CN105330957B - A kind of polypropene composition and preparation method thereof - Google Patents
A kind of polypropene composition and preparation method thereof Download PDFInfo
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- CN105330957B CN105330957B CN201410393456.9A CN201410393456A CN105330957B CN 105330957 B CN105330957 B CN 105330957B CN 201410393456 A CN201410393456 A CN 201410393456A CN 105330957 B CN105330957 B CN 105330957B
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Abstract
The present invention relates to a kind of polypropene composition and preparation method thereof.The polypropene composition contains acrylic resin, polymer composition and damage resistant master batch；The polymer composition contains 40 70 weight % crystalline polypropylene A and 30 60 weight % ethylene propylene elastomeric copolymer B, and the polymer composition and crystalline polypropylene A molecular weight distributing index are all higher than 4, the ratio between the melt index of the polymer composition and the crystalline polypropylene A melt index is 0.7 1.3.Product made of the polypropene composition of the present invention is not only with good stress-whitening resistance also with higher scratch resistant performance, so as to especially suitable for industries such as automobile, household electrical appliances.
Description
Technical field
The present invention relates to a kind of polypropene composition, the method for preparing the polypropene composition, and prepared by this method
Polypropene composition.
Background technology
In recent years, as people keep the requirement of good appearance increasingly to improve in use to product, preparation has
Favorable comprehensive mechanical property, while and can keeps the polypropylene material of good appearance to turn into polypropylene in vapour in use
Car, the development trend of field of household appliances application.
In order to improve polyacrylic impact resistance to meet requirement, conventional method is by polypropylene and rubber or bullet
Property body (such as EP rubbers, polyolefin elastomer) is blended.But this method has some limitations, one of them
It is exactly that harmful effect is produced to modified polypropene surface property (such as scratch resistant, stress whitening).
It is well known that studies on scratch resistance of PP can be poor, it is easy to be scratched under external force, and toughener such as rubber
The addition of glue, elastomer etc. then can further deteriorate polyacrylic scratch resistance.Therefore, when such tenacity-increased profax is applied to electricity
It can be restricted during the field higher to appearance requirement such as device shell, automotive upholstery, be especially applicable to automotive upholstery, such as
Instrument board, door-plate etc..
To solve the above problems, US6541568B1 disclose it is a kind of by add containing big weight phenylethylene copolymer come
Improve the formula of polyacrylic scratch resistance.However, the manufacturing expense of styrene copolymer is expensive, polypropylene can be dramatically increased
The cost of blend.In addition, the styrene copolymer is limited to polyacrylic scratch resistance improvement result.
CN101173074A is disclosed a kind of improves poly- the third of its scratch resistance by adding aliphatic amide lubricant
Alkene constituent and preparation method thereof；CN1580115A is disclosed a kind of improves scratch resistance by adding mar-proof talcum powder
Polypropylene composite and preparation method thereof；CN1631960A discloses one kind by adding the mar-proof talcum of high rigidity, high tenacity
The polypropylene composite of powder to improve its scratch resistance and preparation method thereof.But these methods are needed with rubber content
Increase and increase the dosage of lubricant, and be merely limited by increasing improvement of the dosage of lubricant to scratch resistance.
Asked in addition, the increase of lubricant quantity also results in lubricant precipitation, surfaces of tacky frostization, long-term use of lubricant effect variation etc.
Topic.
Further, since polypropylene own structural characteristics cause polypropylene stress whitening to be present.Acted on by external force
When, the ejection link or product of such as Shooting Technique can be produced crazing in relevant position and extend silver by external force collision, material
Line region is to absorb energy, and crazing region produces and extension will cause product to turn white, and influences outward appearance or produces defective work.This
Outside, when being scraped by external force, stress whitening can further result in the decline of scratch resistant performance.And the addition of rubber or filler is then
The further reduction of stress-whitening resistance may be caused.
To solve the above problems, CN101709124A disclose a kind of anti-folding stress whitening resistant polypropylene material and its
Manufacture method, turn white master batch by adding elastomer and homemade resistance to stress in high impact resistance polypropylene base material to improve material
Toughness and stress-whitening resistance energy.Although described material shows very high shock resistance, COPP dosage
Too much, the rigidity decline of material is caused, while stress-whitening resistance is also high not as desired.CN101058655B is disclosed
A kind of resistance to stress is turned white and the filling modified polypropylene material of stress cracking, improves stress whitening problem by polyethylene, but
Be its using block copolymerization polypropylene, and COPP dosage is excessive, causes the raising to material stress-whitening resistance
It is horizontal limited.
Therefore for how while RPP scratch resistance to improve its stress-whitening resistance, at present still
There is no good method.
The content of the invention
The invention aims to overcome existing polypropene composition to improve prepared therefrom poly- third simultaneously
A kind of the problem of scratch resistance and stress-whitening resistance of alkene product, there is provided polypropene composition and preparation method thereof.
The invention provides a kind of polypropene composition, the polypropene composition contains acrylic resin, combination of polymers
Thing and damage resistant master batch, the polymer composition contain：
(a) 40-70 weight % crystalline polypropylene A, crystalline polypropylene A are selected from Noblen and/or propylene random
Copolymer, on the basis of the gross weight of propylene random co-polymer, the propylene random co-polymer contains 82-99.9 weight %'s
The alpha-olefin knot with 4-10 carbon atom of propylene construction unit, 0-6 weight % ethylene unit unit and 0-12 weight %
Structure unit, and the total content of ethylene unit unit and the alpha-olefin construction unit with 4-10 carbon atom is 0.1-18 weights
% is measured, and
(b) 30-60 weight % ethylene-propylene elastomeric copolymer B, using ethylene-propylene elastomeric copolymer B gross weight as
Benchmark, ethylene-propylene elastomeric copolymer B contain 60-92 weight % propylene construction unit, 8-25 weight % ethylene unit
The alpha-olefin construction unit with 4-10 carbon atom of unit and 0-15 weight %,
Wherein, the polymer composition and the crystalline polypropylene A molecular weight distributing index are all higher than 4；It is described poly-
The ratio between the melt index of polymer composition and the melt index of the crystalline polypropylene A are 0.7-1.3.
