CN106674749B - A kind of polypropylene blow moulding film and preparation method thereof - Google Patents
A kind of polypropylene blow moulding film and preparation method thereof Download PDFInfo
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Abstract
The present invention provides a kind of polypropene compositions for Blown Film, including the high fondant-strength impact polypropylene as basic resin, and the high fondant-strength impact polypropylene includes atactic copolymerized polypropene continuous phase and propylene-ethylene copolymers rubber domain, its room temperature xylene soluble content is greater than or equal to 10 weight %, and is less than or equal to 35 weight %；And the ratio between Mw of the Mw of its room temperature trichloro-benzenes soluble matter and room temperature trichlorine benzene insoluble is greater than 0.4, is less than or equal to 1.The present invention also provides use the composition through polypropylene blow moulding film and preparation method thereof prepared by blow molding, the blown film has shock resistance lear energy strong, the high feature of tensile strength, sterilizes by cooking at a high temperature and the large-scale fields such as pack again especially suitable for cooking food bag, microwave food packaging, doctor.
Description
Technical field
The present invention relates to polymeric material fields, and in particular to a kind of composition for being used to prepare polypropylene blow moulding film, logical
Cross the polypropylene blow moulding film and preparation method thereof that the composition is prepared.
Background technique
Polypropylene (PP) film mechanical strength, good heat resistance and grease resistance with higher and preferable transparent
Property, it is widely used in industry and daily life, especially suitable for cooking food bag, microwave food packaging, medical high temperature
Retort sterilization and large-scale packaging etc. again.
Extrusion blow molding film simple process, equipment are few, have cost advantage.Extrusion blow molding film accounts for all film productions
85%.But for polypropylene film, mainly use extrusion curtain coating single, double for a long time to stretching technique production.Due to
The melt viscosity and melt strength of plain polypropylene resin are low, it is difficult to extrusion-blown modling film forming.Recently as polymerization and catalyst
The progress of technology is suitble to the high bath strength acrylic resin of extrusion-blown modling to be developed.Since this kind of acrylic resin is molten
Body intensity and viscosity are much higher compared with plain polypropylene, therefore can produce polypropylene in traditional polyethylene blown film equipment
Film.Extrusion-blown modling polypropylene film is at low cost, and high production efficiency, tearing strength are big, film thickness range is wide.
In order to improve polypropylene blow moulding film forming applicability, have at present using the addition copolymerization of ethylene list in propylene polymerization processes
The method of body produces polypropylene blown film by raw material of copolymer to produce copolymer.Due to the addition of vinyl monomer, mention
The high toughness of film, but the difference of the vertical and horizontal tearing strength of film is still very big, and causes the heat resistance of film big
Width decline.In addition, the general polyacrylic puncture resistant impact resistance of commercialization is poor, a kind of anti-impact enhanced polypropylene is needed
Preparation for polypropylene blown film.
As it can be seen that exploitation has the polypropylene blown film of the shock resistance, tear-proof and the tensile resistance that further increase, with
Its applicability and the scope of application are further expanded, is still the obvious demand of existing market.
Summary of the invention
The purpose of the present invention is to provide a kind of compositions for being used to prepare polypropylene blow moulding film, are prepared using the composition
Obtained polypropylene blown film.Compared with the existing technology, it is blown using what polypropene composition provided by the invention was prepared
Film is moulded, under the premise of not reducing the heat resistance of film, can be improved the tearing strength of film, improves vertical and horizontal tearing
Intensity reduces the difference of vertical and horizontal tearing strength.
The present invention also provides the preparation methods of the polypropylene blown film, can advantageously utilize general blow molding
Technique is implemented.
According to the present invention, a kind of polypropene composition for Blown Film is provided, including the height as basic resin
Melt strength impact polypropylene, the high fondant-strength impact polypropylene include atactic copolymerized polypropene continuous phase and propylene-second
Olefinic copolymer rubber dispersed phase, wherein the atactic copolymerized polypropene continuous phase includes at least the first atactic copolymerized polypropene and the
Two atactic copolymerized polypropenes, and first atactic copolymerized polypropene and the second atactic copolymerized polypropene are each independently selected from
Propylene-ethylene random copolymer or propylene -1- butene random copolymer or ethylene-propylene -1- butene terpolymers；The height
The room temperature xylene soluble content of melt strength impact polypropylene is greater than or equal to 10 weight %, and is less than or equal to 35 weights
Measure %；And the Mw (weight average molecular weight) of the room temperature trichloro-benzenes soluble matter of the high fondant-strength impact polypropylene and room temperature trichlorine
The ratio between Mw of benzene insoluble is greater than 0.4, is less than or equal to 1, is greater than 0.4, and be less than or equal to 0.8.Above-mentioned high melt is strong
Spending impact polypropylene has excellent rigidity and toughness, is provided simultaneously with higher melt strength, and resin preparation based on this is blown
Film is moulded, obtained film is likewise supplied with high melt strength, rigidity and toughness, especially has stronger anti-impact, stretch-proof
Performance, and have stronger tearing strength and low transverse and longitudinal tearing strength poor.Thus, the present invention provides one kind for making
The composition of standby high fondant-strength impact polypropylene inflation film.
In the present invention, the impact polypropylene of the high fondant-strength refers to the polypropylene comprising features described above.
In the present invention, high fondant-strength refers to that melt strength is greater than 0.1N, especially 0.15-0.25N.Anti-impact basic tree
(23 DEG C) of Izod notch shock of rouge are 70~100KJ/m2。
In the present invention, the content of the rubber phase of base resin is in terms of room temperature xylene soluble content, can be according to
The measurement of CRYSTEX method.Convenient for characterization, the molecular weight of rubber phase is with the Molecular weights of trichloro-benzenes soluble matter.
In base resin used in the present invention, atactic copolymerized polypropene is polypropylene base resin as continuous phase
Certain rigidity is provided, propylene-ethylene copolymers rubber can be improved the toughness of polypropylene base resin as dispersed phase.For
Guarantee product of the invention has a preferable rigid-tough balance, the present invention using ethylene-propylene copolymer as rubber components,
Also, the present inventor has found by a large number of experiments, in the high fondant-strength impact polypropylene material that the present invention uses,
When the ethylene contents in the room temperature xylene soluble part for making the material are greater than or equal to 28 weight %, and less than 45 weight %
When, impact polypropylene material has preferable rigidity and toughness.Especially, in the present invention, by by atactic copolymerized polypropene
Continuous phase is arranged to include at least the first atactic copolymerized polypropene and the second atactic copolymerized polypropene, and described first is random total
Poly- polypropylene and the second atactic copolymerized polypropene be each independently selected from Propylene-ethylene random copolymer or propylene -1- butylene without
Copolymer or ethylene-propylene -1- butene terpolymers are advised, so that continuous phase and dispersed phase be made preferably mutually to compound, are generated
The impact polypropylene material of high fondant-strength and high tenacity, advantageously acts as the base resin of polypropylene blow moulding film.Here, being easy
Understand, so-called " ethylene contents " can be understood as the part being made of in the polymer that vinyl monomer participates in vinyl monomer
Weight content.Herein, other indicate " butene content " in the polymer, and meaning is similar.
