CN104448537B - Polypropene composition and preparation method thereof and by its obtained product - Google Patents
Polypropene composition and preparation method thereof and by its obtained product Download PDFInfo
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- CN104448537B CN104448537B CN201310429271.4A CN201310429271A CN104448537B CN 104448537 B CN104448537 B CN 104448537B CN 201310429271 A CN201310429271 A CN 201310429271A CN 104448537 B CN104448537 B CN 104448537B
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- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
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Abstract
The present invention relates to a kind of polypropene composition and preparation method thereof and by its obtained product.The polypropene composition contains 70 95 weight % crystalline polypropylene A and 5 30 weight % ethylene propylene elastomeric copolymer B, wherein, the polypropene composition and the crystalline polypropylene A molecular weight distributing index are all higher than 4, and the ratio between the melt index of the polypropene composition and melt index of the crystalline polypropylene A are 0.7 1.3.The polypropene composition of the present invention can have high impact resistance and the good transparency, and preparation method economy concurrently while other performance is not reduced.
Description
Technical field
The present invention relates to a kind of polypropene composition, the preparation method of the polypropene composition is prepared using this method
Polypropene composition, and the product as made from the polypropene composition.
Background technology
Polypropylene material the advantages of its of fine quality, inexpensive, high temperature resistant, easy processing are molded in industry-by-industry because all obtaining extensively
Using.In fields such as toy, packaging, medicine equipment, commodity, it is desirable to use the transparency preferably resin.By adding
Clarifier can make HOPP obtain preferable transparency.Random copolymerization is carried out to polypropylene using monomers such as ethene, butylene,
Because the monomer of copolymerization destroys the regularity of propylene monomer arrangement on strand, the fusing point and knot of acrylic resin are reduced
Brilliant degree, further increases the transparency of material.But atactic copolymerized polypropene is similar to HOPP, its impact resistance compared with
Difference, can not especially provide preferable impact strength at low temperature.
Ethylene-propylene elastomeric copolymer is introduced by mechanical mixture or continuous polymerization, polyacrylic impact can be improved strong
Degree obtains high impact copolymer.Usual impact polypropylene is prepared by ziegler natta catalyst in multi-step polymerization reaction.Should
The ethylene-propylene elastomeric copolymer and HOPP of method production can be separated and cause the mist degree of final products to increase,
In addition, generally having by the binary ethylene-propylene elastomeric copolymer of Conventional Ziegler-Natta catalyst preparation very uneven
Composition, so this copolymer generally without the transparency.
Typically, the transparency of high impact copolymer is all very poor, can almost be sayed without what transparency.Specifically, phase
It is less than 20% mist degree for atactic copolymerized polypropene, the mist degree of the impact polypropylene of heterophasic copolymer is up to 98%（《Polypropylene
Handbook》（Chemical Industry Press, in June, 2008 first edition, page 259）.
Homogeneous catalyst, its Typical Representative is metallocene catalyst, with single active center's point feature.Pass through homogeneous catalysis
The Noblen and copolymer of agent polymerization have very narrow molecular weight distribution, general weight average molecular weight and the equal molecule of number
The ratio between amount is 2.5~3.5（《Polypropylene -- principle, technique and technology》, Sinopec publishing house, in June, 2007 first edition,
Page 208）.And Noblen and molecular weight of copolymer wider distribution prepared by Ziegler-Natta catalyst, typically divide equally again
The ratio between son amount and number-average molecular weight are more than 4（《Polypropylene handbook》（Chemical Industry Press, in June, 2008 first edition, the 15th
Page）.By the copolymer of homogeneous catalyst polymerization there is very narrow chemical composition to be distributed（《Polypropylene handbook》（Chemistry
Industrial publishing house, in June, 2008 first edition, page 72）, have very with its binary ethylene-propylene elastomeric copolymer prepared
Uniform composition, transparency is fine.Therefore the preferable shock resistance of transparency poly- third is relatively easily produced using homogeneous catalyst
Alkene.But homogeneous catalyst poor morphology, it is impossible to produced using common industrialization polypropylene plant；Even if by carrier to equal
Phase catalyst is loaded, the problem of morphology Control is still difficult to solve.The cost consumption of homogeneous catalyst will be far above neat
Ge Le-Natta catalyst, therefore its product is difficult to drop to compete with Ziegler-Natta catalyst in field of industrial production.
US4634740A discloses to use obtains and has the third of 70-85 weight % special ethylene contents with special catalyst
The method that alkene-ethylene copolymer is mixed in the molten state with polypropylene.And point out, relatively low or higher second in the copolymer
Alkene content is all without the result required for generation.Preparing such composition needs to be respectively synthesized homopolymer and copolymer, then
Mixed in molten state.This has clearly a need for expending more energy, produces higher cost.Additionally, due to shortage high activity
Catalyst synthesizing ethylene-propylene elastomeric copolymer, it is necessary to which catalyst residue is removed to polymer deliming.
To overcome above-mentioned deficiency, CN1045983A discloses the transparent polypropylene at low temperature with impact resistance and combined
Thing, the transparent polypropylene composition can be in polymerization（Sequential co-polymerization）Directly prepare, and use using magnesium dichloride as carrier
High activity ziegler natta catalyst.Said composition includes crystallization atactic propene copolymer, ethene and propylene and/or C4-C8
Alhpa olefin elastocopolymer, wherein the ethene containing 20-70 weight %.According to the invention, ethylene contents in elastocopolymer
Numerical value be multiplied by the inherent viscosity for the elastocopolymer for being dissolved in dimethylbenzene at room temperature and the inherent viscosity of random copolymer of propylene
（I.V.）Ratio be included in default scope.This method equivalent to by the homopolymer main part of impact polypropylene more
The polypropylene of random copolymerization is changed to, this obviously can decline the rigidity, hardness and heat resistance of final products.