Present invention also offers the preparation method of above-mentioned polypropene composition, this method comprises the following steps：
(1) under the first olefin polymerization conditions, by the first monomer a and the Ziegler-Natta catalysis with high stereoselective
Agent haptoreaction, and unreacted monomer is removed in the mixture obtained after haptoreaction, obtain containing crystalline polypropylene A's
First mixture, wherein, the first monomer a contain propylene and optional ethene and/or α with 4-10 carbon atom-
Alkene；
(2) under the conditions of alkene gas-phase polymerization, second comonomer b and step (1) are obtained described containing crystalline polypropylene A
The first mixture haptoreaction, obtain the second mixture containing crystalline polypropylene A and ethylene-propylene elastomeric copolymer B, and
Unreacted monomer is removed from second mixture, obtains polymer composition, wherein, the second comonomer b contains propylene
And ethene and/or the alpha-olefin with 4-10 carbon atom；
(3) polymer composition, the damage resistant master batch that will be obtained in acrylic resin, step (2), and optional poly- second
Alkene, mineral filler and toughener are dry-mixed, and dry-mixed obtained mixture is carried out into melt blending.
In polypropene composition provided by the invention, the rubber phase particle diameter in polymer composition is smaller and scattered equal
It is even, preferable compatibility is presented with acrylic resin so that the product anti-impact effect formed by the polypropene composition of the present invention
Substantially；Damage resistant master batch can also be dispersed in acrylic resin, and the problem of sample surfaces are tacky is not present.The present invention's is poly-
Product made of propylene compositions is not only with good stress-whitening resistance also with higher scratch resistant performance, so as to especially
Suitable for industries such as automobile, household electrical appliances.
In addition, the preparation technology of the polypropene composition of the present invention is simple, easily operated, suitable for industrial applications.
Other features and advantages of the present invention will be described in detail in subsequent specific embodiment part.
Brief description of the drawings
Accompanying drawing 1 be with reference to preparation example 1 prepare polymer composition dynamic mechanical analysis curve, characteristic feature be -
There are two glass transition points (Tg) at a temperature of 60 DEG C to 20 DEG C；
Accompanying drawing 2 is the dynamic mechanical analysis curve of polymer composition prepared by preparation example 1, and characteristic feature is at -60 DEG C
To there is a glass transition point (Tg) at a temperature of 20 DEG C；
Accompanying drawing 3 is the atomic force microscope images of polymer composition prepared by preparation example 1, shows that component (b) is micro- with 0.3
The particle diameter of rice is highly dispersed in composition.
Embodiment
The embodiment of the present invention is described in detail below.It is it should be appreciated that described herein specific
Embodiment is merely to illustrate and explain the present invention, and is not intended to limit the invention.
The invention provides a kind of polypropene composition, the polypropene composition contains acrylic resin, combination of polymers
Thing and damage resistant master batch, the polymer composition contain：
(a) 40-70 weight % crystalline polypropylene A, crystalline polypropylene A are selected from Noblen and/or propylene random
Copolymer, on the basis of the gross weight of propylene random co-polymer, the propylene random co-polymer contains 82-99.9 weight %'s
The alpha-olefin knot with 4-10 carbon atom of propylene construction unit, 0-6 weight % ethylene unit unit and 0-12 weight %
Structure unit, and the total content of ethylene unit unit and the alpha-olefin construction unit with 4-10 carbon atom is 0.1-18 weights
% is measured, and
(b) 30-60 weight % ethylene-propylene elastomeric copolymer B, using ethylene-propylene elastomeric copolymer B gross weight as
Benchmark, ethylene-propylene elastomeric copolymer B contain 60-92 weight % propylene construction unit, 8-25 weight % ethylene unit
The alpha-olefin construction unit with 4-10 carbon atom of unit and 0-15 weight %,
Wherein, the polymer composition and the crystalline polypropylene A molecular weight distributing index are all higher than 4；It is described poly-
The ratio between the melt index of polymer composition and the melt index of the crystalline polypropylene A are 0.7-1.3.
In the preferred case, the polymer composition passes through in the ziegler natta catalyst with high stereoselective
In the presence of be made with continuous polymerization.The continuous polymerization refers to that preparation process includes the step of at least two orders are carried out,
Wherein, component (a) (i.e. crystalline polypropylene A) and each single step of leisure of component (b) (i.e. ethylene-propylene elastomeric copolymer B)
Middle preparation, moreover, in addition to the first step, later step is in the established polymer of previous step and uses in a previous step
Carried out in the presence of catalyst.
Under above-mentioned preferable case, because the polymer composition uses the metallocene with high stereoselective
Catalyst is made, and the molecular weight distribution of its molecular weight distribution and its component (a) is all higher than 4, preferably greater than 4.5, more preferably
4.5-20(《Polypropylene handbook》(Chemical Industry Press, in June, 2008 first edition, page 15).In the present invention, molecular weight
Distribution is represented with the ratio between weight average molecular weight and number-average molecular weight.
In the present invention, the alpha-olefin with 4-10 carbon atom can for it is commonly used in the art it is various can be with third
Alkene and ethene are copolymerized the compound of conjunction, and the example can be but be not limited to：Butylene (such as 1- butylene), amylene (such as 1- penta
Alkene), 4-methyl-1-pentene, hexene (such as 1- hexenes), at least one of heptene (such as 1- heptene) and octene (such as 1- octenes),
Most preferably 1- butylene.
In the polymer composition, the crystalline polypropylene A is in Noblen and random copolymer of propylene
It is at least one.On the basis of the gross weight of propylene random co-polymer, the propylene random co-polymer preferably comprises 97-99.9 weights
Measure % propylene construction unit, 0-1 weight % ethylene unit unit and 0-2 weight the % α-alkene with 4-10 carbon atom
Hydrocarbon structure unit, and the total content of ethylene unit unit and the alpha-olefin construction unit with 4-10 carbon atom is 0.1-3 weights
Measure %.Under above-mentioned preferable case, the fusing point of the crystalline polypropylene A is more than 150 DEG C so that the polymer composition has
Fusing point more than 150 DEG C, so as to show preferable heat resistance.It is further preferred that the crystalline polypropylene A is that propylene is equal
Polymers, under the preferable case, the polymer composition has good rigidity and heat resistance concurrently.
In the polymer composition, the crystalline polypropylene A can contain more derivative to other olefin-copolymerizations
The construction unit of monomer, so the polymer composition can be made to show more preferable toughness.In the polymer composition,
The ethylene-propylene elastomeric copolymer B can contain a small amount of alpha-olefin construction unit with 4-10 carbon atom, for example,
On the basis of ethylene-propylene elastomeric copolymer B gross weight, the ethylene-propylene elastomeric copolymer B can contain 0.1-15 weights
Measure %, 0.1-5 weight % or 0.1-3 weight % the alpha-olefin construction unit with 4-10 carbon atom.Under preferable case, institute
State ethylene-propylene elastomeric copolymer B and do not include the alpha-olefin construction unit with 4-10 carbon atom substantially；Further preferably
Ground, on the basis of the gross weight of the ethylene-propylene elastomeric copolymer B, the ethylene-propylene elastomeric copolymer B contains 75-92
Weight % propylene construction unit and 8-25 weight % ethylene unit unit；It is further preferred that the ethylene-propylene bullet
Property copolymer B contains 10-18 weight % ethylene unit unit and 82-90 weight % propylene construction unit.
