CN106674749A - Polypropylene blow-molded film and preparation method thereof - Google Patents
Polypropylene blow-molded film and preparation method thereof Download PDFInfo
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- CN106674749A CN106674749A CN201510751575.1A CN201510751575A CN106674749A CN 106674749 A CN106674749 A CN 106674749A CN 201510751575 A CN201510751575 A CN 201510751575A CN 106674749 A CN106674749 A CN 106674749A
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- copolymerized polypropene
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- 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
- C08L23/10—Homopolymers or copolymers of propene
- C08L23/14—Copolymers of propene
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F210/04—Monomers containing three or four carbon atoms
- C08F210/06—Propene
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F210/16—Copolymers of ethene with alpha-alkenes, e.g. EP rubbers
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2500/00—Characteristics or properties of obtained polyolefins; Use thereof
- C08F2500/11—Melt tension or melt strength
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- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2207/00—Properties characterising the ingredient of the composition
- C08L2207/02—Heterophasic composition
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- C08L2308/00—Chemical blending or stepwise polymerisation process with the same catalyst
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- C08L2314/00—Polymer mixtures characterised by way of preparation
- C08L2314/02—Ziegler natta catalyst
Abstract
The invention provides a polypropylene composition which is used to be blow-molded into a film. The polypropylene composition comprises a high-melt strength impact-resistant polypropylene as base resin, moreover, the high-melt strength impact-resistant polypropylene includes a random copolymer polypropylene continuous phase and a propylene-ethylene copolymer rubber dispersed phase, and the room-temperature xylene soluble content is greater than or equal to 10 percent by weight and less than or equal to 35 percent by weight; and furthermore, the ratio of the Mw of room-temperature trichlorobenzene soluble to the Mw of room-temperature trichlorobenzene insoluble is greater than 0.4 an less than or equal to 1. The invention further provides a polypropylene blow-molded film prepared by blow-molding the composition and a preparation method thereof. The polypropylene blow-molded film has the characteristics of high impact resistance and tear resistance and high tensile strength, and is particularly suitable for fields such as cooked food packages, microwave food packages, medical high-temperature cooking disinfection and large heavy packages.
Description
Technical field
The present invention relates to polymeric material field, and in particular to a kind of combination for preparing polypropylene blow moulding film
Thing, the polypropylene blow moulding film prepared by said composition and preparation method thereof.
Background technology
Polypropylene (PP) film is with higher mechanical strength, good heat resistance and grease resistance and preferably
The transparency, it is widely used in industry and daily life, is particularly well-suited to cooking food bag, microwave food
Packaging, doctor sterilize by cooking at a high temperature with it is large-scale it is heavy packaging etc..
Extrusion blow molding film process is simple, equipment are few, with cost advantage.Extrusion blow molding film accounts for all films
The 85% of production.But it is mainly single, double to stretching using extrusion curtain coating for a long time for polypropylene film
Technology production.Due to the melt viscosity and melt strength of plain polypropylene resin it is low, it is difficult to extrusion-blown modling film forming.
Recently as polymerization and the progress of catalyst technology, it is adapted to the high bath strength acrylic resin quilt of extrusion-blown modling
Develop.Due to this kind of acrylic resin melt strength and viscosity it is much higher compared with plain polypropylene, therefore can be with
Polypropylene film is produced on traditional polyethylene blown film equipment.Extrusion-blown modling polypropylene film low cost,
Production efficiency is high, tearing strength is big, film thickness wide ranges.
In order to improve polypropylene blow moulding film forming applicability, have at present using the addition copolymerization second in propylene polymerization processes
The method of alkene monomer produces polypropylene blown film producing copolymer by raw material of copolymer.Due to ethene
The addition of monomer, improves the toughness of film, but the difference of the vertical and horizontal tearing strength of film is still very big,
And cause the heat resistance of film to decline to a great extent.Additionally, the polyacrylic puncture resistant impact resistance of general commercialization
It is poor, need a kind of anti-impact enhanced polypropylene to be used for the preparation of polypropylene blown film.
It can be seen that, exploitation has the polypropylene blow moulding of the shock resistance, tear-proof and tensile resistance that further improve thin
Film, further to expand its applicability and the scope of application, remains the obvious demand of existing market.
The content of the invention
It is an object of the invention to provide a kind of composition for preparing polypropylene blow moulding film, using said composition
The polypropylene blown film for preparing.Relative to prior art, the polypropene composition provided using the present invention
The inflation film for preparing, on the premise of the heat resistance of film is not reduced, it is possible to increase the tear of film is strong
Degree, improves vertical and horizontal tearing strength, reduces the difference of vertical and horizontal tearing strength.
The present invention also provides the preparation method of the polypropylene blown film, can advantageously utilize general blowing
Moulding process is implementing.
According to the present invention, there is provided a kind of polypropene composition for Blown Film, the resin including based on
High fondant-strength impact polypropylene, the high fondant-strength impact polypropylene include atactic copolymerized polypropene it is continuous
Mutually with propylene-ethylene copolymers rubber domain, wherein the atactic copolymerized polypropene continuous phase at least includes first
Atactic copolymerized polypropene and the second atactic copolymerized polypropene, and first atactic copolymerized polypropene and the second nothing
Rule COPP be each independently selected from Propylene-ethylene random copolymer or propylene -1- butene random copolymers or
Ethylene-propylene -1- butene terpolymers；The room temperature xylene soluble part of the high fondant-strength impact polypropylene
Content is more than or equal to 10 weight %, and less than or equal to 35 weight %；And the high fondant-strength anti-impact
The Mw (weight average molecular weight) of polyacrylic room temperature trichloro-benzenes DDGS and the Mw of room temperature trichlorine benzene insoluble it
Than more than 0.4, less than or equal to 1, being greater than 0.4, and less than or equal to 0.8.Above-mentioned high fondant-strength resists
Rush polypropylene and there is excellent rigidity and toughness, be provided simultaneously with higher melt strength, based on this resin-made
Standby inflation film, the film for obtaining is likewise supplied with high melt strength, rigidity and toughness, especially with stronger
Anti-impact, tensile resistance, it is and poor with stronger tearing strength and low transverse and longitudinal tearing strength.Thus,
The invention provides a kind of composition for preparing 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 more than 0.1N, especially 0.15-0.25N.It is anti-
(23 DEG C) of Izod notch shocks for rushing base resin 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 by
Determine according to CRYSTEX methods.Convenient to characterize, the molecular weight of rubber phase is with the molecular weight of trichloro-benzenes DDGS
Meter.