CN1380893A discloses a kind of prolylene polymer composition, and it includes：A) the third of 70-90% (percentage by weight)
Alkene and ethylene atactic copolymer, the ethene containing 1-6%, the content of (about 23 DEG C) insoluble in xylene moiety is many at room temperature
In 93%；B) 10%-30% (percentage by weight) propylene and ethylene copolymer, the ethene containing 8-18%；Wherein, relative to
(A) and (B) gross weight (B) percentage by weight, and relative to the percentage by weight of ethene in (B) of (B) gross weight, the latter
By formula C2B represents, ratio (B)/C between the two2B is 2.5 or lower.This method is by the homopolymerization owner of impact polypropylene
Body portion is replaced by the polypropylene of random copolymerization, and this obviously can decline the rigidity, hardness and heat resistance of final products.
CN1861674A disclose it is a kind of have excellent impact resistance, the polypropene composition of bending modulus and transparency and
Its product.Said composition is included：（a）80-95 weight % highly crystalline random copolymer, the highly crystalline random copolymer be selected from
Propylene -1- the butylene of ethylene-propylene random copolymer containing 1-5 weight % ethene and the 1- butylene containing 2-12 weight % without
Advise at least one of copolymer；With（b）5-20 weight % ethylene-propylene elastomeric copolymer, the ethylene-propylene elastomeric copolymerization
Thing contains 30-50 weight % ethene, wherein, component（b）And component（a）Melt index ratio be 1.5-35.Poly- the third of the invention
Ene compositions are adapted to production cold storage container, refrigerated container, food container, extrusion moulding product, blow-molded article, film, thin
Piece and bottle stopper etc..The homopolymer main part of impact polypropylene is also replaced by the polypropylene of random copolymerization by this method, can also be made
Rigidity, hardness and the heat resistance of final products decline.
CN101506297A discloses a kind of polypropene composition and its product, said composition have mechanical performance with it is transparent
The optimum balance of degree, therefore said composition is particularly suitable for packaging applicationss.Said composition includes：a）Propylene copolymer（A）, it has
There are less than 160 DEG C of fusing point and below 1000MPa bending modulus, and b）Ethylene-propylene elastomeric copolymer（B）, based on ethene-
Propylene elastomeric copolymer（B）Weight, its propylene content be 80-92wt%.Wherein, component a）For random copolymer, it can make final
Rigidity, hardness and the heat resistance of product decline.Component b）To be total to using single site catalysts production from polyolefin elastic
Polymers, this composition has clearly a need for being mixed in molten state.This needs to expend more energy, with higher cost.
CN1957036A discloses a kind of flexible propylene copolymer compositions with the high grade of transparency.The propylene copolymer
Composition includes A）The propylene copolymer of 50%-80% weight, the propylene copolymer includes the 0.05- different from propylene
The alhpa olefin with 2-10 carbon atom of 0.99% weight；And B）A kind of propylene copolymer of 20%-50% weight, described one
Planting propylene copolymer has the alhpa olefin of 2-10 carbon atom comprising the 7.01-20.0% weight different from propylene；The propylene is total to
Ionomer compositions have following characteristic：(i) MFR (230 DEG C/2.16kg) [g/10 minutes] is 1-20；(ii) tensile E modulus is
400-800MPa(ISO527-2：1993).Said composition has preferable toughness, but metallocene catalyst must be used to be given birth to
Production, the catalyst has higher cost, and because its homogeneous speciality is not easy to use on common polyolefin device.
Although using seldom comonomer, rigidity, the hardness of final products are very low.
CN1659224A discloses a kind of propylene copolymer compositions, and it is included：A）Include being different from for 0-10% weight
The acrylic polymers and B of the alkene of propylene）The propylene copolymerization of at least one alkene different from propylene comprising 5-40% weight
Thing, wherein acrylic polymers A and propylene copolymer B are used as the mutually presence of separation, and the haze value of propylene copolymer compositions
≤ 30%, based on the path length of 1 millimeter of propylene copolymer compositions, and fragility/toughness of propylene copolymer compositions
Transition temperature is≤- 15 DEG C.Said composition has preferable toughness, but metallocene catalyst must be used to be produced, the catalysis
Agent has higher cost, and because its homogeneous speciality is not easy to use on common polyolefin device.Although using
Seldom comonomer, rigidity, the hardness of final products is still very low.
Therefore high impact resistance and well saturating can be had concurrently while other performance is not reduced by needing searching one kind badly
Bright property, and the polypropene composition of preparation method economy, this also will be enlarged by the use scope of polypropene composition.
The content of the invention
It is an object of the present invention to provide a kind of polypropene composition, the polypropene composition can not reduce other
While performance, high impact resistance and the good transparency, and preparation method economy are had concurrently.
It is a further object to provide the preparation method of above-mentioned polypropene composition, it the method achieve using company
Prepared by continuous polymerization has high impact resistance and good transparent polypropene composition concurrently.
The invention provides a kind of polypropene composition, on the basis of the gross weight of the polypropene composition, said composition
Contain：
（a）70-95 weight % crystalline polypropylene A, crystalline polypropylene A are selected from Noblen and propylene random copolymerization
At least one of thing, on the basis of the gross weight of propylene random co-polymer, the propylene random co-polymer contains 97-99.9
Weight % propylene construction unit, 0-1 weight % ethylene unit unit and 0-2 weight % the α with 4-10 carbon atom-
Olefin unit, and the total content of ethylene unit unit and the alpha-olefin construction unit with 4-10 carbon atom is 0.1-3
Weight %, and
（b）5-30 weight % ethylene-propylene elastomeric copolymer B, using ethylene-propylene elastomeric copolymer B gross weight as
Benchmark, ethylene-propylene elastomeric copolymer B contains 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 polypropene composition and the crystalline polypropylene A molecular weight distributing index are all higher than 4, described poly-
The ratio between the melt index of propylene compositions and the melt index of the crystalline polypropylene A are 0.7-1.3.