In the present invention, the ratio between the melt index of the polymer composition and the melt index of the crystalline polypropylene A
For 0.7-1.3, preferably 0.75-1.2.Specifically, the melt index of the polymer composition can be 0.1-100g/
10min, preferably 0.5-50g/10min.In the present invention, melt index determines according to ASTM D1238-99 methods.
In the polymer composition, by AFM it is observed that the polymer composition has two
Phase structure.The ethylene-propylene elastomeric copolymer B is preferably scattered in the polymer with particle of the average grain diameter less than 0.5 μm
In composition.In the present invention, the average grain diameter (i.e. granular size) is determined by atomic force microscopy.
In the present invention, the mist degree of the polymer composition is preferably smaller than 60%, more preferably less than 40%, further excellent
Choosing is less than 30%.The mist degree measures according to ASTM D1003 methods, i.e., the result measured on 1mm injected sample thin slice.
In the present invention, the polymer composition has a glass transition point at a temperature of -60 DEG C to 20 DEG C.
In the present invention, on the basis of the gross weight of polymer composition, the polymer composition can also contain 0.1-1
Weight % nucleator.The nucleator can be various nucleators commonly used in the art, such as：Double (bis- tertiary fourths of 2,4-
Base phenyl) sodium phosphate, 2,2 '-methylene-two (4,6- di-n-butyls phenol) sodium phosphate, di-2-ethylhexylphosphine oxide (2,4- di-tert-butyls
Base) the aryl phosphoric acids salt nucleator such as aluminum phosphate；The glucitols such as two benzal sorbierites or its alkyl-substituted derivative is nucleated
Agent, Millad3905, Millad3940 and Millad3988 of Milliken companies etc. can be enumerated as commercially available product；Benzoic acid
Carboxylic acid metal's salt nucleators such as sodium, p-tert-butyl benzoic acid carboxyl aluminium.Polymer composition containing nucleator has higher
Bending modulus and the transparency.
It will be apparent to a skilled person that the content of increase ethylene-propylene elastomeric copolymer can increase polymerization
The impact resistance of compositions, but in the presence of ziegler natta catalyst, the high ethylene-propylene made from continuous polymerization
During the polypropene composition of elastocopolymer content, the tacky situation of ethylene-propylene elastomeric copolymer particle generally can be all run into.
And in order that the performance of copolymer reaches the performance of transparent anti-impact, ethylene-propylene elastomeric copolymer molecule used in copolymer
Amount is all smaller, and this makes ethylene-propylene elastomeric copolymer particle be easier tacky situation occur, so using continuous polymerization
It is difficult to obtain the combination of polymers that ethylene-propylene elastomeric copolymer level accounts for more than the weight % of polymer composition gross weight 30
Thing.Therefore, usually require to prepare transparent impact product using the melt blending of high cost at present.However, the invention of the present invention
People is had found by studying, by that can be realized with continuous polymerization synthesis with higher from specific ziegler natta catalyst
The polymer composition of ethylene-propylene elastomeric copolymer level.
In the present invention, the polymer composition contains the ethylene-propylene elastomeric copolymer B for having more than 30 weight %, this
Sample can make polymer composition show good toughness.
In the polypropene composition of the present invention, in order to further improve the product made of the polypropene composition
Scratch resistance and stress-whitening resistance, relative to the acrylic resin of 100 parts by weight, the polymer composition contains
Amount can be 1-30 parts by weight, preferably 5-20 parts by weight.
In the polypropene composition of the present invention, the acrylic resin can be commonly used in the art various
Acrylic resin.Under preferable case, to make the scratch resistance and stress-whitening resistance of the product made of the polypropene composition
It is further improved, the acrylic resin is selected from the HOPP and melt index that melt index is 3-60g/10min
At least one of COPP for 3-60g/10min, more preferably melt index are 3-60g/10min copolymerization poly- third
Alkene.
The damage resistant master batch preferably is selected from the super high molecular weight siloxanes master batch using polypropylene as carrier, described polyacrylic
Melt index (MI, g/10min) can be 10-15.Because the siloxanes master batch has higher concentration and super high molecular weight knot
Structure and using polypropylene as carrier, so can not only ensure that the surface of the Polypropylene compositions Tetramune is not tacky, and can also
Further improve the scratch resistant performance of product and reduce the generation of stress whitening.The damage resistant master batch can be obtained by commercially available
, for example, purchased from Dow Corning Corporation the trade mark be MB50-001 product.
The present invention is not particularly limited to the content of the damage resistant master batch, typically, for described in 100 parts by weight
Acrylic resin, the content of the damage resistant master batch can be 0.5-15 parts by weight, preferably 1-10 parts by weight.
In a preferred embodiment, in order to further improve the scratch-resistant of the product prepared by the polypropene composition
Wound property and stress-whitening resistance, the polypropene composition preferably also contain polyethylene, and the crystallization of the polyethylene is to rubber
The relexation of grain can further improve stress whitening.Relative to the acrylic resin of 100 parts by weight, the polyethylene
Content can be 0.1-30 parts by weight, preferably 5-15 parts by weight.
The polyethylene can be polyethylene commonly used in the art, it is preferable that the polyethylene is selected from melt index
In the low density polyethylene (LDPE) that high density polyethylene (HDPE) and melt index for 0.2-40g/10min are 0.2-40g/10min at least
It is a kind of.In the present invention, the high density polyethylene (HDPE) refers to that density is 0.946-0.976g/cm3Polyethylene, the low-density
Polyethylene refers to that density is 0.945g/cm3Following polyethylene.
In the present invention, the polypropene composition can also contain mineral filler and/or toughener.Relative to 100 weights
The acrylic resin of part is measured, the content of the mineral filler can be 0-50 parts by weight, preferably 0.1-20 parts by weight；Institute
The content for stating toughener can be 0-30 parts by weight, preferably 0.1-15 parts by weight；And the mineral filler and the toughener
Total content be at least 0.1 parts by weight.
The mineral filler can be mineral filler commonly used in the art, for example, can be talcum powder, wollastonite and
At least one of calcium carbonate.The particle diameter of the mineral filler can be 300~5000 mesh.The toughener can be this area
Conventional use of toughener, such as can be amorphous ethylene-alpha olefin copolymer (such as EP rubbers) and styrenic based thermoplastic
At least one of property elastomer.