In base resin used in the present invention, atactic copolymerized polypropene, as continuous phase, is polypropylene basis
Resin provides certain rigidity, and propylene-ethylene copolymers rubber is used as dispersion phase, it is possible to increase polypropylene basic tree
The toughness of fat.In order to the product for ensureing the present invention has preferable rigid-tough balance, the present invention adopts ethylene-propylene
Copolymer is used as rubber components, also, the present inventor has found through lot of experiments, uses in the present invention
High fondant-strength impact polypropylene material in, the ethene in the room temperature xylene soluble part of the material is made contains
Amount is more than or equal to 28 weight %, and during less than 45 weight %, impact polypropylene material has preferably rigidity
And toughness.Especially, in the present invention, by being arranged to atactic copolymerized polypropene continuous phase at least to include the
One 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 or propylene -1- butene random copolymers
Or ethylene-propylene -1- butene terpolymers, so that continuous phase and dispersion phase are preferably mutually compounded, produce
The impact polypropylene material of high fondant-strength and high tenacity, advantageously acts as the base resin of polypropylene blow moulding film.
Here, it is readily appreciated that, so-called " ethylene contents " can be understood as in the polymer that vinyl monomer is participated in, by second
The weight content of the part that alkene monomer is constituted.Herein, other represent " butene content " in the polymer,
Its meaning is similar.
In order to obtain higher melt strength, high fondant-strength impact polypropylene material used in the present invention it is molten
Melt index range and be preferably controlled in 0.1-15g/10min, further preferably 0.1-6.0g/10min.The melt index exists
230 DEG C, determine under the load of 2.16kg.
For high fondant-strength impact polypropylene, the material due to being heterogeneous structure, the factor of melt strength is affected
Just become complex.The inventors discovered that, in order to ensure the high fondant-strength of base resin and blown film product,
Based on resin impact polypropylene material molecular weight distribution mw/mn (weight-average molecular weight/number-average molecular weight)
Preferably lower than or equal to 10, and more than or 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 second of high fondant-strength impact polypropylene material used in the present invention
Alkene content is 8-20 weight %；And/or butene content is 0-10 weight %.
According to base resin used in the present invention, molecular weight polydispersity index (PI) is 4-10, preferred 4.5-6.
The base resin of the polypropylene blow moulding film provided according to the present invention, it is by the first atactic copolymerized polypropene
In the presence of carry out the random copolymerization reaction of acrylic and obtain comprising the first atactic copolymerized polypropene and second random
The atactic copolymerized polypropene continuous phase of COPP, then in the presence of the atactic copolymerized polypropene continuous phase
Under carry out propylene-ethylene copolyreaction and obtain the polypropylene material comprising propylene-ethylene copolymers rubber phase to make
It is standby.As can be seen here, base resin used in the present invention be high fondant-strength impact polypropylene material be not nothing
Rule COPP continuous phase is simply mixed with propylene-ethylene copolymers rubber domain, but in random copolymerization
Further carry out being obtained after propylene-ethylene copolyreaction on the basis of polypropylene continuous phase comprising random copolymerization
The globality polypropylene material of polypropylene continuous phase and propylene-ethylene copolymers rubber domain.
Base resin used in the present invention also has preferable heat resistance and preferable heat sealability, adopts
Melting peak temperature T of the final acrylic resin that DSC is determinedmMore than or equal to 145 DEG C, less than or equal to 158 DEG C.
According to the present invention, the composition can also optionally include LLDPE.Preferably, institute
The melt flow rate (MFR) scope for stating LLDPE 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 above, carried according to the present invention
For for being not required in the polypropene composition of Blown Film or the method for polypropylene blow moulding film as described below
Add such as this kind of modified component of LLDPE, it is also possible to prepare with including high tenacity and good
The polypropylene blow moulding film of the good combination property of good heat resistance, shown in following article embodiment part, this is the present invention
An advantage be located.Therefore, in some embodiments, 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, and described other processing are helped
Agent is preferably selected from least one in antioxidant, aid anti-oxidants, lubricant and antistatic additive.
Above-mentioned auxiliary agent can be selectively added according to specific needs.The auxiliary agent of selected addition can be polypropylene
The auxiliary agent commonly used in inflation film, such as antioxidant, aid anti-oxidants, lubricant and antistatic additive etc..Auxiliary agent
Consumption is conventional amount used, or is adjusted according to the requirement of actual conditions.
Antioxidant can be for example antioxidant 1010 etc.；Aid anti-oxidants are, for example, aid anti-oxidants 168 etc..Lubrication
Agent is, for example, calcium stearate or magnesium stearate etc..
The present invention also provides a kind of polypropylene blow moulding film, and it passes through as above using what is provided according to the present invention
Composition, is obtained through 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,
Its thickness 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 more than 15MPa, and preferably greater than 25
MPa, such as 25-120MPa；And/or fracture norminal strain is more than 300%, preferably greater than 480%, for example
480-1000%；And/or tearing strength is more than 50N/mm, preferably greater than 150N/mm, for example
150-300N/mm；And/or cross direction tear strength is differed less than 24%, preferably smaller than 20% with machine direction tear,
Also preferably less than 10%, such as 1-10%.
The present invention also provides a kind of preparation method of polypropylene blow moulding film, and methods described includes to be carried according to the present invention
For composition as above carry out extruding pelletization (such as by double screw extruder), then by its (example
Such as pass through inflation film manufacturing machine) Blown Film.
Preferably, extrusion temperature is 150-240 DEG C, preferred 170-220 DEG C；And/or blown film temperature is 170-230 DEG C,
It is preferred that 185-220 DEG C.The extrusion temperature refers to the extrusion temperature that for example extruder is arranged.Blown film temperature refers to example
Such as the film mouth temperature of inflation film manufacturing machine.
Preferably, during Blown Film, blow-up ratio is 1.5-3, preferred 2-2.5.
According to the present invention, the inflation film manufacturing machine for being used can be lower blowing water cold type, flat blowing cold type, it is also possible to
It is traditional up-draught cold type polypropylene blown film unit.