In order to obtain higher melt strength, the melting of high fondant-strength impact polypropylene material used in the present invention refers to
Number range is preferably controlled in 0.1-15g/10min, further preferably 0.1-6.0g/10min.The melt index is at 230 DEG C, 2.16kg
Load under measure.
For high fondant-strength impact polypropylene, due to being the material of heterogeneous structure, the factor for influencing melt strength just becomes
It obtains complex.The inventors discovered that the high fondant-strength in order to guarantee base resin and blown film product, as basic resin
The molecular weight distribution mw/mn (weight-average molecular weight/number-average molecular weight) of impact polypropylene material be preferably lower than or equal to 10, and it is big
In or be equal to 4, for example, 4,5,6,7,8,9 or 10；And/or Mz+1/Mw is preferably greater than or equal to 10, and preferably smaller than 20.
In some preferred embodiments, the ethylene of high fondant-strength impact polypropylene material used in the present invention contains
Amount is 8-20 weight %；And/or butene content is 0-10 weight %.
Used base resin according to the present invention, molecular weight polydispersity index (PI) are 4-10, preferably 4.5-6.
The base resin of the polypropylene blow moulding film provided according to the present invention passes through depositing in the first atactic copolymerized polypropene
Reacting to obtain in the lower random copolymerization for carrying out acrylic includes the first atactic copolymerized polypropene and the second atactic copolymerized polypropene
Then atactic copolymerized polypropene continuous phase carries out propylene-ethylene copolymerization in the presence of the atactic copolymerized polypropene continuous phase
Reaction obtains the polypropylene material comprising propylene-ethylene copolymers rubber phase to prepare.It can be seen that base used in the present invention
Plinth resin, that is, high fondant-strength impact polypropylene material is not atactic copolymerized polypropene continuous phase and propylene-ethylene copolymers rubber
Glue dispersed phase is simply mixed, but further progress propylene-ethylene is copolymerized on the basis of atactic copolymerized polypropene continuous phase
The globality poly- third comprising atactic copolymerized polypropene continuous phase and propylene-ethylene copolymers rubber domain obtained after reaction
Alkene material.
Base resin used in the present invention also has preferable heat resistance and preferable heat sealability, is surveyed using DSC
The melting peak temperature T of fixed final acrylic resinmMore than or equal to 145 DEG C, it is less than or equal to 158 DEG C.
According to the present invention, the composition can also optionally include linear low density polyethylene.Preferably, described linear
The melt flow rate (MFR) range of low density polyethylene (LDPE) is 0.1~3.0g/10min (190 DEG C/2.16kg).
It is described herein to be, due to having used base resin of good performance as described above, provide according to the present invention
For not needing to add as linear in the polypropene composition of Blown Film or the method for polypropylene blow moulding film as described below
This kind of modified component of low density polyethylene (LDPE) can also be prepared with good comprehensive including high tenacity and good heat resistance
The polypropylene blow moulding film of energy, shown in embodiment part as follows, this is an advantage of the invention place.Therefore, in some tools
In body embodiment, composition of the invention does not include linear low density polyethylene.
According to the present invention, the composition can also optionally add other processing aids, other described processing aids are excellent
Choosing is selected from least one of antioxidant, aid anti-oxidants, lubricant and antistatic agent.
Above-mentioned auxiliary agent can be selectively added according to specific needs.The auxiliary agent of selected addition can be polypropylene blow moulding
Common auxiliary agent, such as antioxidant, aid anti-oxidants, lubricant and antistatic agent etc. in film.The dosage of auxiliary agent is conventional use
Amount, or requirement according to the actual situation are adjusted.
Antioxidant can be for example antioxidant 1010 etc.；Aid anti-oxidants are, for example, aid anti-oxidants 168 etc..Lubricant is, for example,
Calcium stearate or magnesium stearate etc..
The present invention also provides a kind of polypropylene blow moulding films, by using the combination as described above provided according to the present invention
Object is made by Blown Film.
According to the present invention, the polypropylene blow moulding film is the film that can adjust thickness with concrete technology according to demand, thick
Degree is generally 5-100 μm, especially 15-60 μm.
According to the present invention, the tensile break stress of the polypropylene blow moulding film is greater than 15MPa, preferably greater than 25MPa, such as
25-120MPa；And/or fracture norminal strain is greater than 300%, preferably greater than 480%, such as 480-1000%；And/or tearing is strong
Degree is greater than 50N/mm, preferably greater than 150N/mm, such as 150-300N/mm；And/or cross direction tear strength and machine direction tear
Difference is less than 24%, and preferably smaller than 20%, also preferably less than 10%, such as 1-10%.
The present invention also provides a kind of preparation method of polypropylene blow moulding film, the method includes providing according to the present invention
Composition as described above carries out extruding pelletization (such as passing through double screw extruder), then by its (such as passing through inflation film manufacturing machine)
Blown Film.
Preferably, extrusion temperature is 150-240 DEG C, preferably 170-220 DEG C；And/or blown film temperature is 170-230 DEG C, it is excellent
Select 185-220 DEG C.The extrusion temperature refers to the extrusion temperature of such as extruder setting.Blown film temperature refers to such as inflation film manufacturing machine
Film mouth temperature.
Preferably, during Blown Film, blow-up ratio 1.5-3, preferably 2-2.5.
According to the present invention, used inflation film manufacturing machine can be lower blowing water cold type, flat blowing cold type, be also possible to tradition
Up-draught cold type polypropylene blown film unit.