Preferably, the polypropene composition passes through in the presence of the ziegler natta catalyst with high stereoselective
It is made with continuous polymerization.
Present invention also offers a kind of preparation method of polypropene composition, the preparation method includes：
（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 from the mixture obtained after haptoreaction, obtain containing crystalline polypropylene A's
First mixture；And
（2）Under the conditions of alkene gas-phase polymerization, by second comonomer b and step（1）What is obtained is 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, polypropene composition is obtained；
Wherein, in step（1）In, the first monomer a contains propylene and optional ethene and/or with 4-10 carbon atom
Alpha-olefin so that step（1）Obtained crystalline polypropylene A contains 97-100 weight % propylene construction unit, 0-1 weight %
Ethylene unit unit and 0-2 weight % the alpha-olefin construction unit with 4-10 carbon atom,
Wherein, in step（2）In, second comonomer b contains propylene and ethene and/or α-alkene with 4-10 carbon atom
Hydrocarbon so that step（2）Obtained ethylene-propylene elastomeric copolymer B contains 60-92 weight % propylene construction unit, 8-25 weights
Amount % ethylene units unit and 0-15 weight % have the alhpa olefin construction unit of 4-10 carbon atom,
On the basis of the total output of the polypropene composition so that step（1）Obtained crystalline polypropylene A weight is
70-95%, step（2）Obtained ethylene-propylene elastomeric copolymer B weight is 5-30%, first olefin polymerization conditions
Cause that the polypropene composition and the crystalline polypropylene A molecular weight distributing index are equal with the alkene gas-phase polymerization condition
More than 4, the ratio between the melt index of the polypropene composition and the crystalline polypropylene A melt index is 0.7-1.3.
Present invention also offers the polypropene composition prepared by the above method.
Present invention provides a kind of product, product polypropene composition provided by the present invention is made.
In the prior art, high impact resistance and good transparent polypropene composition are had concurrently in order to obtain,
Each component must respectively be prepared, then carry out being blended so as to be made in the molten state, otherwise the cyclopentadienyl of costliness must be used
Metallic catalyst produces transparent impact polypropylene.In the present invention there is provided polypropene composition can not reduce other property
While energy, high impact resistance and the good transparency are had concurrently, so as to overcome drawbacks described above present in prior art.
Moreover, the method for the present invention can be prepared by conventional Ziegler Natta catalyst it is above-mentioned have concurrently it is high anti-
Impact and good transparent polypropene composition, significantly reduce production cost.
Other features and advantages of the present invention will be described in detail in subsequent embodiment part.
Brief description of the drawings
Fig. 1 is the atomic force microscopy of polypropene composition prepared by embodiment 1.
Fig. 2 is the atomic force microscopy of polypropene composition prepared by embodiment 3.
Embodiment
The embodiment to the present invention is described in detail below.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, on the basis of the gross weight of the polypropene composition, said composition
Contain：
（a）70-95 weight % crystalline polypropylene A, crystalline polypropylene A are selected from Noblen and propylene random copolymerization
At least one of thing, on the basis of the gross weight of propylene random co-polymer, the propylene random co-polymer contains 97-99.9
Weight % propylene construction unit, 0-1 weight % ethylene unit unit and 0-2 weight % the α with 4-10 carbon atom-
Olefin unit, and the total content of ethylene unit unit and the alpha-olefin construction unit with 4-10 carbon atom is 0.1-3
Weight %, and
（b）5-30 weight % ethylene-propylene elastomeric copolymer B, using ethylene-propylene elastomeric copolymer B gross weight as
Benchmark, ethylene-propylene elastomeric copolymer B contains 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 polypropene composition and the crystalline polypropylene A molecular weight distributing index are all higher than 4, described poly-
The ratio between the melt index of propylene compositions and the melt index of the crystalline polypropylene A are 0.7-1.3.
In the preferred case, the polypropene composition passes through in the ziegler natta catalyst with high stereoselective
In the presence of with continuous polymerization be made.The continuous polymerization refers to that preparation process includes the step of at least two orders are carried out,
Wherein, component（a）（That is crystalline polypropylene A）And component（b）（That is ethylene-propylene elastomeric copolymer B）Each comfortable individually step
Middle prepare, 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 polypropene composition uses the metallocene with high stereoselective
Catalyst is made, its molecular weight distribution and its component（a）And component（b）Molecular weight distribution be 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
In, molecular weight distribution is represented with the ratio between weight average molecular weight and number-average molecular weight.
In the present invention, the ratio between the melt index of the polypropene 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 polypropene composition can be 0.1-100g/
10min, preferably 0.5-50g/10min.In the present invention, melt index is determined according to ASTMD1238-99 methods.
In the preferred case, the polypropene composition contains：（a）70-90 weight % crystalline polypropylene A, and（b）
10-30 weight % ethylene-propylene elastomeric copolymer B.
In the present invention, it is described there is 4-10 carbon atom alpha-olefin can be 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）, heptene（Such as 1- heptene）And octene（Such as 1- octenes）At least one of,
Most preferably 1- butylene.