In the present invention, the polypropene composition can also contain antioxidant.Relative to described poly- the third of 100 parts by weight
Olefine resin, the content of the antioxidant can be 0.1-3 parts by weight.The antioxidant can be antioxygen commonly used in the art
Agent, such as can be antioxidant 1076, antioxidant 1010, irgasfos 168, sulphur ester antioxidant (such as DLTP, DSTP).
In the present invention, the polypropene composition can also contain processing aid commonly used in the art, for example, profit
Lubrication prescription, antistatic additive, dispersant, pigment etc..Relative to the acrylic resin of 100 parts by weight, the processing aid contains
Amount can be 0.1-5 parts by weight.
In the present invention, the polypropene composition can be prepared according to the conventional method, for example, its preparation method can be with
Including by acrylic resin, polymer composition, damage resistant master batch, and it is optional polyethylene, mineral filler, toughener, anti-
Oxygen agent and other processing aids carry out melt blending.
In a preferred embodiment, the preparation method of the polypropene composition includes：First prepare combination of polymers
Thing, then by acrylic resin, the polymer composition prepared, damage resistant master batch, and optional polyethylene, mineral filler, increasing
Tough dose, antioxidant and other processing aids carry out melt blending.
Specifically, the preparation method of the polypropene composition comprises the following steps：
(1) under the first olefin polymerization conditions, by the first monomer a and the Ziegler-Natta catalysis with high stereoselective
Agent haptoreaction, and unreacted monomer is removed in the mixture obtained after haptoreaction, obtain containing crystalline polypropylene A's
First mixture, wherein, the first monomer a contain propylene and optional ethene and/or α with 4-10 carbon atom-
Alkene；
(2) under the conditions of alkene gas-phase polymerization, second comonomer b and step (1) are obtained described containing crystalline polypropylene A
The first mixture haptoreaction, obtain the second mixture containing crystalline polypropylene A and ethylene-propylene elastomeric copolymer B, and
Unreacted monomer is removed from second mixture, obtains polymer composition, wherein, the second comonomer b contains propylene
And ethene and/or the alpha-olefin with 4-10 carbon atom；
(3) polymer composition, the damage resistant master batch that will be obtained in acrylic resin, step (2), and optional poly- second
Alkene, mineral filler and toughener are dry-mixed, and dry-mixed obtained mixture is carried out into melt blending and extruding pelletization.
In the above-mentioned methods, alpha-olefin, the acrylic resin, the damage resistant mother with 4-10 carbon atom
Grain, the polyethylene, the mineral filler and the toughener can be identical with what is be described above.
The present inventor has found in research process：Carrying out comprising at least two using ziegler natta catalyst
During the propylene polymerization of sequential steps, by controlling polymerizing condition so that the melt index of polymer composition and crystalline polypropylene A
Than the specific composition and content in particular range and by controlling crystalline polypropylene A and ethylene-propylene elastomeric copolymer B,
The polymer composition of formation can have the high transparency and impact strength.
In one embodiment, the first monomer a is propylene so that the knot obtained under the first olefin polymerization conditions
Crystal polypropylene A is Noblen.
In a preferred embodiment, the second comonomer b is propylene and ethene so that in alkene gas-phase polymerization bar
The ethylene-propylene elastomeric copolymer B obtained under part contains 75-92 weight % propylene construction unit and 8-25 weight % ethene
Construction unit；It is further preferred that so that ethylene-propylene elastomeric copolymer B contain 82-90 weight % propylene construction unit and
10-18 weight % ethylene unit unit.
In the present invention, " ziegler natta catalyst with high stereoselective " is to refer to preparation isotaxy to refer to
The catalyst of Noblen of the number more than 95%.
The ziegler natta catalyst with high stereoselective can contain：
(i) ingredient of solid catalyst, its main component are magnesium, titanium, halogen and internal electron donor；
(ii) organo-aluminum compound；And
(iii) optional external donor compound,
The average grain diameter of the ziegler natta catalyst with high stereoselective can be more than 30 microns, preferably greatly
In 40 microns.
Preferably, it is used to the present invention as ziegler natta catalyst prepared by carrier using magnesium diaikoxide compound have
It is advantageous.Using the catalyst described in CN102453150A, especially there is advantage for the present invention.
The ingredient of solid catalyst is preferably made by following steps：
(a) under inert gas shielding, using magnesium and alcohol as raw material, the back flow reaction in the presence of halogenating agent, dioxane is obtained
Epoxide magnesium compound；
(b) in the presence of inert diluent, by the magnesium diaikoxide compound that step (a) obtains and titanium compound and it is interior to
Electron compound carries out haptoreaction；
The magnesium diaikoxide compound is spherical particle, and average grain diameter is 10~150 microns, particle diameter distribution index SPAN
<1.1。
Preparation process and the patent application of above-mentioned preferable ziegler natta catalyst and the ingredient of solid catalyst
It is identical described in CN102453150A.
The ziegler natta catalyst with high stereoselective can be used directly, can also pass through pre- complexing and
Added after prepolymerization.
Organo-aluminum compound as the cocatalyst component of catalyst is preferably alkyl aluminum compound, is more preferably selected from three
Alkyl aluminum is (such as：Trimethyl aluminium, triethyl aluminum, triisobutyl aluminium, three n-butylaluminums, trioctylaluminum), aluminium diethyl monochloride, a chlorine
At least one of diisobutyl aluminum, aluminium diethyl monochloride, a chloro-di-isobutyl aluminum, the aluminium ethide of dichloro one and ethyl aluminum dichloride.
With Ti/Al molar ratio computings, the ratio between the ingredient of solid catalyst and the organo-aluminum compound cocatalyst component
Can be 1:25 to 1:1000.
External donor compound as optional catalyst component is preferably organo-silicon compound, and its formula is RnSi
(OR')4-n, 0 ＜ n≤3 in formula, wherein, R and R' are identical or different, and are each independently selected from alkyl, cycloalkyl, aryl and halogen
Substituted alkyl, R can also be halogen or hydrogen atom.Specifically, the organo-silicon compound can be but be not limited only to：Tetramethoxy
Silane, tetraethoxysilane, trimethylmethoxysilane, trimethylethoxysilane, trimethyl phenoxysilane, dimethyl two
Methoxy silane, dimethyldiethoxysilane, methyl-t-butyldimethoxysilane, isopropyl methyl dimethoxysilane,
Two phenoxy group dimethoxysilanes, diphenyl diethoxy silane, phenyltrimethoxysila,e, phenyl triethoxysilane, second
Alkenyl trimethoxy silane, Cyclohexyl Methyl Dimethoxysilane, dicyclopentyl dimethoxyl silane, diisopropyl dimethoxy
Silane, second, isobutyl dimethoxy silane, 2- ethyl piperidine base -2- t-butyldimethoxysilanes, (the fluoro- 2- third of 1,1,1- tri-
Base) -2- ethyl piperidine bases dimethoxysilane, (the fluoro- 2- propyl group of 1,1,1- tri-)-methyl dimethoxysilane etc..