The preparation method of polypropylene blow moulding film according to the present invention further includes base resin i.e. high fondant-strength anti-impact poly- third
The preparation step of alkene, comprising:
Step 1: the random copolymerization of acrylic is reacted, comprising:
First stage: under the action of comprising the Ziegler-Natta catalyst of the first external electron donor, exist in hydrogen
Propylene is carried out in the absence of or to react with the random copolymerization of ethylene and/or 1- butylene, is obtained comprising the first atactic copolymerized polypropene
Reaction stream；
Second stage: the catalyst being added in the second external electron donor and the reaction stream carries out complex reaction, then
Propylene is carried out in the presence of the first atactic copolymerized polypropene and hydrogen to react with the random copolymerization of ethylene and/or 1- butylene, is produced
Raw second atactic copolymerized polypropene, obtains the random copolymerization comprising the first atactic copolymerized polypropene and the second atactic copolymerized polypropene
Polypropylene continuous phase；
Wherein,
First atactic copolymerized polypropene and comprising the first atactic copolymerized polypropene and the second atactic copolymerized polypropene
The melt index that atactic copolymerized polypropene continuous phase measures under 230 DEG C, the load of 2.16kg is respectively 0.001-0.4g/
The 10min and 0.1-15g/10min and weight ratio of first atactic copolymerized polypropene and the second atactic copolymerized polypropene is
40:60-60:40；
Step 2: propylene-ethylene copolyreaction, carries out in the presence of the atactic copolymerized polypropene continuous phase and hydrogen
Propylene-ethylene gas phase copolymerization generates propylene-ethylene copolymers rubber domain, obtains comprising the random copolymerization poly- third
The base resin of alkene continuous phase and propylene-ethylene copolymers rubber domain.It should be understood that the reacting material flow includes first
Unreacted catalyst in stage.
In a preferred embodiment of the invention, the first atactic copolymerized polypropene measures under 230 DEG C, the load of 2.16kg
Melt index be 0.001-0.4g/10min.Preferably, the melt index of first atactic copolymerized polypropene is less than described
The melt index of second atactic copolymerized polypropene.It is further preferred that including the atactic copolymerized polypropene of the first atactic copolymerized polypropene
The melt index measured under 230 DEG C, the load of 2.16kg is 0.1-15g/10min, preferably 0.1-6g/10min.
What preferred embodiment according to the present invention, atactic copolymerized polypropene continuous phase and second step obtained includes the nothing
It is big to advise the ratio between melt index of polypropylene base resin of copolymer polypropylene continuous phase and propylene-ethylene copolymers rubber domain
In or be equal to 0.6, less than 1.
Preferably, the weight ratio of propylene-ethylene copolymers rubber domain and atactic copolymerized polypropene continuous phase is 11-80
∶100。
In the preparation step of base resin of the invention, by the way that the atactic copolymerized polypropene continuous phase of base resin is set
It is set to the combination including at least two atactic copolymerized polypropenes with different melt index, and with special ratios relationship,
Especially it is total in the first atactic copolymerized polypropene and including the first atactic copolymerized polypropene and the random of the second atactic copolymerized polypropene
Poly- polypropylene is respectively provided under conditions of specific different molecular weight and molecualr weight distribution, makes to constitute used in the present invention poly-
Propylene material has specific continuous phase, under being further combined of the continuous phase and specific dispersed phase, that is, rubber phase, generates
Both there is high melt strength, while there is the impact polypropylene material of good rigidity and toughness, and then set based on this
The polypropylene blown film with superperformance can be made in rouge.
Preferred embodiment according to the present invention constitutes the atactic copolymerized polypropene continuous phase tool of base resin of the invention
Have the following characteristics that the melt index measured under 230 DEG C, the load of 2.16kg is 0.1-10g/10min, preferably 0.1-6g/
10min molecular weight distribution mw/mn=6-20, preferably Mw/Mn=10-16；The content that molecular weight is greater than 5,000,000 fractions is greater than or waits
In 1.5 weight %, and it is less than or equal to 5 weight %；Molecular weight is greater than or equal to 15.0 weight % less than the content of 50,000 fractions,
And it is less than or equal to 40 weight %；Mz+1/Mn is greater than or equal to 70, and preferably smaller than 150.Wherein, the molecular weight is greater than 500
Ten thousand fractions and part of the molecular weight distribution curve middle-molecular-weihydroxyethyl greater than 5,000,000 and portion less than 50,000 are respectively referred to less than 50,000 fractions
Point, that this is known to those skilled in the art, readily comprehensible, details are not described herein.
, according to the invention it is preferred to which ethylene contents are 0~6 weight % in atactic copolymerized polypropene continuous phase；And/or butylene
Content is 0~10 weight %.
In the first phase, the dosage of hydrogen for example can be 0-200ppm.In second stage, the dosage of hydrogen is
2000-20000ppm.Method provided by the invention preferably carries out in the reactor of two or more serial operations.
It is according to the method for the present invention the method for the direct catalytic polymerization of Ziegler-Natta catalyst.By using going here and there
Two or more different types of external electron donors are used in multiple reactors of connection respectively, suitable external electron donor is selected to use
It measures, different dosage, the composition of reaction monomers of chain-transferring agent hydrogen etc. in association reaction, preparation have particular melt index
, the atactic copolymerized polypropene continuous phase of extremely wide molecular weight distribution containing a large amount of super high molecular weight components, and on this basis
The combined polymerization of further progress propylene and ethylene obtains being scattered in the rubber phase in continuous phase, then passes through control copolyreaction
Reaction condition obtains the impact polypropylene with high fondant-strength effect composition, structure and the content etc. that control rubber phase.
In method provided by the invention, used catalyst is Ziegler-Natta catalyst, preferably has Gao Li
The catalyst of structure selectivity.The Ziegler-Natta catalyst of high stereoselective described herein, which refers to, can be used for preparing
The catalyst of Noblen of the isotactic index greater than 95%.This kind of catalyst usually contains the solid catalysis of (1) titaniferous
Agent active component, main component are magnesium, titanium, halogen and internal electron donor；(2) organo-aluminum compound cocatalyst component；(3)
External electron donor component.
Solid catalyst activity component in Ziegler-Natta catalyst used in method of the invention (and can claim
Major catalyst) can be it is well known in the art.It is available this kind of to contain the specific of active solid catalyst component (1)
Example see, for example, patent document CN85100997, CN98126383.6, CN98111780.5, CN98126385.2,
In CN93102795.0, CN00109216.2, CN99125566.6, CN99125567.4 and CN02100900.7.These patents
The full content of document is incorporated by reference into the present invention.
Organo-aluminum compound optimizing alkyl calorize in Ziegler-Natta catalyst used in method of the invention is closed
In object, more preferably trialkylaluminium, for example, triethyl aluminum, triisobutyl aluminium, three n-butylaluminums and three hexyl aluminium etc. at least
It is a kind of.
The active solid catalyst component of titaniferous in Ziegler-Natta catalyst used in method of the invention and
The molar ratio of organo-aluminum compound is calculated as 10: 1~500: 1, preferably 25: 1~100: 1 with aluminium/titanium.
According to the present invention, it is R that first external electron donor, which is preferably selected from general formula,1R2Si(OR3)2Compound in extremely
Few one kind；Wherein, R2With R1It is each independently selected from C1-C6Linear or branched alkyl group, C3-C8Naphthenic base and C5-C12Heteroaryl,
R3For C1-C3Straight chain aliphatic.Specific example includes but are not limited to dicyclopentyl dimethoxyl silane, isopropyl cyclopentyl
Dimethoxysilane, isopropyl butyldimethoxysilane, bipyridyl dimethoxysilane, diisopropyl dimethoxy silicon
Alkane etc..
