CN104250396A - Polypropylene composition and polypropylene film - Google Patents

Polypropylene composition and polypropylene film Download PDF

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Publication number
CN104250396A
CN104250396A CN201310269010.0A CN201310269010A CN104250396A CN 104250396 A CN104250396 A CN 104250396A CN 201310269010 A CN201310269010 A CN 201310269010A CN 104250396 A CN104250396 A CN 104250396A
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polypropylene
polypropene composition
propylene
weight
nucleator
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CN104250396B (en
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高达利
邹浩
张师军
徐萌
于鲁强
王良诗
郭梅芳
张丽英
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Sinopec Beijing Research Institute of Chemical Industry
China Petroleum and Chemical Corp
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Sinopec Beijing Research Institute of Chemical Industry
China Petroleum and Chemical Corp
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    • C—CHEMISTRY; METALLURGY
    • 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
    • C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F110/04—Monomers containing three or four carbon atoms
    • C08F110/06—Propene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
    • C08K13/02—Organic and inorganic ingredients
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/24—Acids; Salts thereof
    • C08K3/26—Carbonates; Bicarbonates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/13—Phenols; Phenolates
    • C08K5/134—Phenols containing ester groups
    • C08K5/1345—Carboxylic esters of phenolcarboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2237—Oxides; Hydroxides of metals of titanium
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/24—Acids; Salts thereof
    • C08K3/26—Carbonates; Bicarbonates
    • C08K2003/265—Calcium, strontium or barium carbonate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/002—Physical properties
    • C08K2201/005—Additives being defined by their particle size in general
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/011—Nanostructured additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00—Applications
    • C08L2203/16—Applications used for films
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/24—Crystallisation aids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2207/00—Properties characterising the ingredient of the composition
    • C08L2207/10—Peculiar tacticity
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2314/00—Polymer mixtures characterised by way of preparation
    • C08L2314/02—Ziegler natta catalyst

Abstract

The invention provides a polypropylene composition and a polypropylene film prepared from the polypropylene composition. The polypropylene composition comprises polypropylene filler and a nucleating agent; the molecular weight distribution index of the polypropylene is 2.5-5.5, and the polymer tail index PIHT in molecular weight distribution width is greater than 1.9. The mechanical strength of the polypropylene film is high.