In the polypropene composition of the present invention, in addition to propylene construction unit, the crystalline polypropylene A can be with
Construction unit containing alpha-olefin comonomer.Because co-monomer content is less, the polypropene composition is shown preferably
Heat resistance.The crystalline polypropylene A can be selected from Noblen, the second containing 0.1-1 weight % ethylene unit units
Alkene-random copolymer of propylene or have containing 0.1-2 weight % 4-10 carbon atom alhpa olefin construction unit propylene random
Copolymer.When the crystalline polypropylene A is above-mentioned optional Noblen or random copolymer of propylene, the crystallization poly- third
Alkene A fusing point is more than 150 DEG C so that the polypropene composition has the fusing point more than 150 DEG C, so as to show preferably resistance to
Hot property.In the preferred case, the crystalline polypropylene A is Noblen, under the preferable case, the Polypropylene compositions
Thing has good rigidity and heat resistance concurrently.
In the polypropene composition of the present invention, the ethylene-propylene elastomeric copolymer B can contain a small amount of tool
There is the alpha-olefin construction unit of 4-10 carbon atom, for example, on the basis of ethylene-propylene elastomeric copolymer B gross weight, it is described
Ethylene-propylene elastomeric copolymer B can have 4-10 carbon containing 0.1-15 weight %, 0.1-5 weight % or 0.1-3 weight %
The alpha-olefin construction unit of atom.Under preferable case, the ethylene-propylene elastomeric copolymer B, which does not include substantially, has 4-10
The alpha-olefin construction unit of individual carbon atom；It is further preferred that using the gross weight of the ethylene-propylene elastomeric copolymer B as base
Standard, 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 elastomeric copolymer B contain 10-18 weight % ethylene unit unit and
82-90 weight % propylene construction unit.
The polypropene composition of the present invention, by AFM it is observed that the polypropene composition has
There is two phase structure.The particle that the ethylene-propylene elastomeric copolymer B is preferably less than 0.5 μm with average grain diameter is scattered in described poly-
In propylene compositions.In the present invention, the average grain diameter（That is granular size）Determined by atomic force microscopy.
In the present invention, the mist degree of the polypropene composition is preferably smaller than 60%, more preferably less than 30%, further excellent
Choosing is less than 20%.The mist degree is measured according to ASTM D1003 methods, i.e., the result measured on 1mm injected sample thin slice.
In the present invention, on the basis of the gross weight of polypropene composition, the polypropene composition can also contain 0.1-1
Weight % nucleator.The nucleator can be various nucleators commonly used in the art, for example：Double (tertiary fourths of 2,4- bis-
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 nucleation such as two benzal sorbierites or its alkyl-substituted derivative
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.Polypropene composition containing nucleator has higher
Bending modulus and the transparency.
In the present invention, the polypropene composition can also improve the antioxygen of polypropene composition containing antioxidant
Property.The antioxidant can be various antioxidant commonly used in the art, be not particularly limited.Usually, the antioxidant can be with
For the combination of primary antioxidant and auxiliary antioxidant, wherein, the primary antioxidant has the function of capture polymer peroxy radical,
Hindered phenol series antioxidant can be selected from；The auxiliary antioxidant can be effectively in decomposing copolymer hydroperoxides, prevent it
Homolysis produces new free radical, triggers the progress of Auto-oxidation reaction, for example, can be selected from phosphite ester system antioxidant and sulphur
For the one or more in ester system antioxidant.In the present invention, the example of the antioxidant can include but is not limited to：The uncles of 2,6- bis-
Butyl -4- methylphenols, β-positive octadecanol ester of (3,5- di-tert-butyl-hydroxy phenyls) propionic acid, four [β-(the tertiary fourths of 3,5- bis-
Base -4- hydroxy phenyls) propionic acid] pentaerythritol ester（That is, antioxidant 1010）, double [3- (3,5- di-t-butyls-the 4- of thio diethylene
Hydroxy phenyl) propionic ester, 1,3,5- trimethyls -2,4,6- three (3,5- di-tert-butyl-4-hydroxyl benzyls) benzene, 1,3,5- tri- (3,
5- di-tert-butyl-4-hydroxyl benzyls) -1,3,5- triazines -2,4,6 (1H, 3H, 5H)-triketone, three (2- methyl -4- hydroxyl -5- uncles
Butyl benzene) butane and 2,2 '-di-2-ethylhexylphosphine oxide (4- methyl-6-tert-butylphenols).Specifically, the example of the auxiliary antioxidant can
Think but be not limited to：Three [2,4- di-tert-butyl-phenyls] phosphite esters（That is, irgasfos 168）, four (2,4- di-tert-butylphenols) -4,
4 '-xenyl diphosphites, three nonylated phenyl phosphite esters, double (2,4- DI-tert-butylphenol compounds) pentaerythrite diphosphorous acids
The double octadecyls of ester, thio-2 acid and dilauryl thiodipropionate.From the further angle for improving antioxygenic property,
The antioxidant is anti-using phosphite ester and/or monothioester as auxiliary preferably using phenol system antioxidant as primary antioxidant
Oxygen agent.The ratio of the primary antioxidant and the auxiliary antioxidant can be the conventional selection of this area.Usually, the master resists
The weight ratio of oxygen agent and the auxiliary antioxidant can be 1：0.5-2.The content of the antioxidant can be the routine of this area
Selection, for example：On the basis of the gross weight of polypropene composition, the content of the antioxidant can be 0.15-0.8 weight %, excellent
Elect 0.2-0.4 weight % as.
In the present invention, the polypropene composition can also improve the anti-quiet of polypropene composition containing antistatic additive
Electrically.Antistatic additive can be but be not limited to monoglyceride class, ethyoxyl amine.The content of the antistatic additive can be this area
Conventional selection, for example：On the basis of the gross weight of polypropene composition, the content of the antistatic additive can be 0.02-1 weights
Measure %.
In the present invention, composition of the invention can also improve the aesthetic property of polypropene composition containing colouring agent.
Colouring agent generally according to end article the need for be added.