The molar ratio of the organo-aluminum compound and the first external electron donor is calculated as 1: 1~100: 1 with aluminium/silicon, preferably
10: 1~60: 1.
In the method according to the invention, the catalyst comprising the first external electron donor can be added directly into the first step without
It advises in copolymerization reactor, the known pre-contact of industry and/or prepolymerization can also be passed through and then be added to the first step being randomly total to
In poly- reactor.The prepolymerization refers to that catalyst carries out the prepolymerization of certain multiplying power at a lower temperature, ideal to obtain
Particle shape and dynamic behavior control.The prepolymerization can be the continuous prepolymerization of liquid-phase bulk, can also be molten in inertia
Batch pre-polymerization in the presence of agent.Prepolymerization temperature is usually -10~50 DEG C, preferably 5~30 DEG C.Before prepolymerization technology
Pre-contacting steps is optionally set.The pre-contacting steps refers to co-catalyst in catalyst system, external electron donor and master
Catalyst (solid active center component) carries out the complex reaction of catalyst system, to obtain the caltalyst with polymerization activity
System.It is -10~50 that the temperature of pre-contacting steps, which usually controls,.DEG C, preferably 5~30 DEG C.
According to the present invention, second external electron donor is selected from the chemical combination as shown in chemical general formula (I), (II) and (III)
At least one of object；
Wherein R1And R2It is each independently selected from C1-C20One of straight chain, branching or cricoid aliphatic group, R3、
R4、R5、R6、R7And R8It is each independently selected from hydrogen atom, halogen atom, C1-C20Linear or branched alkyl group, C3-C20Naphthenic base,
C6-C20Aryl, C7-C20Alkaryl and C7-C20One of aralkyl, and R3、R4、R5、R6、R7And R8In any two between
Optionally key is linked to be ring；R9、R10And R11It is each independently C1-C3Straight chain aliphatic, R12For C1-C6Linear or branched alkyl group
Or C3-C8Naphthene group.The specific example of second external electron donor includes but are not limited to 2,2- diisobutyl -1,3- dimethoxy
Base propane, 2,2- phenyl -1,3- dimethoxy propane, 2,2- benzyl -1,3- dimethoxy propane, 2- isopropyl -2- isoamyl
Bis- (cyclohexyl methyl) -1,3- dimethoxy propanes of base -1,3- dimethoxy propane, 2,2-, 2- isopropyl -2-3,7- diformazan are pungent
Base-dimethoxy propane, 2,2- isopropyl -1,3- dimethoxy propane, 2- isopropyl -2- cyclohexyl methyl -1,3- dimethoxy
Propane, 2,2- diisobutyl -1,3- di ethyl propyl ether, 2,2- diisobutyl -1,3- dipropoxy propane, 2- isopropyl -2-
Isopentyl -1,3- di ethyl propyl ether, 2- isopropyl -2- isopentyl -1,3- dipropoxy propane, 2,2- bis- (cyclohexyl methyls) -
1,3- di ethyl propyl ether, trimethoxysilane, isobutyl triethoxy silane, isopro-pyltriethoxysilane, four
Ethoxysilane silane etc..
The molar ratio of the organo-aluminum compound and the second external electron donor is calculated as 1: 1~60 with aluminium/silicon or with aluminium/oxygen:
1, preferably 5: 1~30: 1.
The molar ratio of some embodiments according to the present invention, second external electron donor and the first external electron donor is
1-30, also preferably 5-30.
In the method for the invention, preferably make the second outer electron and the before the random copolymerization reaction of second stage
Catalytic component in one stage reaction product comes into full contact with.In some preferred embodiments, the second dispatch from foreign news agency daughter can be with
It is added on the feeding line after reactor before second stage reactor in the first stage, or in second stage reactor
Feed pipe front end, it is pre- the purpose is to be carried out first with the catalyst in the reaction product of first stage before second stage is reacted
Haptoreaction.
Preferably, in second step, the dosage of ethylene is the 20-60% for the total volume that ethylene accounts for ethylene and propylene.?
In two steps, the volume ratio of the total amount of hydrogen and ethylene and propylene is 0.02-1.Meanwhile as described above, in the first phase, hydrogen
Dosage for example can be 0-200ppm.In second stage, the dosage of hydrogen can be 2000-20000ppm.In the present invention
In, have high fondant-strength to obtain, is provided simultaneously with the impact polypropylene material of higher rigidity and toughness, dispersed phase and company
The control of the composition of continuous phase, structure or performance is particularly significant.The present invention can be prepared by these preferred conditions to be had favorably
In the ethylene contents of the molecular weight distribution, rubber phase that achieve the object of the present invention, so that obtaining has the anti-impact of more preferable performance poly-
Propylene material.
In a preferred embodiment of the invention, the yield of the first atactic copolymerized polypropene and the second atactic copolymerized polypropene
It is 40: 60-60: 40.The productivity ratio of propylene-ethylene copolymers rubber domain and atactic copolymerized polypropene continuous phase is 11-80:
100。
The polymerization reaction of the first step can carry out in Liquid-liquid, or in gas phase-gas phase, or be combined using liquid-gas
Technology carries out.When carrying out liquid phase polymerization, polymerization temperature is 0~150 DEG C, preferably 60~100 DEG C；Polymerization pressure should be higher than that third
Saturated vapour pressure of the alkene under corresponding polymerization temperature.In gas-phase polymerization, polymerization temperature is 0~150 DEG C, is with 60~100 DEG C
It is good；Polymerization pressure can be normal pressure or higher, and preferably pressure is 1.0~3.0MPa (gauge pressure, similarly hereinafter).
The polymerization reaction of second step carries out in the gas phase.The gas-phase reactor can be gas-phase fluidized-bed, gas phase moving bed,
Or bubble agitation bed reactor.The temperature of polymerization is 0~150 DEG C, preferably 60~100 DEG C.Polymerization pressure is lower than propylene point
Depress liquefied any pressure.
Preferred embodiment according to the present invention, the reaction temperature of first stage are 50-100 DEG C, preferably 60-85 DEG C；The
The reaction temperature of two-stage is 55-100 DEG C, preferably 60-85 DEG C；The reaction temperature of second step is 55-100 DEG C, preferably 60-85
℃。
In a preferred embodiment of the invention, method of the invention further includes using α or β crystalline substance nucleating agent to made
Standby obtained impact polypropylene material is further modified, to improve the rigidity or toughness of polyacrylic resin material.Applicable α it is brilliant and
β crystalline substance is nucleater modified, is known technology in the industry.The weight of usual nucleating agent and the ratio of polypropylene total weight are (0.005~3)
∶100。
According to the method for the present invention, polymerization reaction can be carried out continuously, and also may be carried out batchwise.