The preparation method of polypropylene blow moulding film of the invention, is high fondant-strength anti-impact also including base resin
Polyacrylic preparation process, including：
The first step：The random copolymerization reaction of acrylic, including：
First stage：In the presence of the Ziegler-Natta catalyst comprising the first external electron donor,
Hydrogen carries out the random copolymerization reaction of propylene and ethene and/or 1- butylene presence or absence of under, comprising
The reaction stream of the first atactic copolymerized polypropene；
Second stage：The second external electron donor is added to carry out being complexed instead with the catalyst in the reaction stream
Should, propylene is then carried out in the presence of the first atactic copolymerized polypropene and hydrogen with ethene and/or 1- butylene
Random copolymerization reaction, produce the second atactic copolymerized polypropene, obtain comprising the first atactic copolymerized polypropene
With the atactic copolymerized polypropene continuous phase of the second atactic copolymerized polypropene；
Wherein,
First atactic copolymerized polypropene and comprising the first atactic copolymerized polypropene and the second random copolymerization poly- third
At 230 DEG C, the melt index determined under the load of 2.16kg is respectively the atactic copolymerized polypropene continuous phase of alkene
0.001-0.4g/10min and 0.1-15g/10min and first atactic copolymerized polypropene and second it is random altogether
It is 40: 60-60: 40 to gather polyacrylic weight ratio；
Second step：Propylene-ethylene copolyreaction, in the presence of the atactic copolymerized polypropene continuous phase and hydrogen
Propylene-ethylene gas phase copolymerization is carried out, propylene-ethylene copolymers rubber domain is produced, is obtained comprising described
The base resin of atactic copolymerized polypropene continuous phase and propylene-ethylene copolymers rubber domain.It should be understood that
The reacting material flow includes unreacted catalyst in the first stage.
In a preferred embodiment of the invention, the first atactic copolymerized polypropene is at 230 DEG C, the load of 2.16kg
The melt index of lower measure is 0.001-0.4g/10min.Preferably, the melting of first atactic copolymerized polypropene
Melt index of the index less than second atactic copolymerized polypropene.It is further preferred that poly- including the first random copolymerization
At 230 DEG C, the melt index determined under the load of 2.16kg is the atactic copolymerized polypropene of propylene
0.1-15g/10min, preferred 0.1-6g/10min.
Preferred embodiment of the invention, atactic copolymerized polypropene continuous phase and second step obtain comprising institute
State atactic copolymerized polypropene continuous phase and propylene-ethylene copolymers rubber domain polypropylene base resin it is molten
Melt the ratio of index more than or equal to 0.6, less than 1.
Preferably, propylene-ethylene copolymers rubber domain is with the weight ratio of atactic copolymerized polypropene continuous phase
11-80∶100。
In the preparation process of the base resin of the present invention, by the way that the atactic copolymerized polypropene of base resin is continuous
Mutually it is set to include that there are different melt index, and at least two random copolymerizations with special ratios relation are poly-
The combination of propylene, it is especially random in the first atactic copolymerized polypropene and including the first atactic copolymerized polypropene and second
The atactic copolymerized polypropene of COPP has respectively the bar of specific different molecular weight and molecualr weight distribution
Under part, make composition polypropylene material used in the present invention that there is specific continuous phase, the continuous phase with it is specific
Dispersion phase be to produce both have high melt strength under being further combined of rubber phase, while with good
The impact polypropylene material of rigidity and toughness, and then based on this resin can be obtained gathering with superperformance
Propylene inflation film.
Preferred embodiment of the invention, the atactic copolymerized polypropene for constituting the base resin of the present invention is continuous
Mutually there is following feature：At 230 DEG C, the melt index determined under the load of 2.16kg is 0.1-10g/10min,
It is preferred that 0.1-6g/10min molecular weight distribution mw/mns=6-20, preferred Mw/Mn=10-16；Molecular weight is more than
The content of 5000000 fractions is more than or equal to 1.5 weight %, and less than or equal to 5 weight %；Molecular weight is less than 5
The content of ten thousand fractions is more than or equal to 15.0 weight %, and less than or equal to 40 weight %；Mz+1/Mn is more than
Or equal to 70, and preferably smaller than 150.Wherein, the molecular weight is more than 5,000,000 fractions and less than 50,000 fractions
Refer to part of the molecular weight distribution curve middle-molecular-weihydroxyethyl more than 5,000,000 and the part less than 50,000 respectively, this is for this
Art personnel are known, easy to understand, be will not be described here.
, according to the invention it is preferred to ethylene contents are 0～6 weight % in atactic copolymerized polypropene continuous phase；With/
Or butene content is 0～10 weight %.
In the first phase, the consumption of hydrogen for example can be 0-200ppm.In second stage, the use of hydrogen
Measure as 2000-20000ppm.The method that the present invention is provided is preferably in the reaction of two or more serial operations
Carry out in device.
The method according to the invention is the method for the direct catalytic polymerization of Ziegler-Natta catalyst.By using in string
Use two or more different types of external electron donors in multiple reactors of connection respectively, select suitable outer give
Electron consumption, consumption, composition of reaction monomers of chain-transferring agent hydrogen different in association reaction etc., prepare
Random copolymerization with particular melt index, the extremely wide molecular weight distribution containing a large amount of super high molecular weight components gathers
Propylene continuous phase, and the combined polymerization of propylene and ethene is further carried out on this basis, obtain being scattered in continuous phase
In rubber phase, then control composition, structure and the content of rubber phase by controlling the reaction condition of copolyreaction
Deng impact polypropylene of the acquisition with high fondant-strength effect.
In the method that the present invention is provided, the catalyst for being used is Ziegler-Natta catalyst, is preferably had
The catalyst of high stereoselective.The Ziegler-Natta catalyst of high stereoselective described herein is referred to can be with
For preparing the catalyst of Noblen of the isotactic index more than 95%.This kind of catalyst is usually contained
(1) the solid catalyst activity component of titaniferous, its main component is 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 the method for the present invention (again may be used
Claim major catalyst) can be well known in the art.It is operational this kind of containing active solid catalyst group
The instantiation of point (1) see, for example, patent document CN85100997, CN98126383.6,
CN98111780.5、CN98126385.2、CN93102795.0、CN00109216.2、CN99125566.6、
In CN99125567.4 and CN02100900.7.The full content of these patent documents is incorporated by reference into this
In bright.
The preferred alkyl calorize of the organo-aluminum compound in Ziegler-Natta catalyst used in the method for the present invention
Compound, more preferably trialkylaluminium, for example, triethyl aluminum, triisobutyl aluminium, three n-butylaluminums and three hexyls
At least one in aluminium etc..
The active solid catalyst component of the titaniferous in Ziegler-Natta catalyst used in the method for the present invention
10: 1～500 are calculated as with the mol ratio of organo-aluminum compound with aluminium/titanium: 1, preferably 25: 1～100: 1.