The invention provides a kind of preparation method of polypropene composition, the preparation method may comprise steps of：
（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 from the mixture obtained after haptoreaction, obtain containing crystalline polypropylene A's
First mixture；And
（2）Under the conditions of alkene gas-phase polymerization, by second comonomer b and step（1）What is obtained is 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, polypropene composition is obtained；
Wherein, in step（1）In, the first monomer a contains propylene and optional ethene and/or with 4-10 carbon atom
Alpha-olefin so that step（1）Obtained crystalline polypropylene A contains 97-100 weight % propylene construction unit, 0-1 weight %
Ethylene unit unit and 0-2 weight % the alpha-olefin construction unit with 4-10 carbon atom,
Wherein, in step（2）In, second comonomer b contains propylene and ethene and/or α-alkene with 4-10 carbon atom
Hydrocarbon so that step（2）Obtained ethylene-propylene elastomeric copolymer B contains 60-92 weight % propylene construction unit, 8-25 weights
Amount % ethylene units unit and 0-15 weight % have the alhpa olefin construction unit of 4-10 carbon atom,
On the basis of the total output of the polypropene composition so that step（1）Obtained crystalline polypropylene A weight is
70-95%, step（2）Obtained ethylene-propylene elastomeric copolymer B weight is 5-30%, first olefin polymerization conditions
Cause that the polypropene composition and the crystalline polypropylene A molecular weight distributing index are equal with the alkene gas-phase polymerization condition
More than 4, the ratio between the melt index of the polypropene composition and the crystalline polypropylene A melt index is 0.7-1.3.
In the preferred case, by controlling first olefin polymerization conditions and the alkene gas-phase polymerization condition so that institute
The melt index for stating polypropene composition is 0.1-100g/10min, more preferably 0.5-50g/10min.First alkene gathers
Conjunction condition and the alkene gas-phase polymerization condition cause the melt index of the polypropene composition with the crystalline polypropylene A's
The ratio between melt index is 0.75-1.3, preferably 0.75-1.2.
In the methods described that provides of the present invention, the alpha-olefin with 4-10 carbon atom can be with being described above
It is identical.
The present inventor has found in research process：Carrying out at least including two using ziegler natta catalyst
During the propylene polymerization of sequential steps, by controlling polymerizing condition so that the melt index of polypropene 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 polypropene composition of formation can have the high transparency and impact strength.
Preparation in accordance with the present invention, in one embodiment, the first monomer a are propylene so that first
The crystalline polypropylene A obtained under olefin polymerization conditions is Noblen.
Preparation in accordance with the present invention, in a preferred embodiment, the second comonomer b are propylene and second
Alkene so that the ethylene-propylene elastomeric copolymer B obtained under the conditions of alkene gas-phase polymerization contains 75-92 weight % propylene structure
The ethylene unit unit of unit and 8-25 weight %；It is further preferred that so that ethylene-propylene elastomeric copolymer B contains 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 method according to the invention, the ziegler natta catalyst with high stereoselective can be normal for this area
It is various to be catalyzed the catalyst that propylene carries out isotactic polymerization.Usually, it is described neat with high stereoselective
Lattice are strangled Natta catalyst and contained：（1）The solid catalyst activity component of titaniferous, its main component be magnesium, titanium, halogen and it is interior to electricity
Daughter；（2）Organo-aluminum compound cocatalyst component；And（3）Optional external electron donor component.
The available this kind of instantiation containing active solid catalyst component be disclosed in CN85100997,
CN98126383.6、CN98111780.5、CN98126385.2、CN93102795.0、CN00109216.2、
In CN99125566.6, CN99125567.4, CN02100900.7.Described catalyst can be used directly, can also be passed through
Added after pre- complexing and prepolymerization.Catalyst described in CN85100997, CN98111780.5 and CN02100900.7, is used
Especially there is advantage in the catalyst of the present invention.
It is preferably alkyl aluminum compound as the organo-aluminum compound of the cocatalyst component of catalyst, is more preferably selected from three
Alkyl aluminum（Such as：Trimethyl aluminium, triethyl aluminum, triisobutyl aluminium, three n-butylaluminums, trioctylaluminum etc.）, aluminium diethyl monochloride, one
At least one in chloro-di-isobutyl aluminum, aluminium diethyl monochloride, a chloro-di-isobutyl aluminum, the aluminium ethide of dichloro one and ethyl aluminum dichloride
Kind.
With Ti/Al molar ratio computings, the solid catalyst activity component and organo-aluminum compound cocatalyst component of titaniferous it
Than that can be 1:25 to 1:1000.
It is preferably organo-silicon compound as the external donor compound of optional catalyst component, 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, can also be then added to after pre- complexing known to industry and/or prepolymerization 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 temperature preferably is 0 to 40 DEG C.In advance
The multiple of polymerization can be controlled at 0.5 to 1000 times, and multiple preferably is 1.0 to 500 times.
Preparation in accordance with the present invention, the first olefinic polymerization and alkene gas-phase polymerization can be carried out continuously, can also between
Have a rest progress.Continuous polymerization can use more than two tandem reactors to carry out.
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., above liquid phase Deng, Gas-phase reactor
Reactor and Gas-phase reactor can also arbitrarily matched combineds.
Preparation in accordance with the present invention, first olefin polymerization conditions can include：Temperature is 50-100 DEG C, preferably
For 60-95 DEG C；Pressure is 1-8MPa, preferably 1.2-5.5MPa；Time is 30-180 minutes, preferably 45-120 minutes.
In the present invention, 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.
Preparation in accordance with the present invention, the alkene gas-phase polymerization condition can include：Temperature is 50-100 DEG C, preferably
For 60-95 DEG C；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：To step（2）Obtained polypropylene
Composition is granulated, and adds nucleator when polypropene composition is granulated.Preferably, the consumption of the nucleator causes
Contain 0.1-1 weight % in the polypropene composition obtained after granulation（It is preferred that 0.2-0.5 weight %）Nucleator.The nucleation
Agent can be identical with what is be described above.