In the preparation step of base resin of the invention, the second external electron donor of addition can be with first stage propylene
It reacts with the catalytic active center in the copolymerization product material of ethylene and/or butylene, generates new catalytic active center,
Second stage continues to cause propylene and ethylene and/or butene polymerization into the nothing with first stage products obtained therefrom mass difference great disparity
Advise copolymerized polymer.Second external electron donor has higher hydrogen response than the first external electron donor, can be in a small amount of hydrogen
In the presence of gas, high fusion index polymer is prepared.Then obtained by being controlled as controlling the reaction condition of second step polymerization reaction
The molecular weight of polymer, this step is extremely important, the hydrogen response being added using second stage in the first step it is good second
External electron donor obtains the rubber phase molecular weight to match with continuous phase under specific density of hydrogen, to obtain with good
The polypropylene material of good performance, and then the polypropylene blown film with excellent properties is prepared, this is outstanding advantages of the invention
One of.The Nomenclature Composition and Structure of Complexes control of rubber phase component ensure that it has high fondant-strength, and the certain content of rubber components guarantees
It is compared with high impact resistance, and furthermore suitable molecular weight distribution also makes polymer have good processing performance.That is,
The present invention prepares continuous phase by the way that multiple propylene random copolyreaction stages are arranged, and continuous phase and rubber domain is selected to prepare
The suitable each response parameter and reaction condition of step, to regulate and control the structure and property of generated continuous phase and rubber domain
Energy and their combination relationship obtain the polypropylene material with excellent performance on this basis.Based on this polypropylene
Therefore resin, the polypropylene blow moulding film being prepared using blow moulding process also have corresponding excellent performance.
Polypropylene base resin that is of the invention prepared and using, can be used general blow moulding process and obtains poly- third
Alkene inflation film, changing most of polypropylene film moldings can only be by curtain coating, the status of the technological formings such as biaxial tension.Make
The polypropylene film obtained with blow moulding process has shock resistance lear energy strong, and the high feature of tensile strength is especially suitable
It sterilizes by cooking at a high temperature for cooking food bag, microwave food packaging, doctor and the large-scale fields such as pack again.
Polypropylene blow moulding film non-crosslinking structure made according to the present invention can be recycled according to general polypropylene modified material
It utilizes, does not cause secondary pollution, meet the requirement of circular economy.
Base resin related content of the invention is in patent application 201410602224X and patent application
It is recorded in 2014106023083, it is incorporated by reference herein.
Specific embodiment
Below will by specific embodiment, the present invention is described further, but do not constitute to any limit of the invention
System.
Raw material in following embodiment and comparative example includes:
Plain polypropylene: Yanshan Mountain branch company, Sinopec Group, the trade mark 4908；
High fondant-strength copolymer polypropylene: Borealis WB260HMS；
Normal linear low density polyethylene (LDPE): Yangtze branch company, Sinopec Group, 7042；
Antioxidant 1010: Basf China Co., Ltd, technical grade；
Irgasfos 168: Basf China Co., Ltd, technical grade.
It is commercially available that other are raw materials used.
The related data of polymer are obtained by following test method in embodiment and comparative example:
1) (the i.e. characterization rubber-phase content of the ethylene contents in room temperature xylene soluble content and room temperature xylene soluble part
And the ethylene contents of rubber phase), it is measured using CRYSTEX method, using the production of Polymer Char company, Spain
CRYST-EX instrument (CRYST-EX EQUIPMENT, IR4+Detector), select a series of room temperature xylene soluble contents not
Same sample is corrected as standard specimen, and the room temperature xylene soluble content of standard specimen is measured using ASTM D5492.Instrument is certainly
Body institute band infrared detector can test propylene weight content in soluble matter, contain for characterizing the ethylene in room temperature xylene soluble part
Measure (ethylene contents in rubber phase)=100%- propylene weight content.
2) melt drawn test machine: RheotensTM97, German Goettfert company；Resin stretched intensity presses GB/T
1040.2 method measures.
3) melt mass flow rate (also known as melt index, MFR): according to ASTM D1238 the method, with CEAST public affairs
7026 type fusion index instruments are taken charge of, are measured under 230 DEG C, 2.16kg load.
4) it bending modulus: is measured according to 9341 the method for GB/T.
5) it simply supported beam notch impact strength: is measured according to 1043.1 the method for GB/T.
6) ethylene contents: being measured using infrared spectroscopy (IR) method, is demarcated using the standard specimen of nuclear magnetic resonance method determination.It is described
Magnetic nuclear resonance method uses Switzerland Bruker company AVANCE III 400MHz nuclear magnetic resonance chemical analyser (NMR), 10 millimeters of probes
Measurement.Solvent is deuterated o-dichlorohenzene, and about 250mg sample is placed in 2.5ml deuterated solvent, in 140 DEG C of oil bath heating dissolution examinations
Sample forms homogeneous solution.13C-NMR is acquired, 125 DEG C of probe temperature, using 90 ° of pulses, sampling time AQ is 5 seconds, delay time
D1 is 10 seconds, scanning times 5000 times or more.The common NMR requirement of experiment of the execution such as other operation, spectral peak identifications.
7) butene content: being measured using infrared spectroscopy (IR) method, is demarcated using the standard specimen of nuclear magnetic resonance method determination.It is described
Magnetic nuclear resonance method uses Switzerland Bruker company AVANCE III 400MHz nuclear magnetic resonance chemical analyser (NMR), 10 millimeters of probes
Measurement.Solvent is deuterated o-dichlorohenzene, and about 250mg sample is placed in 2.5ml deuterated solvent, in 140 DEG C of oil bath heating dissolution examinations
Sample forms homogeneous solution.13C-NMR is acquired, 125 DEG C of probe temperature, using 90 ° of pulses, sampling time AQ is 5 seconds, delay time
D1 is 10 seconds, scanning times 5000 times or more.The common NMR requirement of experiment of the execution such as other operation, spectral peak identifications.Bibliography
Including Eric T.Hsieh, and James C.Randall, Ethylene-1-Butene Copolymers.1.Comonomer
Sequence Distribution, Macromolecules, 15,353-360 (1982).
8) molecular weight polydispersity index (PI): resin sample is molded into the thin slice of 2mm at 200 DEG C, using the U.S.