According to the present invention, first external electron donor is preferably selected from formula for R1R2Si(OR3)2Compound
In at least one；Wherein, R2With R1It is each independently selected from C1-C6Straight or branched alkyl, C3-C8Ring
Alkyl and C5-C12Heteroaryl, R3For C1-C3Straight chain aliphatic.Instantiation includes but are not limited to two
Cyclopenta dimethoxysilane, isopropyl cyclopentyl dimethoxysilane, isopropyl butyldimethoxysilane,
Bipyridyl dimethoxysilane, diisopropyl dimethoxy silane etc..
The mol ratio of the organo-aluminum compound and the first external electron donor is calculated as 1: 1～100 with aluminium/silicon: 1, preferably
For 10: 1～60: 1.
In the method according to the invention, the catalyst comprising the first external electron donor can be added directly into first
In step random copolymerization reactor, it is also possible to after pre-contact that industry is known altogether and/or prepolymerization, be then added to
In first step random copolymerization reactor.The prepolymerization refers to that catalyst carries out at a lower temperature certain multiplying power
Prepolymerization, to obtain preferable particle shape and dynamic behavior control.The prepolymerization can be liquid-phase bulk
Continuous prepolymerization, can also be batch pre-polymerization in the presence of an inert solvent.Prepolymerization temperature is usually
- 10～50 DEG C, preferably 5～30 DEG C.Pre-contacting steps was optionally set before prepolymerization technology.It is described pre-
Contact procedure refers to co-catalyst in catalyst system, external electron donor and major catalyst (solid active central. set
Point) complex reaction of catalyst system is carried out, to obtain the catalyst system with polymerization activity.Pre-contact is walked
Rapid temperature is generally controlled to -10～50.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 in thing；
Wherein R1And R2It is each independently selected from C1-C20In straight chain, branched or ring-type aliphatic group
One kind, R3、R4、R5、R6、R7And R8It is each independently selected from hydrogen atom, halogen atom, C1-C20Straight chain
Or branched alkyl, C3-C20Cycloalkyl, C6-C20Aryl, C7-C20Alkaryl and C7-C20In aralkyl one
Kind, and R3、R4、R5、R6、R7And R8In any two between be optionally bonded cyclization；R9、R10
And R11It is each independently C1-C3Straight chain aliphatic, R12For C1-C6Straight or branched alkyl or C3-C8
Naphthene group.The instantiation of the second external electron donor includes but are not limited to 2,2- diisobutyl -1,3- dimethoxies
Base propane, 2,2- phenyl -1,3- dimethoxy propanes, 2,2- benzyl -1,3- dimethoxy propanes, 2- isopropyl -2-
Isopentyl -1, double (cyclohexyl methyl) -1,3- dimethoxy propanes of 3- dimethoxy propanes, 2,2-, 2- isopropyl -2-3,7-
Dimethyl octyl-dimethoxy propane, 2,2- isopropyl -1,3- dimethoxy propanes, 2- isopropyl -2- cyclohexyl methyl -1,3-
Dimethoxy propane, 2,2- diisobutyl -1,3- di ethyl propyl ethers, 2,2- diisobutyl -1,3- dipropoxy propane,
2- isopropyl -2- isopentyl -1,3- di ethyl propyl ethers, 2- isopropyl -2- isopentyl -1,3- dipropoxy propane, 2,2-
Double (cyclohexyl methyl) -1,3- di ethyl propyl ethers, trimethoxysilane, isobutyl triethoxy silane,
Isopro-pyltriethoxysilane, tetraethoxysilane silane etc..
The organo-aluminum compound is calculated as with the mol ratio of the second external electron donor with aluminium/silicon or with aluminium/oxygen
1: 1～60: 1, preferably 5: 1～30: 1.
Some embodiments of the invention, second external electron donor and the first external electron donor mole
Than for 1-30, also preferably 5-30.
In the method for the invention, preferably the second outer electron was made before the random copolymerization reaction of second stage
It is fully contacted with the catalytic component in first stage product.In some preferred embodiments, second
Dispatch from foreign news agency daughter can be added on the feeding line after reactor in the first stage before second stage reactor, or
Person in the feed pipe front end of second stage reactor, its objective is second stage react before first with the first rank
Catalyst in the product of section carries out pre-contact reaction.
Preferably, in second step, the consumption of ethene accounts for the 20-60% of the cumulative volume of ethene and propylene for ethene.
In second step, hydrogen is 0.02-1 with the volume ratio of ethene and the total amount of propylene.Meanwhile, as described above,
In first stage, the consumption of hydrogen for example can be 0-200ppm.In second stage, the consumption of hydrogen can be with
For 2000-20000ppm.In the present invention, possess high fondant-strength to obtain, be provided simultaneously with higher firm
The control of the composition, structure or performance of the impact polypropylene material of property and toughness, dispersion phase and continuous phase is very heavy
Will.The present invention can prepare the molecular weight for being advantageously implemented the purpose of the present invention by these preferred conditions
Distribution, the ethylene contents of rubber phase, so as to obtain the impact polypropylene material with more preferable performance.
In a preferred embodiment of the invention, the first atactic copolymerized polypropene and the second atactic copolymerized polypropene
Yield is 40: 60-60: 40.The product of propylene-ethylene copolymers rubber domain and atactic copolymerized polypropene continuous phase
Rate ratio is 11-80: 100.
The polymerisation of the first step in Liquid-liquid, or can be carried out in gas phase-gas phase, or using liquid-
Gas combination technique is carried out.When liquid phase polymerization is carried out, polymerization temperature is 0～150 DEG C, preferably 60～100 DEG C；
Polymerization pressure should be higher than that saturated vapour pressure of the propylene under corresponding polymerization temperature.The polymerization temperature in gas-phase polymerization
For 0～150 DEG C, preferably 60～100 DEG C；Polymerization pressure can be normal pressure or higher, and preferred pressure is
1.0～3.0MPa (gauge pressure, similarly hereinafter).
The polymerisation of second step is carried out in the gas phase.The Gas-phase reactor can be gas-phase fluidized-bed, gas phase is moved
Dynamic bed, or bubble agitation bed reactor.The temperature of polymerization is 0～150 DEG C, preferably 60～100 DEG C.Polymerization
Pressure is less than any pressure liquefied under partial pressure of propylene.