With Al/Si molar ratio computings, the ratio between the alkyl aluminum compound and the organo-silicon compound can be 3：1 to 100：
1。
It is anti-that three kinds of components of the ziegler natta catalyst with high stereoselective can be added directly into polymerization
Answer in device, pre- complexing and/or prepolymerization known to industry can also be passed through and then be added in reactor.Prepolymerization can be with
It is carried out continuously, can also be intermittently carried out in atent solvent under the conditions of liquid-phase bulk.Pre-polymerization reactor can continuously be stirred
Mix kettle, annular-pipe reactor etc..Prepolymerized temperature can be controlled between -10 to 60 DEG C, and preferable temperature is 0 to 40 DEG C.In advance
The multiple of polymerization can be controlled at 0.5 to 1000 times, and preferable multiple is 1.0 to 500 times.
In the above-mentioned methods, the first olefinic polymerization and alkene gas-phase polymerization can be carried out continuously, and can also intermittently be carried out.Even
Continuous polymerization can be carried out using more than two tandem reactors.
First olefinic polymerization can be carried out in liquid phase, can also be carried out in gas phase.Reactor used in first olefinic polymerization
It can be Liquid-phase reactor, or Gas-phase reactor.Liquid-phase reactor can be annular-pipe reactor and stirred tank reactor
Can be horizontal type agitated bed reactor, vertical mixing bed reactor and fluidized-bed reactor etc. Deng, Gas-phase reactor, above liquid phase
Reactor and Gas-phase reactor can also arbitrarily matched combineds.
In the above-mentioned methods, first olefin polymerization conditions can include：Temperature is 50-100 DEG C, preferably 60-95
℃；Pressure is 1-8MPa, preferably 1.2-5.5MPa；Time is 30-180 minutes, preferably 45-120 minutes.In the present invention
In, pressure refers to reactor gauge pressure.
The reactor of alkene gas-phase polymerization can be anti-for horizontal type agitated bed reactor, vertical mixing bed reactor, fluid bed
Answer device etc., above Gas-phase reactor can arbitrarily matched combined.
In the above-mentioned methods, the alkene gas-phase polymerization condition can include：Temperature is 50-100 DEG C, preferably 60-95
℃；Pressure is 1-4MPa, preferably 1.2-3.5MPa；Time is 10-180 minutes, preferably 10-90 minutes.
In the present invention, the preparation method of the polypropene composition can also include：By the polymer composition
Before melt blending together with other components, the polymer composition obtained to step (2) is granulated, and in polymer group
Compound adds nucleator when being granulated.Preferably, contain in the polymer composition that the dosage of the nucleator to obtain after being granulated
There is 0.1-1 weight % (preferably 0.2-0.5 weight %) nucleator.The nucleator can be identical with what is be described above.
In the present invention, the temperature of the melt blending can be blending temperature used in the processing of usual polypropylene, should
It should be selected in the range of not only ensureing acrylic resin melting completely but also will not decompose it.Specifically, the melt blending
Temperature can be 190-230 DEG C, preferably 200-230 DEG C.
In the present invention, the preparation method of the polypropene composition can also include：Squeezed after melt blending
Go out to be granulated.Preferably, the process of the melt blending and the extruding pelletization is kneaded in unit in double screw extruder or BUSS
Carry out.
Present invention also offers the polypropene composition prepared by the above method.
On the one hand the polypropene composition has damage resistant master batch, the damage resistant master batch can be effectively dispersed in poly- third
In olefine resin, polyacrylic scratch resistant performance can be significantly improved and the problem of sample surfaces are tacky is not present；On the other hand have
Particle diameter is smaller and finely dispersed rubber phase so that the structure that the polypropene composition is formed can when by external impacts
Effectively absorb extraneous impact energy, anti-impact positive effect and polyacrylic stress whitening can be effectively improved.
Therefore, the product that the polypropene composition prepared using the method for the present invention is formed has good scratch resistant performance
With stress-whitening resistance energy, so as to especially suitable for industries such as automobile, household electrical appliances.
The invention will be further described by the following examples.
Corresponding method of testing is as follows：
The invention will be further described by the following examples.
Corresponding method of testing is as follows：
Melt index (MFR)：According to ASTM D1238-99, determined under 230 DEG C, 2.16kg load.
Monomeric building blocks content in copolymer：Determined with fourier infrared method.
Xylene soluble content：Determined by ASTM D5492-98.
Melting temperature (Tm)：Determined using the DSC7 type differential scanning calorimeters instrument of Perkin Elmer companies, test model
Enclose from 50 DEG C to 200 DEG C, sample is first risen to 200 DEG C to eliminate thermal history, then by 10 DEG C/min's by 10 DEG C/min speed
Speed is down to 50 DEG C, measures its crystallization temperature and crystallization enthalpy, then rises to 200 DEG C by 10 DEG C/min speed, measure its fusing point and
Melting enthalpy.
Tensile strength：Injected sample is measured according to ASTM D638.
Bending modulus：Injected sample is measured according to ASTM D790.
Cantilever beam impact strength (Izod notch shocks)：According to ASTD D256, measurement is noted respectively at 23 DEG C and -20 DEG C
Mould sample.
Heat distortion temperature (HDT)：Determined according to ASTM D648.
Mist degree：According to ASTM D1003, the mist degree of the injected sample of 1 millimeters thick of measurement.
Light transmittance：According to ASTM D1003, the light transmittance of the injected sample of 1 millimeters thick of measurement.
Catalyst average grain diameter：Using the laser particle analyzers of Malvern Mastersizer TM 2000, n-hexane dispersant
Laser diffractometry measures the average particle diameter size of catalyst.
Glass transition temperature (Tg)：Using dynamic mechanical analysis (DMA), TA RSAIII type solid rheometer test temperature models
Enclose for -90 DEG C to 50 DEG C, test specimen is injection batten, heating rate 3 DEG C/min, frequency 1Hz, three-point bending pattern.