ARES (advanced rheometer expansion system) rheometer of Rheometric Scientific Inc, under 190 DEG C and nitrogen protection
To sample carry out dynamic frequency scanning, select parallel plate fixtures, determine strain amplitude appropriate with guarantee experiment linear zone into
Row, measures storage modulus (G '), Loss modulus (G ") of sample etc. with the variation of frequency.Molecular weight polydispersity index PI=105/
Gc, wherein Gc(unit: Pa) is the modulus value of G '-frequency curve and G "-frequency curve point of intersection.
9) molecular weight (Mw、Mn) and molecular weight distribution (Mw/Mn, Mz+1/Mw): use Britain Polymer Laboratories
GPCIR instrument (the IR5 Concentration Testing that company produces 220 gel permeation chromatograph of PL0GPC or Polymer Char company, Spain produces
Device) measurement sample molecular weight and molecular weight distribution, chromatographic column be 3 series connection PLgel 13um Olexis columns, solvent and flowing
It is mutually 1,2,4- trichloro-benzenes (antioxidant 2 containing 250ppm, 6- dibutyl p-cresol), 150 DEG C of column temperature, flow velocity 1.0ml/min is adopted
Universal calibration is carried out with PL company EasiCal PS-1 Narrow distribution polystyrene standard items.The wherein system of room temperature trichloro-benzenes soluble matter
Standby process is as follows: precise sample and trichlorine benzene solvent dissolve 5 hours at 150 DEG C, adopt after standing 15 hours at 25 DEG C
It is filtered with quantitative glass filter paper, obtains the solution of room temperature trichloro-benzenes soluble matter for measuring.Using the polypropylene pair of known concentration
GPC area under the curve is corrected, and determines the content of room temperature trichloro-benzenes soluble matter, and the molecular weight data of room temperature trichlorine benzene insoluble is adopted
It is calculated with the GPC data of the GPC data of raw sample and room temperature trichloro-benzenes soluble matter.
10) thickness calibration is poor: randomly selecting three sections of long 50cm of same batch, the film of wide 50cm is surveyed at random in every section
The film thickness (mm) of 20 points is measured, amounts to 60 data points, finds out standard deviation using following equation:
μ is the average thickness of 60 data points, and Xi is the thickness of each point, and N=60, σ are standard deviation.
11) it tensile break stress and fracture norminal strain: is tested according to national standard GB/T 1040.3-2006.
12) it angle tear strength: is tested according to professional standard QB/T 1130-1991.
Other productions and test equipment include:
Inflation film manufacturing machine: German Collin Blown Film Line Type 180/400.
Double screw extruder: the ZSK-25 of the Nanjing Ke Beilong Machinery Co., Ltd..
The preparation of polypropylene base resin HMSPP801:
Propylene polymerization carries out on polypropylene plant, and the capital equipment of the device includes prepolymerization reactor, the first ring
Pipe reactor, the second annular-pipe reactor and third gas-phase reactor.Polymerization and steps are as follows.
(1) prepolymerization
Major catalyst (DQC-401 catalyst, Beijing Ao Da branch company, middle Effect of Catalysis In Petrochemistry agent company provide), co-catalyst
(triethyl aluminum), the first external electron donor (diisopropyl dimethoxy silane, DIPMS) are after 6 DEG C, 20min pre-contact, continuously
Ground addition continuously stirs autoclave prepolymerization reactor and carries out pre-polymerization reactor.Triethyl aluminum (TEA) into prepolymerization reactor flows
Amount is 6.33g/hr, and diisopropyl dimethoxy silane flow is 0.3g/hr, and major catalyst flow is 0.6g/hr, TEA/
DIPMS ratio is 50 (mol/mol).Prepolymerization carries out under propylene liquid-phase bulk environment, and temperature is 15 DEG C, and the residence time is about
4min, the pre-polymerization multiple of catalyst is about 80~120 times under this condition.
(2) step 1: propylene and ethylene random copolymerization
First stage: pre-polymerization rear catalyst is continuously into completion first stage propylene in the first annular-pipe reactor and on a small quantity
Ethylene random copolymerization, wherein the ethylene additional amount of the first endless tube is 10000ppm.First annular-pipe reactor polymerization reaction
Temperature 70 C, reaction pressure 4.0MPa；Not hydrogenation in the charging of first annular-pipe reactor, the density of hydrogen of on-line chromatograph detection
< 10ppm obtains the first atactic copolymerized polypropene A.
Second stage: in 2, the 2- bis- with addition 0.63g/hr in concatenated second annular-pipe reactor of the first annular-pipe reactor
Isobutyl group -1,3- dimethoxy propane (DIBMP) is mixed with the reaction stream from the first annular-pipe reactor, TEA/DIBMP ratio
For 5 (mol/mol), wherein DIBMP is the second external electron donor.70 DEG C of the polymeric reaction temperature of second annular-pipe reactor, instead
Answer pressure 4.0MPa；It is additionally added a certain amount of hydrogen with propylene feed, density of hydrogen is 1000ppm in on-line chromatograph detection charging,
The second atactic copolymerized polypropene B is generated in the second annular-pipe reactor, is obtained comprising the first atactic copolymerized polypropene and the second nothing
Advise the atactic copolymerized polypropene continuous phase of copolymer polypropylene.
(3) step 2: Propylene polymerization closes reaction
A certain amount of hydrogen, H are added in third reactor2/(C2+C3)=0.06 (mol/mol), C2/(C2+C3)=0.4
(mol/mol)(C2And C3Respectively refer to for ethylene and propylene), continue to cause ethylene/propylene copolymer conjunction reaction in third reactor, instead
75 DEG C of temperature are answered, propylene-ethylene copolymers rubber domain C is generated.
Final product contains the first atactic copolymerized polypropene, the second atactic copolymerized polypropene and propylene-ethylene copolymers
Rubber domain, activity and heat drying through wet nitrogen removal unreacted catalyst, obtains polymer powders.Polymerization is obtained
Powder in the hard of the irgasfos 168 additive of 0.1wt%, the antioxidant 1010 additive of 0.1wt% and 0.05wt% is added
Resin acid calcium, is granulated with double screw extruder.Resulting polymers analysis result and polymer physics performance are listed in Tables 1 and 2.
The preparation of polypropylene base resin HMSPP802:
Used catalyst, pre- complexing, polymerization process condition and auxiliary formula and additional amount are identical as HMSPP801.With
HMSPP801 the difference is that: the comonomer ethylene additional amount of first stage and second stage in the first step are changed to
30000ppm.Resulting polymers analysis result and polymer physics performance are listed in Tables 1 and 2.