Preferred embodiment of the invention, the reaction temperature of first stage is 50-100 DEG C, preferred 60-85 DEG C；
The reaction temperature of second stage is 55-100 DEG C, preferred 60-85 DEG C；The reaction temperature of second step is 55-100 DEG C,
It is preferred that 60-85 DEG C.
In a preferred embodiment of the invention, the method for the present invention is also included using α or β crystalline substance nucleators pair
Preparation-obtained impact polypropylene material is further modified, to improve the rigid or tough of polyacrylic resin material
Property.Applicable α is brilliant and β crystalline substances are nucleater modified, is the technology known altogether in the industry.The weight and poly- third of usual nucleator
The ratio of alkene gross weight is (0.005～3): 100.
The method according to the invention, polymerisation can be carried out continuously, it is also possible to intermittently carry out.
In the preparation process of the base resin of the present invention, the second external electron donor of addition can be with the first stage
Propylene reacts with the catalytic active center in the copolymerization product material of ethene and/or butylene, generates new catalysis
Activated centre, second stage continue to cause propylene and ethene and/or butene polymerization into first stage products obtained therefrom
The random copolymerization polymer of mass difference great disparity.Second external electron donor has higher than the first external electron donor
Hydrogen response, can prepare high fusion index polymer in the presence of a small amount of hydrogen.Then by control
Controlling the molecular weight of resulting polymers, this step is extremely important, utilizes for the reaction condition of second step polymerisation
The second good external electron donor of second stage is added in the first step hydrogen response, in specific density of hydrogen
Under, the rubber phase molecule amount matched with continuous phase is obtained, so as to obtain the polypropylene material with superperformance,
And then the polypropylene blown film with excellent properties is prepared, this is one of outstanding advantages of the present invention.Rubber phase
The Nomenclature Composition and Structure of Complexes control of component ensure that it possesses high fondant-strength, and the certain content of rubber components ensure that it
Compared with high impact resistance, in addition suitable molecular weight distribution also causes polymer to have good processing characteristics.Also
To say, the present invention prepares continuous phases by arranging multiple propylene random copolyreaction stages, and select continuous phase and
Suitable each response parameter and reaction condition of rubber domain preparation process is regulating and controlling produced continuous phase
With the structure and performance and combinations thereof relation of rubber domain, obtain on this basis and there is premium properties
Polypropylene material.The resin based on this polypropylene, then the polypropylene prepared through blow moulding process
Therefore blown film also possesses corresponding premium properties.
Polypropylene base resin that is of the invention prepared and adopting, it is possible to use general blow moulding process is obtained
Polypropylene blown film, changing most of polypropylene film shapings can only be by techniques such as curtain coating, biaxial tensiones
The present situation of shaping.The polypropylene film obtained using blow moulding process, it is strong with shock resistance lear energy,
The characteristics of tensile strength is high, is particularly well-suited to cooking food bag, microwave food packaging, medical thermophilic digestion
The field such as sterilization and large-scale heavy packaging.
Polypropylene blow moulding film non-crosslinking structure constructed in accordance, can be according to general polypropylene modified material
Recycle, do not cause secondary pollution, meet the requirement of recycling economy.
The base resin related content of the present invention is in patent application 201410602224X and patent application
Described in 2014106023083, here its be incorporated by reference.
Specific embodiment
Below will by specific embodiment, the present invention is described further, but do not constitute the present invention appointed
What is limited.
Raw material in following examples and comparative example includes：
Plain polypropylene：Yanshan Mountain branch company of Sinopec Group, the trade mark 4908；
High fondant-strength COPP：Borealis WB260HMS；
Normal linear low density polyethylene (LDPE)：Yangtze branch company of Sinopec Group, 7042；
Antioxidant 1010：Basf China Co., Ltd, technical grade；
Irgasfos 168：Basf China Co., Ltd, technical grade.
Other are raw materials used be it is commercially available.
Embodiment data relevant with polymer in comparative example are obtained by following test method：
1) ethylene contents in room temperature xylene soluble content and room temperature xylene soluble part (characterize rubber
The ethylene contents of phase content and rubber phase), determined using CRYSTEX methods, using Spain Polymer Char
CRYST-EX instruments (CRYST-EX EQUIPMENT, the IR4 of company's production+Detector), be from one
The different sample of row room temperature xylene soluble content is corrected as standard specimen, the room temperature xylene soluble of standard specimen
Thing content is determined using ASTM D5492.Instrument itself institute band infrared detector can test propylene weight in DDGS
Amount content, for characterizing room temperature xylene soluble part in ethylene contents (ethylene contents in rubber phase)=100%-
Propylene weight content.
2) melt drawn test machine：RheotensTM97, German Goettfert companies；Resin stretched intensity is pressed
The methods of GB/T 1040.2 are measured.
3) melt mass flow rate (also known as melt index, MFR)：According to ASTM D1238 methods describeds,
With the type fusion index instrument of CEAST companies 7026, at 230 DEG C, determine under 2.16kg load.
4) bending modulus：Determine according to the methods describeds of GB/T 9341.
5) simply supported beam notch impact strength：Determine according to the methods describeds of GB/T 1043.1.
6) ethylene contents：Determined using infrared spectrum (IR) method, using the standard specimen of nuclear magnetic resonance method determination
Demarcate.The magnetic nuclear resonance method adopts Bruker companies of Switzerland AVANCE III 400MHz NMR spectrums
Instrument (NMR), 10 millimeters of probes are determined.Solvent is deuterated o-dichlorohenzene, and about 250mg samples are placed in 2.5ml
In deuterated solvent, in 140 DEG C of oil bath heating dissolved samples homogeneous solution is formed.Collection 13C-NMR, probe temperature
125 DEG C of degree, using 90 ° of pulses, sampling time AQ is 5 seconds, and time delay D1 is 10 seconds, scanning times 5000
More than secondary.Other operations, spectral peak identification etc. perform conventional NMR requirement of experiment.