In the present invention, for the antioxidant of the polypropene composition that improves preparation, the preparation of the polypropene composition
Method adds antioxidant when being additionally may included in polypropene composition granulation.Preferably, the consumption of the antioxidant causes granulation
Contain 0.15-0.8 weight % in the polypropene composition obtained afterwards（It is preferred that 0.2-0.4 weight %）Antioxidant.The antioxidant
Can be identical with what is be described above.
In the present invention, add when the preparation method of the polypropene composition is additionally may included in polypropene composition granulation
Plus other auxiliary agents such as antistatic additive and/or colouring agent.
Present invention also offers the polypropene composition prepared by the above method.
Present invention also offers the product being made up of above-mentioned polypropene composition.The product has well transparent and anti-
Impact.The product can be cold storage container, refrigerated container, food container, extrusion moulding product, blow-molded article, fibre
Dimension, film, thin slice or bottle stopper.
The present invention will be described in detail by way of examples below.
Experimental result in embodiment is obtained according to following test method, is being not particularly limited in following test method
In the case of operated under room temperature environment：
Melt index（MFR）：According to ASTM D1238, determined under 230 DEG C, 2.16kg load.
Co-monomer content：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, first rise to 200 DEG C to eliminate thermal history by 10 DEG C/min speed by sample, then by 10 DEG C/min's
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 is measured.
Light transmittance：According to ASTM D1003, the light transmittance of the injected sample of 1 millimeters thick is measured.
Atomic force microscopy：Polypropylene is molded batten through cryogenic freezing to ultra-thin section after subzero 50 degrees Celsius, sees
Examine tangent plane.Vecco companies of U.S. Naonscope IIIa type multiple mode scanning force microscopes, J probes, tapping-mode, scanning
10 microns × 10 microns or 5 microns × 5 microns of scope, gathers phasor.
Molecular weight distributing index Mw/Mn：Oozed using Polymer Laboratories companies of Britain production PL-GPC220 gels
The molecular weight distribution of saturating chromatograph determination sample, chromatographic column is Plgel10 μm of MIXED-B post of 3 series connection, solvent and mobile phase
For 1,2,4- trichloro-benzenes, 150 DEG C of column temperature, using the pervasive mark of PL companies EasiCal PS-1 Narrow distribution polystyrenes standard specimen progress
Fixed, detector uses the infrared concentration detectors of IR5 of POLYCHAR companies.
Polypropene composition in of the invention and embodiment is obtained by the following method, and material amounts therein and polymerization are anti-
Condition is answered to be listed in Table 1 below.
Polymerisation is carried out on set of horizontal type gas phase polypropylene pilot-plant, polymer reactor be two series connection it is horizontal
Stirred autoclave, polymerization and step are as follows：
Major catalyst（The active solid catalyst component of titaniferous）The method described using embodiment in CN1258683A 1 is obtained
Arrive, internal electron donor compound therein uses diisobutyl phthalate.
Major catalyst, co-catalyst（Triethyl aluminum）, external electron donor horizontal stir is added continuously 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 is taken away by the propylene vaporization sprayed.The polymer of generation is discharged by the end of stirred tank.Catalyst and poly-
Compound is moved in the way of approaching laminar flow in reactor, and polymerization temperature is 66 DEG C, reaction pressure 2.3MPa, and the residence time is
90 minutes.
Polymer is discharged from first reactor, and by the equipment 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 is taken away by the propylene vaporization sprayed.The polymer of generation is discharged by the end of stirred tank.
Catalyst and polymer are moved in the way of approaching laminar flow in reactor, and polymerization temperature is 66 DEG C, reaction pressure 2.2MPa,
It is 60 minutes during stop.
React that obtained polymer is degassed, after wet nitrogen deactivation processing, obtain polymeric articles.
Gas in the continuous analysis reactor of gas-chromatography is used as molecular weight regulator using hydrogen in two reactors
The composition of body（Ethene, propylene, butylene and hydrogen）
0.1 parts by weight are separately added into powder according to the obtained parts by weight of polypropene composition 100
IRGAFOS168 additives（Purchased from Ciba Co., Ltd）, 0.1 parts by weight IRGANOX1010 additives（Purchased from vapour bar
Refine Co., Ltd）With the calcium stearate of 0.05 parts by weight（Purchased from Ciba Co., Ltd）, and add purchased from Milliken
The Millad3988 additives of company（Specific consumption is referring to table 2）, 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.
Comparative example 1
Polymerisation is carried out on above-mentioned horizontal pneumatic heterophasic polypropylene pilot-plant, and reaction is carried out according to the method described above.Using
External electron donor be diisopropyl dimethoxy silane, first reactor polymerisation be propylene homo, polymerization temperature is 66
DEG C, reaction pressure 2.3MPa, the residence time is 90 minutes.Second reactor also carries out propylene homo, and polymerization temperature is 66 DEG C, instead
Pressure 2.2MPa is answered, the residence time is 60 minutes.React that obtained polymer is degassed, after wet nitrogen deactivation processing, gathered
Composition powder.Reaction condition and product property are as shown in table 1.Product adds additive granulation, and testability after injected sample is made
Can be as shown in table 2.
Comparative example 2
Polymerisation is carried out according to the method for comparative example 1, the difference is that the external electron donor used is diisobutyl diformazan
TMOS, and without using second reactor, reaction condition and product property are as shown in table 1.Product adds additive granulation, system
Test performance is as shown in table 2 after into injected sample.