The preparation of polypropylene base resin HMSPP803:
Used catalyst, pre- complexing, polymerization process condition and auxiliary formula and additional amount are identical as HMSPP801.With
HMSPP801 the difference is that: the comonomer ethylene of first stage and second stage in the first step are changed to 1- butylene,
One and second the additional amount of endless tube be 10mol%.Resulting polymers analysis result and polymer physics performance are listed in table 1 and table
2。
The preparation of polypropylene base resin HMSPP804:
Used catalyst, pre- complexing, polymerization process condition and auxiliary formula and additional amount are identical as HMSPP801.With
HMSPP801 the difference is that: the comonomer ethylene of first stage and second stage in the first step are changed to ethylene+1- fourth
Alkene, the ethylene additional amount of the first and second endless tubes are 6000ppm, and 1- butylene additional amount is 5mol%.Resulting polymers point
Analysis result and polymer physics performance are listed in Tables 1 and 2.
The result shown in the Tables 1 and 2, which can be seen that the polypropylene material being prepared according to the method for the present invention, to be had
Higher melt strength, tensile strength and bending modulus and higher notch impact strength.This polypropylene material is conduct
The excellent base resin of polypropylene blow moulding film.
Embodiment 1-10
The preparation of polypropylene base resin
Work is prepared respectively according to the preparation method of above-mentioned HMSPP801, HMSPP802, HMSPP803 and HMSPP804
For high fondant-strength impact polypropylene HMSPP801, HMSPP802, HMSPP803 and HMSPP804 of basic resin.
The preparation of polypropylene blown film
According to specific formula shown in table 3, a certain number of high melts of the anti-impact being prepared by special process are weighed
Strength polypropylene, that is, HMSPP601 or HMSPP602 (100 parts by weight), with a certain number of antioxidant 1010s (about 0.2 weight
Part), aid anti-oxidants 168 (about 0.1 parts by weight), calcium stearate (about 0.1 parts by weight) mixing, stir evenly.Then twin-screw is used
Extruder mixing granulation, extruder temperature of each section are set for example are as follows: 170 DEG C, 180 DEG C, 190 DEG C, 200 DEG C, 210 DEG C, 215 DEG C
(head).Obtained pellet squeezes out blown film on inflation film manufacturing machine, and inflation film manufacturing machine temperature of each section is set for example are as follows: and 170 DEG C, 180 DEG C, 190
DEG C, 200 DEG C, 210 DEG C, 210 DEG C, 210 DEG C, 210 DEG C (die temperature).Blow-up ratio is about 2.5.In addition, Examples 1 to 10, mould
Mouth temperature and blow-up ratio are also varied, and specifically refer to table 3.
Mechanics and optical performance test are carried out to the polypropylene blown film being prepared, the results are shown in Table 3.
Comparative example 1-3
Referring to the preparation step of the polypropylene blow moulding film of embodiment 1-10, replaced using common atactic copolymerized polypropene 4908
HMSPP801, HMSPP802, HMSPP803 and HMSPP804 are tested, and specific formula and process conditions and are prepared
The performance of polypropylene blown film is referring to table 3.
Comparative example 4
Referring to the preparation step of the polypropylene blow moulding film of embodiment 1-10, using high fondant-strength copolymer polypropylene
After WB260HMS is blended with linear low density polyethylene 7042 modified materials (weight ratio 100: 4) replace HMSPP801,
HMSPP802, HMSPP803 and HMSPP804 are tested, and specific formula and process conditions and the polypropylene being prepared are blown
The performance of film is moulded referring to table 3.
By embodiment 1-10 can be seen that HMSPP801, HMSPP802, the HMSPP803 prepared through the invention and
HMSPP804 high fondant-strength impact polypropylene melt strength with higher, tensile strength and bending modulus and it is higher lack
Mouth impact strength, has good blow processability energy.
It is acquired by blown film process using high fondant-strength impact polypropylene prepared by the present invention as basic resin
Inflation film have significantly higher tensile break stress and preferable tear resistance；Especially compared with comparative example 1-4
Compared with the properties of the polypropylene blow moulding film provided according to the present invention are obviously due to comparative example (as shown in table 3).And in practical behaviour
In work, common impact copolymer polypropylene blow molding process is difficult to adjust, complex process, and obtained blown film thickness is uneven, mechanics
Performance is poor.
In addition, prior: first, use blow molding prepared by serial high melt strength, propylene of the present invention
Film have the characteristics that the direction MD, TD stretch and tear resistance it is close, change previous polypropylene blow moulding film TD directional performance compared with
The worse disadvantage in the direction MD increases the reliability and widespread popularity used；Second, the film provided according to the present invention has
In the lower situation of film thickness, performance still keeps 90% or more feature of conventional film thickness film properties, this can be advantageously reduced
Materials'use increases the added value of product of Unit Weight；Third, the thickness calibration difference of the inflation film provided according to the present invention compared with
It is small, illustrate that the resin is more uniform using the thickness of film obtained by blow molding process, is conducive to the raising of mechanical property.
Although the present invention has been described in detail, it will be understood by those skilled in the art that in spirit and scope of the invention
Modification will be apparent.However, it should be understood that various aspects, the different specific embodiments that the present invention records are (square
Case) each section and the various features enumerated can be combined or all or part of exchange.In above-mentioned each specific embodiment
In, those can suitably be combined with other embodiment with reference to the embodiment of another embodiment, this is will be by this
Field technical staff is to understand.In addition, it will be understood to those of skill in the art that the description of front is only exemplary mode,
It is not intended to limit the present invention.
Claims (14)
1. a kind of polypropylene blow moulding film is made by using composition by Blown Film, this is used for the poly- of Blown Film
Propylene compositions, including the high fondant-strength impact polypropylene as basic resin, the high fondant-strength impact polypropylene packet
Atactic copolymerized polypropene continuous phase and propylene-ethylene copolymers rubber domain are included, wherein the atactic copolymerized polypropene is continuous
Mutually include at least the first atactic copolymerized polypropene and the second atactic copolymerized polypropene, and first atactic copolymerized polypropene and
Second atactic copolymerized polypropene is each independently selected from Propylene-ethylene random copolymer, propylene -1- butene random copolymer or second
Alkene-propylene -1- butene terpolymers；
The room temperature xylene soluble content of the high fondant-strength impact polypropylene be greater than or equal to 10 weight %, and be less than or
Equal to 35 weight %；And
The Mw of the room temperature trichloro-benzenes soluble matter of the high fondant-strength impact polypropylene and the ratio between the Mw of room temperature trichlorine benzene insoluble
Greater than 0.4, and it is less than or equal to 1；The melt index that the base resin measures under 230 DEG C, the load of 2.16kg is 0.1-
15g/10min；The molecular weight distribution mw/mn of the base resin is less than or equal to 10, and is greater than or equal to 4；And/or Mz+1/Mw
More than or equal to 10, and less than 20；The molecular weight polydispersity index PI of the base resin is 4-10；The second of the base resin
Alkene content is 8-20 weight %；And/or butene content is 0-10 weight %；The base resin passes through poly- in the first random copolymerization
The copolyreaction that acrylic is carried out in the presence of propylene is obtained comprising the first atactic copolymerized polypropene and the second random copolymerization poly- third
Then the atactic copolymerized polypropene continuous phase of alkene carries out propylene-ethylene in the presence of the atactic copolymerized polypropene continuous phase
Copolyreaction obtains the polypropylene material comprising propylene-ethylene copolymers rubber domain to prepare；First random copolymerization
The melt index that polypropylene and the atactic copolymerized polypropene continuous phase measure under 230 DEG C, the load of 2.16kg is respectively
0.001-0.4g/10min and 0.1-15g/10min；And first atactic copolymerized polypropene and the second random copolymerization poly- third
The weight ratio of alkene is 40:60-60:40.