7) butene content：Determined using infrared spectrum (IR) method, using the standard specimen of nuclear magnetic resonance method determination
Demarcate.The magnetic nuclear resonance method adopts Bruker companies of Switzerland AVANCE III 400MHz NMR spectrums
Instrument (NMR), 10 millimeters of probes are determined.Solvent is deuterated o-dichlorohenzene, and about 250mg samples are placed in 2.5ml
In deuterated solvent, in 140 DEG C of oil bath heating dissolved samples homogeneous solution is formed.Collection 13C-NMR, probe temperature
125 DEG C of degree, using 90 ° of pulses, sampling time AQ is 5 seconds, and time delay D1 is 10 seconds, scanning times 5000
More than secondary.Other operations, spectral peak identification etc. perform conventional NMR requirement of experiment.Bibliography includes 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, is adopted
ARES (the senior flow graph extension system) flow graph of U.S. Rheometric Scientific Inc, at 190 DEG C and
Nitrogen protection under dynamic frequency scanning is carried out to sample, from parallel plate fixtures, it is determined that appropriate strain amplitude with
Ensure that experiment is carried out in linear zone, the storage modulus (G ') of determination sample, Loss modulus (G ") etc. are with frequency
Change.Molecular weight polydispersity index PI=105/Gc, wherein Gc(unit：Pa it is) G '-frequency curve and G "-
The modulus value of frequency curve point of intersection.
9) molecular weight (Mw、Mn) and molecular weight distribution (Mw/Mn, Mz+1/Mw)：Using Britain Polymer
What the Laboratories companies product gel permeation chromatographs of PL0GPC 220 or Polymer Char companies of Spain produced
The molecular weight and molecular weight distribution of GPCIR instrument (IR5 concentration detectors) determination sample, chromatographic column is 3 series connection
PLgel 13um Olexis posts, solvent and mobile phase are 1,2, the 4- trichloro-benzenes (antioxidant 2,6- containing 250ppm
DBPC), 150 DEG C of column temperature, flow velocity 1.0ml/min is poly- using PL companies EasiCal PS-1 narrow ditributions
Polystyrene standards carry out universal calibration.The preparation process of wherein room temperature trichloro-benzenes DDGS is as follows：Precise
Sample and trichlorine benzene solvent, dissolve 5 hours at 150 DEG C, and after standing 15 hours at 25 DEG C quantitative glass is adopted
Filter paper is filtered, and obtaining the solution of room temperature trichloro-benzenes DDGS is used to determine.Using the polypropylene of concentration known to GPC
Area under the curve is corrected, and determines the content of room temperature trichloro-benzenes DDGS, the molecular weight of room temperature trichlorine benzene insoluble
Data are calculated using the GPC data of raw sample and the GPC data of room temperature trichloro-benzenes DDGS.
10) thickness calibration is poor：Randomly select three sections of long 50cm of same batch, the film of wide 50cm, in per section
The film thickness (mm) of 20 points of random measurement, altogether 60 data points, using following equation standard is obtained
Difference：
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) tensile break stress and fracture norminal strain：Tested according to GB GB/T 1040.3-2006.
12) angle tear strength：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 Ke Beilong Nanjing Machinery Co., Ltd..
The preparation of polypropylene base resin HMSPP801：
Propylene polymerization is carried out on polypropylene plant, the capital equipment of the device include prepolymerization reactor, the
One annular-pipe reactor, the second annular-pipe reactor and the 3rd Gas-phase reactor.Polymerization and step are as follows.
(1) prepolymerization
Major catalyst (DQC-401 catalyst, sinopec catalyst Co. Beijing Ao Da branch companies provide), help
Catalyst (triethyl aluminum), 6 DEG C of the first external electron donor (diisopropyl dimethoxy silane, DIPMS) Jing,
After 20min pre-contact, it is added continuously and continuously stirs autoclave prepolymerization reactor and carry out pre-polymerization reactor.Into
Triethyl aluminum (TEA) flow of prepolymerization reactor is 6.33g/hr, and diisopropyl dimethoxy silane flow is
0.3g/hr, major catalyst flow is 0.6g/hr, and TEA/DIPMS ratios are 50 (mol/mol).Prepolymerization is third
Carry out under alkene liquid-phase bulk environment, temperature is 15 DEG C, and the time of staying is for about 4min, and catalyst is pre- under the conditions of this
Poly- multiple is for about 80～120 times.
(2) first step：Propylene and ethylene random copolymerization
First stage：Pre-polymerization rear catalyst continuously into complete in the first annular-pipe reactor first stage propylene with
A small amount of ethylene random copolymerization, wherein the ethene addition of the first endless tube is 10000ppm.First endless tube is anti-
Answer 70 DEG C of device polymeric reaction temperature, reaction pressure 4.0MPa；Not hydrogenation in the charging of the first annular-pipe reactor,
The density of hydrogen ＜ 10ppm of on-line chromatograph detection, obtain the first atactic copolymerized polypropene A.
Second stage：The 2,2- of 0.63g/hr is added in the second annular-pipe reactor connected with the first annular-pipe reactor
Diisobutyl -1,3- dimethoxy propanes (DIBMP) mix with the reaction stream from the first annular-pipe reactor,
TEA/DIBMP ratios are 5 (mol/mol), and wherein DIBMP is the second external electron donor.Second endless tube is anti-
Answer 70 DEG C of the polymeric reaction temperature of device, reaction pressure 4.0MPa；A certain amount of hydrogen is additionally added with propylene feed,
Density of hydrogen is 1000ppm in the detection charging of line chromatogram, and the second random copolymerization is produced in the second annular-pipe reactor
Polypropylene B, obtains the random copolymerization poly- third comprising the first atactic copolymerized polypropene and the second atactic copolymerized polypropene
Alkene continuous phase.
(3) second step：Propylene polymerization closes reaction
A certain amount of hydrogen, H are added in the 3rd reactor2/(C2+C3)=0.06 (mol/mol), C2/(C2+C3)=0.4
(mol/mol)(C2And C3Ethene and propylene are referred to respectively), continue to cause ethylene/propene in the 3rd reactor
Copolymerization, 75 DEG C of reaction temperature produces propylene-ethylene copolymers rubber domain C.
Final product contains the first atactic copolymerized polypropene, the second atactic copolymerized polypropene and propylene-ethylene copolymerization
Thing rubber domain, the wet nitrogen of Jing removes the activity and heat drying of unreacted catalyst, obtains polymer powders.
Irgasfos 168 additive, the antioxidant 1010 addition of 0.1wt% of 0.1wt% are added in the powder that polymerization is obtained
Agent and the calcium stearate of 0.05wt%, are granulated with double screw extruder.Resulting polymers analysis result and polymer
Physical property is listed in Tables 1 and 2.
The preparation of polypropylene base resin HMSPP802：
Catalyst, pre- complexing, polymerization process condition and auxiliary formula and addition and the HMSPP801 for being used
It is identical.It is with HMSPP801 differences：The comonomer of first stage and second stage in the first step
Ethene addition is changed to 30000ppm.Resulting polymers analysis result and polymer physics performance are listed in the He of table 1
Table 2.