Atomic force microscopy：Polypropylene is molded batten through cryogenic freezing to ultra-thin section after subzero 50 degrees Celsius, sees
Examine section.Vecco companies of U.S. Naonscope IIIa type multiple mode scanning force microscopes, J probes, tapping-mode, scanning
5 μm of 5 μ m of scope, gather phasor.
Molecular weight distributing index (Mw/Mn)：It is solidifying using Polymer Laboratories companies of Britain production PL-GPC 220
The molecular weight distribution of glue penetration chromatograph determination sample, chromatographic column are Plgel10 μm of MIXED-B post of 3 series connection, solvent and stream
Dynamic is mutually 1,2,4- trichloro-benzenes, 150 DEG C of column temperature, is carried out using PL companies EasiCal PS-1 Narrow distribution polystyrenes standard specimen pervasive
Demarcation, detector use the infrared concentration detectors of IR5 of POLYCHAR companies.
Preparation example：Prepare polymer composition
Following preparation example and obtained by the following method with reference to the polymer composition in preparation example, material amounts therein and
Polymeric reaction condition is listed in Table 1 below.
Polymerisation is carried out on set of horizontal type gas phase polypropylene pilot-plant, and polymer reactor is connected horizontal for two
Stirred autoclave, polymerization and step are as follows：
Major catalyst (ingredient of solid catalyst) uses the method that embodiment 1 describes in CN102453150A to obtain, wherein
Internal electron donor compound use n-butyl phthalate.
Major catalyst, co-catalyst (triethyl aluminum), external electron donor are added continuously horizontal stir under the carrying of propylene
Mix reactor and carry out polymerisation.Catalyst enters from first stirred tank front end, the polymerization generation crystallization under conditions of gas phase
Polypropylene A, reaction heat are taken away by the propylene vaporization sprayed.The polymer of generation is discharged by the end of stirred tank.Catalyst and poly-
Compound moves in a manner of close to laminar flow in reactor, and polymerization temperature is 66 DEG C or assigned temperature, reaction pressure 2.3MPa,
Residence time is 90 minutes.
Polymer is discharged from first reactor, the equipment by being equipped with transfer between two reactors, polymer is shifted
To second Horizontal stirring reactor.Polymer enters from second stirred tank front end, the polymerization generation second under conditions of gas phase
Alkene-propylene elastomeric copolymer B, reaction heat are taken away by the propylene vaporization sprayed.The polymer of generation is discharged by the end of stirred tank.
Catalyst and polymer move in a manner of close to laminar flow in reactor, and polymerization temperature is 66 DEG C or assigned temperature, is reacted
Pressure 2.2MPa, it is 60 minutes during stop.
React that obtained polymer is degassed, after wet nitrogen deactivation processing, obtain polymer composition.
Gas in the continuous analysis reactor of gas-chromatography is used as molecular weight regulator using hydrogen in two reactors
The composition (ethene, propylene, butylene and hydrogen) of body.
The IRGAFOS of 0.1 parts by weight is separately added into powder according to the obtained parts by weight of polymer composition 100
168 additives (being purchased from Ciba Co., Ltd), the IRGANOX1010 additives of 0.1 parts by weight are (limited purchased from Ciba
Company) and 0.05 parts by weight calcium stearate (being purchased from Ciba Co., Ltd), and add purchased from Milliken companies
Millad3988 additives (specific dosage is referring to table 2), are granulated with double screw extruder.
Injection machine prepares the injected sample for meeting ASTM standard, and determines its physical property, and measurement result is as shown in table 2.
With reference to preparation example 1
Polymerisation is carried out on above-mentioned horizontal pneumatic heterophasic polypropylene pilot-plant, and the catalyst particle size used is 59 microns,
Reaction is carried out according to the method described above.For the external electron donor used for diisopropyl dimethoxy silane, first reactor polymerization is anti-
Propylene homo is should be, polymerization temperature is 66 DEG C, reaction pressure 2.3MPa, and the residence time is about 90 minutes.Second reactor is third
Alkene copolymerization prepares component (b), and ethene, propylene are added in reactor, and polymerization temperature is 66 DEG C, reaction pressure 2.2MPa, during stop
Between be 60 minutes.React that obtained polymer is degassed, after wet nitrogen deactivation processing, obtain product.Reaction condition and product
Can be as shown in table 1.Product adds additive and is granulated, but non-Added Nucleating Agents, and the injected sample DP1 of polymer composition is made, its
Test performance is as shown in table 2.The dynamic mechanical analysis curve of the polymer composition of preparation is as shown in figure 1, can from figure
Go out, there are two glass transition points (Tg) at a temperature of -60 DEG C to 20 DEG C.
With reference to preparation example 2
Using with reference to the catalyst used in preparation example 1, polymer composition is prepared according to the method described above, the difference is that first
The polymerization temperature of reactor is 85 DEG C, changes added hydrogen, and change the composition and content of component (b).Reaction condition and
Product property is as shown in table 1.Product adds additive and is granulated, and the injected sample DP2 of polymer composition, its test performance is made
As shown in table 2.
Preparation example 1
Using with reference to the catalyst used in preparation example 1, polymer composition is prepared according to the method described above, the difference is that changing
Added hydrogen, the polymerization temperature of second reactor is 85 DEG C, changes the composition and content of component (b).Reaction condition and product
Performance is as shown in table 1.Product adds additive and is granulated, and the injected sample P1 of polymer composition, its test performance such as table 2 is made
It is shown.The dynamic mechanical analysis curve of the polymer composition of preparation is as shown in Fig. 2 it can be seen that at -60 DEG C to 20
There is a glass transition point (Tg) at a temperature of DEG C.The atomic force microscopy of the polymer composition of preparation such as Fig. 3
It is shown, it can be seen that the polymer composition has two phase structure, and show component (b) with about 0.3 micron
Particle diameter is highly dispersed in composition.
Preparation example 2
Using with reference to the catalyst used in preparation example 1, polymer composition is prepared according to the method described above, the difference is that changing
Added hydrogen, the polymerization temperature of second reactor is 85 DEG C, changes the composition and content of component (b).Reaction condition and product
Performance is as shown in table 1.Product adds additive and is granulated, and the injected sample P2 of polymer composition, its test performance such as table 2 is made
It is shown.
