noblen, preferably Noblen (HPP) other polypropylene.

7. the polypropene composition (PC) according to any one of preceding claims 1~6, wherein be based on the polypropylene The total amount of composition, the polypropene composition further include the mineral filler of 1~45 weight %.

8. polypropene composition (PC) according to claim 7, wherein the mineral filler is selected from glass fibre, carbon fiber Dimension, phyllosilicate, mica, wollastonite or their mixture.

9. a kind of method for being used to prepare polypropene composition (PC) described in any one of preceding claims 1~8, including with Lower step:

(i) more than one polypropylene (P) are provided；

(ii) more than one additives (A) are provided, wherein the melting temperature that every kind of additive (A) is measured by DSC be 100 DEG C with On；

(iii) polypropylene described in melting mixing (P) and the additive (A)；

Wherein,

There is no the additives that the melting temperature measured by DSC is lower than 100 DEG C in the polypropylene (P)；And

Additive of the melting temperature lower than 100 DEG C by DSC measurement is not added in the method.

10. a kind of product includes polypropene composition (PC) described in any one of preceding claims 1~8.

11. product according to claim 10, wherein the product is injection-molded item, such as automotive interior and outside portion Part, preferably lamp housing.

12. the application for the additive that the melting temperature by DSC measurement is 100 DEG C or more, for reducing poly- comprising more than one The mist degree of the polypropene composition (PC) of propylene (P).