The preparation of polypropylene base resin HMSPP803：
Catalyst, pre- complexing, polymerization process condition and auxiliary formula and addition and the HMSPP801 for being used
It is identical.It is with HMSPP801 differences：The comonomer of first stage and second stage in the first step
Ethene is changed to 1- butylene, and the addition of the first and second endless tubes is 10mol%.Resulting polymers analysis result
Tables 1 and 2 is listed in polymer physics performance.
The preparation of polypropylene base resin HMSPP804：
Catalyst, pre- complexing, polymerization process condition and auxiliary formula and addition and the HMSPP801 for being used
It is identical.It is with HMSPP801 differences：The comonomer of first stage and second stage in the first step
Ethene is changed to ethene+1- butylene, and the ethene addition of the first and second endless tubes is 6000ppm, and 1- butylene is added
Amount is 5mol%.Resulting polymers analysis result and polymer physics performance are listed in Tables 1 and 2.
The polypropylene material that the method according to the invention is prepared is can be seen that from the result shown in Tables 1 and 2
Material has higher melt strength, tensile strength and bending modulus and higher notch impact strength.It is this poly-
Propylene material is the excellent base resin as polypropylene blow moulding film.
Embodiment 1-10
The preparation of polypropylene base resin
According to the preparation method point of above-mentioned HMSPP801, HMSPP802, HMSPP803 and HMSPP804
The high fondant-strength impact polypropylene HMSPP801 of resin based on not preparing, HMSPP802,
HMSPP803 and HMSPP804.
The preparation of polypropylene blown film
Ju Ti Pei Fang according to table 3, weighs a number of anti-impact height prepared through special process
Melt strength polypropylene is HMSPP601 or HMSPP602 (100 weight portion), with a number of antioxygen
Agent 1010 (about 0.2 weight portion), aid anti-oxidants 168 (about 0.1 weight portion), calcium stearate (about 0.1 weight
Amount part) mixing, stir.Then double screw extruder mixing granulation, each section of temperature of extruder is used to set example
Such as it is：170 DEG C, 180 DEG C, 190 DEG C, 200 DEG C, 210 DEG C, 215 DEG C (head).The pellet for obtaining is in inflation film manufacturing machine
Upper extrusion blown film, each section of temperature of inflation film manufacturing machine sets and is, for example,：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 for about 2.5.In addition, embodiment 1～10, die orifice
Temperature and blow-up ratio are also varied from, and specifically refer to table 3.
Polypropylene blown film to preparing carries out mechanics and optical performance test, the results are shown in Table 3.
Comparative example 1-3
With reference to the preparation process of the polypropylene blow moulding film of embodiment 1-10, using common atactic copolymerized polypropene 4908
Replace HMSPP801, HMSPP802, HMSPP803 and HMSPP804 tested, Ju Ti Pei Fang and
The performance of process conditions and the polypropylene blown film for preparing is referring to table 3.
Comparative example 4
With reference to the preparation process of the polypropylene blow moulding film of embodiment 1-10, using high fondant-strength COPP
WB260HMS carries out that post-modification material (weight compares 100: 4) replacement is blended with LLDPE 7042
HMSPP801, HMSPP802, HMSPP803 and HMSPP804 are tested, Ju Ti Pei Fang and technique
The performance of condition and the polypropylene blown film for preparing is referring to table 3.
By embodiment 1-10 can be seen that by the present invention prepare HMSPP801, HMSPP802,
HMSPP803 and HMSPP804 high fondant-strengths impact polypropylene has higher melt strength, tensile strength
With bending modulus and higher notch impact strength, with good blow processability energy.
Resin based on the high fondant-strength impact polypropylene prepared by the present invention, by blown film process, institute
The inflation film for obtaining has significantly higher tensile break stress and preferable tear resistance；Especially with it is right
Ratio 1-4 compares, according to the present invention provide polypropylene blow moulding film properties substantially due to comparative example (such as
Shown in table 3).And in practical operation, common impact copolymer polypropylene blow molding process is difficult to adjust, technique is multiple
Miscellaneous, the blown film thickness for obtaining is uneven, and mechanical property is poor.
Additionally, prior is：First, using prepared by serial high melt strength, propylene of the present invention
Inflation film have MD, TD direction stretch and tear resistance it is close the characteristics of, change conventional polypropylene and blow
Plastic film TD directional performances increased the reliability and widespread popularity for using compared with the worse shortcoming in MD directions；
Second, had in the case of film thickness is relatively low according to the film that the present invention is provided, performance remains on conventional thickness
The feature of film performance more than 90%, this can advantageously reduce materials'use, and the product for increasing Unit Weight is added
Value；3rd, the thickness calibration difference of the inflation film provided according to the present invention is less, illustrates the resin using blowing
The thickness of technique gained film is more uniformly distributed, and is conducive to the raising of mechanical property.
Although the present invention is described in detail, it will be understood by those skilled in the art that in spirit of the invention and model
Modification in enclosing will be apparent.However, it should be understood that each side, difference that the present invention is recorded
The each several part of specific embodiment (scheme) and the various features enumerated can be combined or all or part of exchange.
In each above-mentioned specific embodiment, those can be appropriate with reference to the embodiment of another embodiment
Ground is combined with other embodiment, and this is will be to understand by those skilled in the art.Additionally, this area skill
Art personnel will be understood that, description above is only the mode of example, it is no intended to limit the present invention.
Claims (14)
1. a kind of polypropene composition for Blown Film, the high fondant-strength anti-impact of resin including based on
Polypropylene, the high fondant-strength impact polypropylene includes atactic copolymerized polypropene continuous phase and propylene-ethylene copolymerization
Thing rubber domain, wherein the atactic copolymerized polypropene continuous phase at least include the first atactic copolymerized polypropene and
Second atactic copolymerized polypropene, and first atactic copolymerized polypropene and the second atactic copolymerized polypropene are each
Independently selected from Propylene-ethylene random copolymer, propylene -1- butene random copolymers or ethylene-propylene -1- butylene three
Membered copolymer；
The room temperature xylene soluble content of the high fondant-strength impact polypropylene is more than or equal to 10 weight %,
And less than or equal to 35 weight %；And
The Mw of the room temperature trichloro-benzenes DDGS of the high fondant-strength impact polypropylene and room temperature trichlorine benzene insoluble
The ratio of Mw be more than 0.4, and less than or equal to 1.