Embodiment 1
Polymerisation is carried out on above-mentioned horizontal pneumatic heterophasic polypropylene pilot-plant, and reaction is carried out according to the method described above.Polymerization
The external electron donor used is reacted for second, isobutyl dimethoxy silane, and first reactor is that propylene homo prepares component（a）, gather
It is 66 DEG C to close temperature, reaction pressure 2.3MPa, and the residence time is 90 minutes.Second reactor is that propylene copolymerization prepares component（b）,
Ethene and propylene are added in reactor, polymerization temperature is 66 DEG C, and reaction pressure 2.2MPa, the residence time is 60 minutes.React
The polymer that arrives is degassed, after wet nitrogen deactivation processing, obtains polypropene composition.Reaction condition and the product property such as institute of table 1
Show.Polypropene composition adds additive granulation, test performance after injected sample is made as shown in table 2.The polypropylene group of preparation
The atomic force microscopy of compound as shown in figure 1, it can be seen that the polypropene composition has two phase structure,
And show component（b）It is highly dispersed in about 0.2 micron of particle diameter in composition.
Embodiment 2
Polymerisation is carried out on above-mentioned horizontal pneumatic heterophasic polypropylene pilot-plant, and reaction is carried out according to the method described above.Polymerization
The external electron donor used is reacted for diisopropyl dimethoxy silane, and first reactor is that propylene homo prepares component（a）, gather
It is 66 DEG C to close temperature, reaction pressure 2.3MPa, and the residence time is 90 minutes.Second reactor is that propylene copolymerization prepares component（b）,
Ethene and propylene are added in reactor, polymerization temperature is 66 DEG C, and reaction pressure 2.2MPa, the residence time is about 60 minutes.Reaction
Obtained polymer is degassed, after wet nitrogen deactivation processing, obtains polypropene composition.Reaction condition and product property such as table 1
It is shown.Polypropene composition adds additive granulation, test performance after injected sample is made as shown in table 2.
Embodiment 3
Method according to embodiment 2 prepares polypropene composition, the difference is that changing component（b）Composition and content.Instead
Answer condition and product property as shown in table 1.Product adds additive granulation, test performance after injected sample is made as shown in table 2.
The atomic force microscopy of the polypropene composition of preparation is as shown in Fig. 2 it can be seen that the polypropene composition
With two phase structure, and show component（b）It is highly dispersed in about 0.3 micron of particle diameter in composition.
Embodiment 4
Method according to embodiment 2 prepares polypropene composition, the difference is that changing component（b）Composition and content.Instead
Answer condition and product property as shown in table 1.Product adds additive granulation, test performance after injected sample is made as shown in table 2.
Embodiment 5
Method according to embodiment 1 prepares polypropene composition, and the external electron donor used is diisobutyl dimethoxy
Silane, the difference is that changing component（b）Composition and content.Reaction condition and product property are as shown in table 1.Product adds addition
Agent is granulated, and test performance after injected sample is made as shown in table 2.
Embodiment 6
Polymerisation is carried out on above-mentioned horizontal pneumatic heterophasic polypropylene pilot-plant, and reaction is carried out according to the method described above.Polymerization
The external electron donor used is reacted for Cyclohexyl Methyl Dimethoxysilane, and first reactor is that propylene homo prepares component（a）,
Polymerization temperature is 66 DEG C, reaction pressure 2.3MPa, and the residence time is 90 minutes.Second reactor is that propylene copolymerization prepares component
（b）, reactor is interior to add ethene, propylene and butylene, and polymerization temperature is 66 DEG C, and reaction pressure 2.2MPa, the residence time is 60 points
Clock.React that obtained polymer is degassed, after wet nitrogen deactivation processing, obtain polypropene composition.Reaction condition and product
Can be as shown in table 1.Polypropene composition adds additive granulation, test performance after injected sample is made as shown in table 2.
Table 1
Note：P is diisopropyl dimethoxy silane；B is second, isobutyl dimethoxy silane；C is cyclohexyl methyl diformazan
TMOS；MFRa+b/MFRaRefer to the melt index ratio of polypropene composition and crystalline polypropylene A.
Table 2
HOPP of the polypropene composition relative to comparative example of the present invention it can be seen from the result of Tables 1 and 2
Impact resistance is improved largely, while other performance is not reduced, and has the good transparency concurrently.
Claims (19)
1. a kind of polypropene composition, it is characterised in that on the basis of the gross weight of the polypropene composition, said composition contains
Have：
(a) 70-95 weight % crystalline polypropylene A, crystalline polypropylene A is in Noblen and random copolymer of propylene
At least one, on the basis of the gross weight of propylene random co-polymer, the propylene random co-polymer contain 97-99.9 weight
Measure % propylene construction unit, 0 to the ethylene unit unit less than 1 weight % and 0-2 weight % there is 4-10 carbon atom
Alpha-olefin construction unit, and the total content of ethylene unit unit and the alpha-olefin construction unit with 4-10 carbon atom is
0.1-3 weight %, and
(b) 5-30 weight % ethylene-propylene elastomeric copolymer B, on the basis of ethylene-propylene elastomeric copolymer B gross weight,
Ethylene-propylene elastomeric copolymer B contains 60-92 weight % propylene construction unit, 8-25 weight % ethylene unit unit
And the 0-15 weight % alpha-olefin construction unit with 4-10 carbon atom,
Wherein, the polypropene composition and the crystalline polypropylene A molecular weight distributing index are all higher than 4, the polypropylene
The ratio between the melt index of composition and the melt index of the crystalline polypropylene A are 0.7-1.3.
2. polypropene composition according to claim 1, wherein, the polypropene 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 1, wherein, should on the basis of the gross weight of the polypropene composition
Composition contains：
(a) 70-90 weight % crystalline polypropylene A, and
(b) 10-30 weight % ethylene-propylene elastomeric copolymer B.