2. polypropylene blow moulding film according to claim 1, which is characterized in that the base resin at 230 DEG C, 2.16kg's
The melt index measured under load is 0.1-6g/10min.
3. polypropylene blow moulding film according to claim 1 or 2, which is characterized in that the composition further includes linear low close
Spend polyethylene and/or other processing aids.
4. polypropylene blow moulding film according to claim 3, which is characterized in that other described processing aids be selected from antioxidant,
At least one of aid anti-oxidants, lubricant and antistatic agent.
5. polypropylene blow moulding film according to claim 1, which is characterized in that the polypropylene blow moulding film with a thickness of 15-
60μm。
6. polypropylene blow moulding film according to claim 1, which is characterized in that the tension failure of the polypropylene blow moulding film is answered
Power is greater than 15MPa；And/or fracture norminal strain is greater than 300%；And/or tearing strength is greater than 50N/mm；And/or laterally tearing
Intensity is differed with machine direction tear less than 20%.
7. polypropylene blow moulding film according to claim 6, which is characterized in that the tension failure of the polypropylene blow moulding film is answered
Power is greater than 25MPa；And/or fracture norminal strain is greater than 480%；And/or tearing strength is greater than 90N/mm；And/or laterally tearing
Intensity is differed with machine direction tear less than 10%.
8. a kind of method for preparing the polypropylene blow moulding film as described in any one of claim 5-7, the method includes by institute
It states composition and carries out extruding pelletization, then by its Blown Film.
9. according to the method described in claim 8, it is characterized in that, the temperature of the extrusion is 150-240 DEG C；And/or it is described
The temperature of blown film is 170-230 DEG C.
10. according to the method described in claim 9, it is characterized in that, the temperature of the extrusion is 170-220 DEG C；And/or it is described
The temperature of blown film is 185-220 DEG C.
11. according to the method described in claim 8, it is characterized in that, the method also includes the preparation step of base resin, institute
Stating preparation step includes:
Step 1: the random copolymerization of acrylic is reacted, comprising:
First stage: under the action of comprising the Ziegler-Natta catalyst of the first external electron donor, in hydrogen presence or not
In the presence of carry out propylene reacted with the random copolymerization of ethylene and/or 1- butylene, obtain include the first atactic copolymerized polypropene it is anti-
Answer logistics；
Second stage: the catalyst being added in the second external electron donor and the reaction stream carries out complex reaction, then the
It carries out propylene in the presence of one atactic copolymerized polypropene and hydrogen to react with the random copolymerization of ethylene and/or 1- butylene, generation the
Two atactic copolymerized polypropenes obtain the random copolymerization poly- third comprising the first atactic copolymerized polypropene and the second atactic copolymerized polypropene
Alkene continuous phase；
Step 2: propylene-ethylene copolyreaction, it is included in the presence of the atactic copolymerized polypropene continuous phase and hydrogen and carries out
Propylene-ethylene gas phase copolymerization generates propylene-ethylene copolymers rubber domain, obtains comprising the random copolymerization poly- third
The base resin of alkene continuous phase and propylene-ethylene copolymers rubber domain.
12. according to the method for claim 11, which is characterized in that
It is R that first external electron donor, which is selected from general formula,1R2Si(OR3)2At least one of compound；Wherein, R2With R1Respectively
From independently selected from C1-C6Linear or branched alkyl group, C3-C8Naphthenic base and C5-C12Heteroaryl, R3For C1-C3Linear aliphatic base
Group；
Second external electron donor is selected from such as at least one of chemical general formula (I), (II) and (III) compound represented；
Wherein, R1And R2It is each independently selected from C1-C20One of straight chain, branching or cricoid aliphatic group, R3、R4、
R5、R6、R7And R8It is each independently selected from hydrogen atom, halogen atom, C1-C20Linear or branched alkyl group, C3-C20Naphthenic base, C6-
C20Aryl, C7-C20Alkaryl and C7-C20One of aralkyl；R9、R10And R11It is each independently C1-C3Linear aliphatic base
Group, R12For C1-C6Linear or branched alkyl group or C3-C8Naphthene group；
Also, the molar ratio of second external electron donor and the first external electron donor is 5-30.
13. method according to claim 11 or 12, which is characterized in that the atactic copolymerized polypropene obtained through the first step connects
It is continuous mutually obtained with second step it is poly- comprising the atactic copolymerized polypropene continuous phase and propylene-ethylene copolymers rubber domain
The ratio between melt index of propylene material is greater than or equal to 0.6, and less than 1.
14. method according to claim 11 or 12, which is characterized in that ethylene contents in the random polypropylene continuous phase
For 0~6 weight %；And/or butene content is 0~10 weight %.
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| CN109608570A (en) * | 2018-11-30 | 2019-04-12 | 陕西延长中煤榆林能源化工有限公司 | Propylene, ethylene, butene-1 copolymer polypropylene material and its industrialized preparing process |
| EP3738742B1 (en) * | 2019-05-16 | 2022-01-05 | Borealis AG | Heterophasic polypropylene composition |
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| CN103748163A (en) * | 2011-07-15 | 2014-04-23 | 博里利斯股份公司 | Unoriented film |
| CN105622819A (en) * | 2014-10-31 | 2016-06-01 | 中国石油化工股份有限公司 | Method for preparing impact-resistant polypropylene material with high melt strength |
| CN105623103A (en) * | 2014-10-31 | 2016-06-01 | 中国石油化工股份有限公司 | Impact-resistant polypropylene material with high melt strength |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103748163A (en) * | 2011-07-15 | 2014-04-23 | 博里利斯股份公司 | Unoriented film |
| CN105622819A (en) * | 2014-10-31 | 2016-06-01 | 中国石油化工股份有限公司 | Method for preparing impact-resistant polypropylene material with high melt strength |
| CN105623103A (en) * | 2014-10-31 | 2016-06-01 | 中国石油化工股份有限公司 | Impact-resistant polypropylene material with high melt strength |
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