2. composition according to claim 1, it is characterised in that the ethylene contents of the base resin are
8-20 weight %；And/or butene content is 0-10 weight %.
3. composition according to claim 1 and 2, it is characterised in that the base resin at 230 DEG C,
The melt index determined under the load of 2.16kg is 0.1-15g/10min, preferred 0.1-6g/10min.
4. the composition according to any one in claim 1-3, it is characterised in that the base resin
Molecular weight distribution mw/mn be less than or equal to 10, and more than or equal to 4；And/or Mz+1/Mw be more than or
Equal to 10, and less than 20.
5. the composition according to any one in claim 1-4, it is characterised in that the base resin
Obtain random comprising first by the copolyreaction for carrying out acrylic in the presence of the first atactic copolymerized polypropene
The atactic copolymerized polypropene continuous phase of COPP and the second atactic copolymerized polypropene, then described random common
Carry out propylene-ethylene copolyreaction in the presence of poly- polypropylene continuous phase to obtain comprising propylene-ethylene copolymers rubber
The polypropylene material of dispersion phase is preparing.
6. the composition according to any one in claim 1-5, it is characterised in that the composition is also
Including LLDPE and/or other processing aids, described other processing aids be preferably selected from antioxidant,
At least one in aid anti-oxidants, lubricant and antistatic additive.
7. a kind of polypropylene blow moulding film, it passes through using the composition as any one of claim 1-6,
It is obtained through Blown Film, preferably the thickness of the polypropylene blow moulding film is 15-60 μm.
8. polypropylene blow moulding film according to claim 7, it is characterised in that the polypropylene blow moulding film
Tensile break stress is more than 15MPa, preferably greater than 25MPa；It is excellent and/or fracture norminal strain is more than 300%
Choosing is more than 480%；And/or tearing strength is more than 50N/mm, preferably greater than 90N/mm；And/or laterally tear
Intensity is differed less than 20%, preferably smaller than 10% with machine direction tear.
9. a kind of method for preparing polypropylene blow moulding film as claimed in claim 7 or 8, methods described include by
The composition carries out extruding pelletization, then by its Blown Film.
10. method according to claim 9, it is characterised in that the temperature of the extrusion is 150-240 DEG C,
It is preferred that 170-220 DEG C；And/or the temperature of the blown film is 170-230 DEG C, preferred 185-220 DEG C.
11. methods according to claim 9 or 10, it is characterised in that methods described also includes basic tree
The preparation process of fat, the preparation process includes：
The first step：The random copolymerization reaction of acrylic, including：
First stage：In the presence of the Ziegler-Natta catalyst comprising the first external electron donor,
Hydrogen carries out the random copolymerization reaction of propylene and ethene and/or 1- butylene presence or absence of under, comprising
The reaction stream of the first atactic copolymerized polypropene；
Second stage：The second external electron donor is added to carry out being complexed instead with the catalyst in the reaction stream
Should, propylene is then carried out in the presence of the first atactic copolymerized polypropene and hydrogen with ethene and/or 1- butylene
Random copolymerization reaction, produce the second atactic copolymerized polypropene, obtain comprising the first atactic copolymerized polypropene
With the atactic copolymerized polypropene continuous phase of the second atactic copolymerized polypropene；
Wherein,
First atactic copolymerized polypropene and the atactic copolymerized polypropene continuous phase at 230 DEG C, 2.16kg's
The melt index determined under load is respectively 0.001-0.4g/10min and 0.1-15g/10min；And described first
The weight ratio of atactic copolymerized polypropene and the second atactic copolymerized polypropene is 40:60-60:40；
Second step：Propylene-ethylene copolyreaction, is included in depositing for the atactic copolymerized polypropene continuous phase and hydrogen
Propylene-ethylene gas phase copolymerization is carried out under, propylene-ethylene copolymers rubber domain is produced, comprising
The base resin of the atactic copolymerized polypropene continuous phase and propylene-ethylene copolymers rubber domain.
12. methods according to claim 11, it is characterised in that
First external electron donor is R selected from formula1R2Si(OR3)2Compound at least one；Its
In, R2With R1It is each independently selected from C1-C6Straight or branched alkyl, C3-C8Cycloalkyl and C5-C12It is miscellaneous
Aryl, R3For C1-C3Straight chain aliphatic；
Second external electron donor is selected from least in the compound as shown in chemical general formula (I), (II) and (III)
Kind；
Wherein, R1And R2It is each independently selected from C1-C20In straight chain, branched or ring-type aliphatic group
One kind, R3、R4、R5、R6、R7And R8It is each independently selected from hydrogen atom, halogen atom, C1-C20It is straight
Chain or branched alkyl, C3-C20Cycloalkyl, C6-C20Aryl, C7-C20Alkaryl and C7-C20In aralkyl
It is a kind of；R9、R10And R11It is each independently C1-C3Straight chain aliphatic, R12For C1-C6Straight or branched
Alkyl or C3-C8Naphthene group；
Also, the mol ratio of second external electron donor and the first external electron donor is 5-30.
13. methods according to claim 11 or 12, it is characterised in that it is random that the Jing first steps are obtained
COPP continuous phase and second step obtain comprising the atactic copolymerized polypropene continuous phase and propylene-ethylene
The ratio of the melt index of the polypropylene material of copolymer rubber dispersion phase is more than or equal to 0.6, and less than 1.
14. methods according to any one in claim 11-13, it is characterised in that described random poly-
Ethylene contents are 0～6 weight % in propylene continuous phase；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 |
| CN109651547A (en) * | 2017-10-10 | 2019-04-19 | 中国石油天然气股份有限公司 | Atactic copolymerized polypropene and preparation method thereof |
| CN113924201A (en) * | 2019-05-16 | 2022-01-11 | 博里利斯股份公司 | 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 |
| 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 |
| 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 |
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| CN103748163A (en) * | 2011-07-15 | 2014-04-23 | 博里利斯股份公司 | Unoriented film |
| 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 |
| 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 |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109651547A (en) * | 2017-10-10 | 2019-04-19 | 中国石油天然气股份有限公司 | Atactic copolymerized polypropene and preparation method thereof |
| CN109651547B (en) * | 2017-10-10 | 2022-06-03 | 中国石油天然气股份有限公司 | Random copolymerized polypropylene and preparation method thereof |
| 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 |
| CN113924201A (en) * | 2019-05-16 | 2022-01-11 | 博里利斯股份公司 | Heterophasic polypropylene composition |
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| CN106674749B (en) | 2019-04-19 |
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