4. the polypropene composition according to any one in claim 1-3, wherein, the crystalline polypropylene A is propylene
Homopolymer.
5. the polypropene composition according to any one in claim 1-3, wherein, it is common with the ethylene-propylene elastomeric
On the basis of polymers B gross weight, ethylene-propylene elastomeric copolymer B contains 10-18 weight % ethylene unit unit and 82-
90 weight % propylene construction unit.
6. the polypropene composition according to any one in claim 1-3, wherein, the melting of the polypropene composition
Index is 0.1-100g/10min.
7. the polypropene composition according to any one in claim 1-3, wherein, with the gross weight of the polypropene composition
On the basis of amount, nucleator of the polypropene composition also containing 0.1-1 weight %.
8. the polypropene composition according to any one in claim 1-3, wherein, the polypropene composition according to
The mist degree that ASTM D1003 methods are determined is less than 60%.
9. the polypropene composition according to any one in claim 1-3, wherein, the ethylene-propylene elastomeric copolymerization
The particle that thing B is less than 0.5 μm with average grain diameter is scattered in the polypropene composition.
10. a kind of preparation method of polypropene composition, the preparation method comprises the following steps：
(1) under the first olefin polymerization conditions, the first monomer a is connect with the ziegler natta catalyst with high stereoselective
Reaction is touched, and unreacted monomer is removed from the mixture obtained after haptoreaction, first containing crystalline polypropylene A is obtained
Mixture；And
(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, polypropene composition is obtained；
Wherein, in step (1), the first monomer a contains propylene and optional ethene and/or α with 4-10 carbon atom-
Alkene so that the crystalline polypropylene A that step (1) is obtained contains 97-100 weight % propylene construction unit, 0 to less than 1 weight
% ethylene unit unit and the 0-2 weight % alpha-olefin construction unit with 4-10 carbon atom are measured,
Wherein, in step (2), second comonomer b contains propylene and ethene and/or the alpha-olefin with 4-10 carbon atom,
So that the ethylene-propylene elastomeric copolymer B that step (2) is obtained contains 60-92 weight % propylene construction unit, 8-25 weight %
Ethylene unit unit and 0-15 weight % have the alhpa olefin construction unit of 4-10 carbon atom,
On the basis of the total output of the polypropene composition so that the weight for the crystalline polypropylene A that step (1) is obtained is 70-
95%, the ethylene-propylene elastomeric copolymer B that step (2) is obtained weight are 5-30%, first olefin polymerization conditions and institute
Alkene gas-phase polymerization condition is stated so that the polypropene composition and the crystalline polypropylene A molecular weight distributing index are all higher than
4, the ratio between the melt index of the polypropene composition and the crystalline polypropylene A melt index is 0.7-1.3.
11. method according to claim 10, wherein, the crystalline polypropylene A that step (1) is obtained is Noblen.
12. method according to claim 10, wherein, the ethylene-propylene elastomeric copolymer B that step (2) is obtained contains 10-
18 weight % ethylene unit unit and 82-90 weight % propylene construction unit.
13. method according to claim 10, wherein, the alpha-olefin with 4-10 carbon atom is 1- butylene.
14. method according to claim 10, wherein, first olefin polymerization conditions include：Temperature is 50-100 DEG C,
Pressure is 1-8MPa, and the time is 30-180 minutes.
15. method according to claim 10, 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.
16. the method according to any one in claim 10-15, wherein, methods described also includes obtaining step (2)
Polypropene composition granulated, and add when polypropene composition is granulated nucleator, the consumption of the nucleator makes
Nucleator containing 0.1-1 weight % in the polypropene composition obtained after must granulating.
17. the polypropene composition prepared as the method described in any one in claim 10-16.
18. a kind of product, the product is made as the polypropene composition described in any one in claim 1-9 and 17.
19. product according to claim 18, wherein, the product is cold storage container, refrigerated container, packaging for foodstuff appearance
Device, extrusion moulding product, blow-molded article, fiber, film, thin slice or bottle stopper.
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| CN105524351B (en) * | 2014-10-27 | 2019-03-26 | 中国石油化工股份有限公司 | The preparation method of non-woven fabrics raw material and preparation method thereof and non-woven fabrics |
| CN105623074B (en) * | 2014-10-27 | 2018-12-28 | 中国石油化工股份有限公司 | The preparation method of non-woven fabrics raw material and preparation method thereof and non-woven fabrics |
| CN105218718A (en) * | 2015-09-23 | 2016-01-06 | 神华集团有限责任公司 | A kind of transparent polypropylene resin and preparation method thereof |
| CN106554448B (en) * | 2015-09-30 | 2019-07-30 | 中国石油化工股份有限公司 | High-impact transparent polypropylene resin |
| EP3168261B1 (en) * | 2015-11-10 | 2019-08-28 | Borealis AG | Heterophasic polypropylene composition |
| ES2765401T3 (en) * | 2015-12-21 | 2020-06-09 | Borealis Ag | Items with improved optical properties |
| CN108223202A (en) * | 2016-12-21 | 2018-06-29 | 丁大烈 | internal combustion engine system and combustion engine energy-saving emission-reducing system |
| SG10201903296WA (en) * | 2019-04-12 | 2020-09-29 | Thai Polyethylene Co Ltd | A Polypropylene Composition for Retort Packaging Application |
| EP4206276A4 (en) * | 2020-08-27 | 2024-10-16 | China Petroleum & Chemical Corp | Polypropylene composition, preparation method therefor, and article made therefrom |
| CN116063789B (en) * | 2021-11-01 | 2024-07-02 | 中国石油化工股份有限公司 | Heterophasic polypropylene composition, and preparation method and application thereof |
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