Preparation example 3
Polymerisation is carried out on above-mentioned horizontal pneumatic heterophasic polypropylene pilot-plant, and the catalyst particle size used is 35 microns,
Reaction is carried out according to the method described above.For the external electron donor used for diisopropyl dimethoxy silane, first reactor polymerization is anti-
Propylene and ethylene random copolymerization is should be, polymerization temperature is 66 DEG C, reaction pressure 2.3MPa, and the residence time is 90 minutes.Second reaction
Device is that propylene copolymerization prepares component (b), and ethene, propylene are added in reactor, and polymerization temperature is 66 DEG C, reaction pressure 2.2MPa,
Residence time is about 60 minutes.React that obtained polymer is degassed, after wet nitrogen deactivation processing, obtain product.Reaction condition
It is as shown in table 1 with product property.Product adds additive and is granulated, but non-Added Nucleating Agents, and the injection sample of polymer composition is made
Product P3, its test performance are as shown in table 2.
Preparation example 4
Polymerisation is carried out on above-mentioned horizontal pneumatic heterophasic polypropylene pilot-plant, and the catalyst particle size used is 30 microns,
Reaction is carried out according to the method described above.For the external electron donor used for second, isobutyl dimethoxy silane, first reactor polymerization is anti-
Propylene homo is should be, polymerization temperature is 75 DEG C, reaction pressure 2.3MPa, and the residence time is 90 minutes.Second reactor is propylene
Copolymerization prepares component (b), and ethene, propylene are added in reactor, and polymerization temperature is 75 DEG C, reaction pressure 2.2MPa, the residence time
It is about 60 minutes.React that obtained polymer is degassed, after wet nitrogen deactivation processing, obtain polymer composition.Reaction condition
It is as shown in table 1 with product property.Product adds additive and is granulated, but non-Added Nucleating Agents, and the injection sample of polymer composition is made
Product P4, its test performance are as shown in table 2.
Preparation example 5
Method according to preparation example 4 prepares polymer composition, the difference is that the content of increase component (b).Reaction condition
It is as shown in table 1 with product property.Final polymer particle is tacky, and experiment can not be carried out continuously.It can be seen that in above-mentioned metallocene
In the case that catalyst particle size is 30 microns, with poly- the third of the high ethylene-propylene elastomeric copolymer level of continuous polymerization preparation
During ene compositions, it is difficult to obtain ethylene-propylene elastomeric copolymer level and account for more than the weight % of polymer composition gross weight 30
Polymer composition.
Table 1
Note：P is diisopropyl dimethoxy silane；B is second, isobutyl dimethoxy silane；MFRa+b/MFRaRefer to polymerize
The melt index ratio of compositions and crystalline polypropylene A.
Table 2
Embodiment
The corresponding detection method of following examples and comparative example is as follows：
The scratch resistant performance of polypropene composition is according to germany volkswagen PV3952 standard testings.Test temperature：23±5℃；
Support force：10N；Scratch speed：1000mm/min.In same sample region, before measuring sample scuffing respectively with spectral photometric colour measuring meter
Surface light scattering value afterwards, the quality of studies on scratch resistance of PP is measured with light scattering difference DELTA E before and after scuffing, Δ E values are smaller, show
The scratch resistance of product is better.
The stress-whitening resistance of polypropene composition can be according to germany volkswagen PV3966 standard testings.Height of the fall ball is selected
500mm standards.The quality of polypropylene stress-whitening resistance, Δ are measured with the scattering difference DELTA E ' of ball falling impact sample front and rear surfaces
E ' values are smaller, show that the stress-whitening resistance of product is better.
The source of the raw material used in following examples and comparative example is as follows：
Acrylic resin：Purchased from Sinopec Beijing Yanshan Petrochemical Co., trade mark K7726, according to ASTM
The melt index of D1238-99 measure is 26g/10min.
Talcum powder：Purchased from mining industry Co., Ltd of Dalian Fuji, particle diameter is 2500 mesh.
EP rubbers：Purchased from Dow Chemical, the trade mark is NORDEL IP.
Damage resistant master batch：Purchased from Dow Corning Corporation, trade mark MB50-001.
Polyethylene：Purchased from Sinopec Beijing Yanshan Petrochemical Co., trade mark 3300J, according to ASTM D1238-99
The melt index of measure is 2.5g/10min.
Antioxidant：Purchased from Ciba fine chemicals, trade mark B225.
Calcium stearate：Purchased from Ciba fine chemicals.
BUSS as melt blending equipment is kneaded unit and is purchased from BUSS companies of Switzerland, trade mark MKD-30.
Embodiment 1-6 and comparative example 1-3
Each component shown in table 3 is respectively put into homogenizer, stirred 3 minutes under 300 revs/min of rotating speed,
Each component is set to be sufficiently mixed uniformly；Mixed material is then subjected to melt blending and extruding pelletization, then injects and makes through injector
Sample, obtain the product of polypropene composition.Then the polypropylene articles of preparation are subjected to scratch resistant performance and resistance to stress is turned white
The test of performance, it the results are shown in Table 3.
Table 3
The product that it can be seen from the data of table 3 prepared by polypropene composition according to the present invention has preferable
Scratch resistant performance and stress-whitening resistance.
The preferred embodiment of the present invention described in detail above, still, the present invention are not limited in above-mentioned embodiment
Detail, in the range of the technology design of the present invention, a variety of simple variants can be carried out to technical scheme, this
A little simple variants belong to protection scope of the present invention.
It is further to note that each particular technique feature described in above-mentioned embodiment, in not lance
In the case of shield, can be combined by any suitable means, in order to avoid unnecessary repetition, the present invention to it is various can
The combination of energy no longer separately illustrates.
In addition, various embodiments of the present invention can be combined randomly, as long as it is without prejudice to originally
The thought of invention, it should equally be considered as content disclosed in this invention.
Claims (23)
- A kind of 1. polypropene composition, it is characterised in that the polypropene composition contain acrylic resin, polymer composition and Damage resistant master batch, the polymer composition contain：(a) 40-70 weight % crystalline polypropylene A, crystalline polypropylene A are selected from Noblen and/or propylene random is copolymerized Thing, on the basis of the gross weight of propylene random co-polymer, the propylene random co-polymer contains 82-99.9 weight % propylene The alpha-olefin structure list with 4-10 carbon atom of construction unit, 0-6 weight % ethylene unit unit and 0-12 weight % Member, and the total content of ethylene unit unit and the alpha-olefin construction unit with 4-10 carbon atom is 0.1-18 weight %, with And(b) 30-60 weight % ethylene-propylene elastomeric copolymer B, using ethylene-propylene elastomeric copolymer B gross weight as base Standard, ethylene-propylene elastomeric copolymer B contain 60-92 weight % propylene construction unit, 8-25 weight % ethylene unit list The alpha-olefin construction unit with 4-10 carbon atom of member and 0-15 weight %,Wherein, the polymer composition and the crystalline polypropylene A molecular weight distributing index are all higher than 4；The polymer The ratio between the melt index of composition and the melt index of the crystalline polypropylene A are 0.7-1.3, and the damage resistant master batch is with poly- Propylene is the super high molecular weight siloxanes master batch of carrier, and the polyacrylic melt index is 10-15g/10min, for 100 weights The acrylic resin of part is measured, the content of the damage resistant master batch is 1-10 parts by weight.
- 2. polypropene composition according to claim 1, wherein, the polymer composition with the vertical structure of height by selecting It is made in the presence of the ziegler natta catalyst of selecting property with continuous polymerization.
- 3. polypropene composition according to claim 2, wherein, point of polymer composition and the crystalline polypropylene A Son amount distribution is 4.5-20.
- 4. according to the polypropene composition described in any one in claim 1-3, wherein, the crystalline polypropylene A is propylene Homopolymer；The ethylene-propylene elastomeric copolymer B contain 10-18 weight % ethylene unit unit and 82-90 weight % third Alkene construction unit.
- 5. according to the polypropene composition described in any one in claim 1-3, wherein, the melting of the polymer composition Index is 0.1-100g/10min.
- 6. according to the polypropene composition described in any one in claim 1-3, wherein, the melting of the polymer composition Index is 0.5-50g/10min.
- 7. according to the polypropene composition described in any one in claim 1-3, wherein, the ethylene-propylene elastomeric copolymerization Thing B is scattered in the polymer composition with particle of the average grain diameter less than 0.5 μm.
- 8. according to the polypropene composition described in any one in claim 1-3, wherein, the polymer composition according to The mist degree of ASTM D1003 methods measure is less than 60%.
- 9. according to the polypropene composition described in any one in claim 1-3, wherein, the polymer composition is -60 DEG C to there is a glass transition point at a temperature of 20 DEG C.
- 10. according to the polypropene composition described in any one in claim 1-3, wherein, relative to described in 100 parts by weight Acrylic resin, the content of the polymer composition is 1-30 parts by weight.
- 11. according to the polypropene composition described in any one in claim 1-3, wherein, relative to described in 100 parts by weight Acrylic resin, the content of the polymer composition is 5-20 parts by weight.
- 12. according to the polypropene composition described in any one in claim 1-3, wherein, the polypropene composition also contains There is polyethylene, relative to the acrylic resin of 100 parts by weight, the content of the polyethylene is 0.1-30 parts by weight.
- 13. according to the polypropene composition described in any one in claim 1-3, wherein, the polypropene composition also contains There is polyethylene, relative to the acrylic resin of 100 parts by weight, the content of the polyethylene is 5-15 parts by weight.
- 14. according to the polypropene composition described in any one in claim 1-3, wherein, the polypropene composition also contains There are mineral filler and/or toughener, relative to the acrylic resin of 100 parts by weight, the content of the mineral filler is 0- 50 parts by weight, the content of the toughener is 0-30 parts by weight, and the total content of the mineral filler and the toughener is at least For 0.1 parts by weight.
- 15. the preparation method of the polypropene composition in claim 1-14 described in any one, this method comprise the following steps：(1) under the first olefin polymerization conditions, the first monomer a and the ziegler natta catalyst with high stereoselective are connect Reaction is touched, and unreacted monomer is removed in the mixture obtained after haptoreaction, obtains first containing crystalline polypropylene A Mixture, wherein, the first monomer a contains propylene and optional ethene and/or the alpha-olefin with 4-10 carbon atom；(2) under the conditions of alkene gas-phase polymerization, by second comonomer b and step (1) obtain it is described containing crystalline polypropylene A the One mixture haptoreaction, obtains the second mixture containing crystalline polypropylene A and ethylene-propylene elastomeric copolymer B, and from this Unreacted monomer is removed in second mixture, obtains polymer composition, wherein, the second comonomer b contain propylene and Ethene and the alpha-olefin with 4-10 carbon atom；(3) polymer composition, the damage resistant master batch that will be obtained in acrylic resin, step (2), and optional polyethylene, Mineral filler and toughener are dry-mixed, and dry-mixed obtained mixture is carried out into melt blending.
- 16. the method according to claim 11, wherein, the ziegler natta catalyst with high stereoselective Particle diameter is more than 30 microns.
- 17. the method according to claim 11, wherein, the ziegler natta catalyst with high stereoselective Carrier is magnesium diaikoxide compound.
- 18. according to the method described in any one in claim 15-17, wherein, the neat lattice with high stereoselective Natta catalyst is strangled to contain：(i) ingredient of solid catalyst；(ii) organo-aluminum compound；And(iii) optional external donor compound,The ingredient of solid catalyst is made by following steps：(a) under inert gas shielding, using magnesium and alcohol as raw material, the back flow reaction in the presence of halogenating agent, dialkoxy is obtained Magnesium compound；(b) in the presence of inert diluent, magnesium diaikoxide compound and titanium compound and interior electron that step (a) is obtained Body compound carries out haptoreaction；The magnesium diaikoxide compound is spherical particle, and average grain diameter is 10~150 microns, particle diameter distribution index SPAN< 1.1。
- 19. according to the method for claim 15, wherein, first olefin polymerization conditions include：Temperature is 50-100 DEG C, Pressure is 1-8MPa, and the time is 30-180 minutes.
- 20. according to the method for claim 15, wherein, first olefin polymerization conditions include：Temperature is 60-95 DEG C, Pressure is 1.2-5.5MPa, and the time is 45-120 minutes.
- 21. according to the method for claim 15, wherein, the alkene gas-phase polymerization condition includes：Temperature is 50-100 DEG C, Pressure is 1-4MPa, and the time is 10-180 minutes.
- 22. according to the method for claim 15, wherein, the alkene gas-phase polymerization condition includes：Temperature is 60-95 DEG C, Pressure is 1.2-3.5MPa, and the time is 10-90 minutes.
- 23. the polypropene composition prepared as the method described in any one in claim 15-22.
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| CN102372874A (en) * | 2010-08-19 | 2012-03-14 | 中国石油化工股份有限公司 | Stress whitening resistant and scratch resistant polypropylene composition, and preparation method thereof |
| CN103201339A (en) * | 2010-11-12 | 2013-07-10 | 博里利斯股份公司 | Heterophasic propylene copolymers with improved stiffness/impact/flowability balance |
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| CN102372874A (en) * | 2010-08-19 | 2012-03-14 | 中国石油化工股份有限公司 | Stress whitening resistant and scratch resistant polypropylene composition, and preparation method thereof |
| CN103201339A (en) * | 2010-11-12 | 2013-07-10 | 博里利斯股份公司 | Heterophasic propylene copolymers with improved stiffness/impact/flowability balance |
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