Description

A kind of polypropene composition and polypropylene film
Technical field
The present invention relates to a kind of polypropene composition and a kind of polypropylene film.
Background technology
Acrylic resin is widely used with the feature that the mechanical property of its excellence, optical property and light weight valency are excellent.Particularly Biaxially oriented polypropylene film (BOPP) (BOPP) film, due to its have that matter is soft, transparency is high, nontoxic, good waterproof performance and physical strength advantages of higher, many fields such as packaging, compound, printing can be used to.
In recent years, in order to improve the performance of BOPP film, widen the purposes of product, people fill various functional filler to realize often through in film polypropylene matrix.Such as, CN101676324A discloses a kind of BiOriented Polypropylene Films pearlescent synthetic paper dedicated parent material, and this masterbatch contains the titanium dioxide of the acrylic resin of 27-40 % by weight, the functional filler of 58-70 % by weight, the oxidation inhibitor of 0.2-0.5 % by weight, the lubricant of 0.2-1 % by weight, the white dyes of 0.2-0.5 % by weight and 0.5-1.5 % by weight.Although adopt the BiOriented Polypropylene Films that obtains of the method to have good pearl effect, ornamental stronger, but, acrylic resin wherein used is plain polypropylene resin, along with the rising of filler content, after particularly adding high amount of inorganic filler, often there is the significantly reduction of mechanical property in polypropylene film goods, degraded toughness makes it apply and receives many restrictions.
Summary of the invention
The object of the invention is to overcome the existing polypropylene film shortcoming that mechanical strength can be deteriorated after adding filler, and a kind of polypropene composition and the polypropylene film still after adding filler with higher mechanical strength are provided.
The invention provides a kind of polypropene composition, wherein, this polypropene composition contains polypropylene, filler and nucleator; Described polyacrylic molecular weight distributing index is 2.5-5.5, the polymer hangover indices P I in molecular weight distribution width hTbe greater than 1.9.
Present invention also offers a kind of polypropylene film be made up of described polypropene composition.
The polypropylene film prepared by polypropene composition provided by the invention has good mechanical strength.As can be seen from the result of embodiment, the longitudinal tensile of polypropylene film provided by the invention can reach more than 3.49GPa, cross directional stretch modulus can reach more than 5.32GPa, and longitudinal fracture intensity can reach more than 72MPa, and cross-breaking strength can reach more than 105MPa.Infer its reason, may be due to: on the one hand, the narrower polypropylene of molecular weight distributing index has wider newton platform area in flow process, the change that its viscosity fluctuates with shearing rate is less, the easier stability contorting of extrusion capacity, and the possibility that in film process, surface imperfection occurs can be reduced in, thus improve the mechanical strength of polypropylene film.In addition, can improve the adding of nucleator and add by filler the defect that brought mechanical strength declines, there is the effect that can play nucleator compared with the polypropylene of narrow molecular weight distributions exponential sum higher polymer hangover index better, obtain the polypropylene film that mechanical strength is higher.On the other hand, polymer hangover indices P I hTmore significant macromolecular chain tail end is there is in higher showing in polypropylene.Theoretical according to polypropylene homogeneous nucleation, macromolecular chain tail end can Preferential Nucleation in crystallization, makes that polyacrylic Tc raises, crystallization velocity is accelerated, and is conducive to improving rigidity, shortening shaping cycle and improve shaping efficiency.In a word, the consistency of polypropylene provided by the invention and filler is good, is beneficial to the dispersed of high levels of filler, coordinates the nucleator of seldom amount just can significantly improve the crystal property of polypropylene film, thus significantly improves the mechanical strength of film.
A preferred embodiment of the invention, when the content of described polyacrylic isotaxy five unit group [mmmm] is greater than 85%, can make melt polypropylene in flow process, have wider newton platform area, thus the possibility that in film process, surface imperfection occurs can be reduced in more significantly, and be conducive to the crystallinity improving film, make the stretching of film more even, thin film alignment Du Genggao, thus the mechanical property improving two-way stretch height filled polypropylene film.
A preferred embodiment of the invention, adopt two-stage polymerization legal system for polypropylene, the first step carries out prepolymerization at a lower temperature, second step then improves the temperature of polyreaction, and the polypropylene obtained can be made like this to have narrower molecular weight distribution, higher tacticity and larger polymer hangover indices P I hT, thus make polypropylene itself have higher crystal property and crystallization regularity, make only there is a small amount of pars amorpha in polypropylene, be conducive to the further raising of thin film mechanics intensity.
According to another kind of preferred implementation of the present invention, in described polyacrylic preparation process, when described Z-N (Ziegler-Natta) catalyzer is preferably containing external donor compound, the further raising of the polypropylene tacticity obtained can not only be made, but also significantly can reduce the content of xylene soluble part, thus widen the Application Areas of described polypropene composition and polypropylene film.
Other features and advantages of the present invention are described in detail in embodiment part subsequently.
Embodiment
Below the specific embodiment of the present invention is described in detail.Should be understood that, embodiment described herein, only for instruction and explanation of the present invention, is not limited to the present invention.
Polypropene composition provided by the invention contains polypropylene, filler and nucleator; Described polyacrylic molecular weight distributing index is 2.5-5.5, is preferably 3.0-4.9; Polymer hangover indices P I in molecular weight distribution width hTbe greater than 1.9, be preferably greater than 2.1.
PI hThigher, show in polypropylene, to there is more significant macromolecular chain tail end.Described polymer hangover indices P I hTcalculate as follows: PI hT=10 5× (Mz/Mp)/Mw, wherein, Mp is peak molecular weight, and Mw is weight-average molecular weight, and Mz is Z-average molecular weight, and unit is g/mol.Described Mp, Mw, Mz and molecular weight distributing index can pass through gel permeation chromatograph (GPC) and measure.
The content of the present invention to material each in described polypropene composition is not particularly limited, and such as, with the described polypropylene of 100 weight parts for benchmark, the content of described filler can be 10-85 weight part, is preferably 20-55 weight part; The content of described nucleator can be 0.01-0.5 weight part, is preferably 0.05-0.25 weight part.
According to the present invention, in order to make the polypropylene film prepared by described polypropene composition, there is higher intensity, the content of described polyacrylic isotaxy five unit group [mmmm] is preferably greater than 85%, is preferably greater than 90% further, more preferably greater than 93%.
According to the present invention, in described polyacrylic preparation process, insert and/or " 1,3 " insertion because " 2,1 " may occur propylene monomer, cause the regularity of polypropylene molecule chain structure to destroy, fusing point reduces, thus affects polyacrylic use temperature.The defect structure so caused is referred to as position heterogeneous structure (regio-irregularity) here.The structural formula of the position heterogeneous structure of isotatic polypropylene is as follows:
" 2,1 " inserts the head-header structure (erythro form) caused
" 2,1 " inserts the head-header structure (Soviet Union's formula) caused
" 1,3 " insert the position heterogeneous structure caused
According to the present invention, in order to make the polypropylene film prepared by described polypropene composition have higher intensity, under preferable case, the position heterogeneous structure caused by described polypropylene does not insert containing propylene 2,1 insertion and 1,3.It should be noted that, " not containing " mentioned here does not refer to and absolutely not contains, and refers to propylene 2, and it is very low that content are inserted in 1 insertion and 1,3, is usually less than 0.01%, beyond the Monitoring lower-cut of instrument.
According to the present invention, described polyacrylic Tc Tc is preferably greater than 113 DEG C, more preferably greater than 115 DEG C, the crystalline structure of polypropylene after crystallization that obtain can be made so more perfect, thus improve the mechanical strength of polypropylene film more significantly.
According to the present invention, in described polypropylene, the content of xylene soluble part is preferably less than 4.4 % by weight, is preferably less than 2.3 % by weight further, is more preferably less than 1.6 % by weight.As a rule, xylene soluble content is low, and polyacrylic degree of isotacticity is higher, therefore rigidity and thermotolerance better.In addition, concerning some is applied to the polypropylene film of contact food, medicine or solvent, xylene soluble content is lower, then transportable go out dissolved or the substances content that extracts lower, use reliably safer.
According to the present invention, the melt mass flow rate MFR of described polypropylene at 230 DEG C, under the effect of 2.16kg load is preferably 2-5g/10min.In the present invention, described melt mass flow rate MFR measures according to the method specified in ISO1133, and wherein, probe temperature is 230 DEG C, and load is 2.16kg.
According to the present invention, described polypropylene can according to well known to a person skilled in the art that various method prepares, and such as, described polypropylene is prepared by the method comprised the following steps:
(1) under Z-N (Ziegler-Natta) catalyzer exists, by propylene-10 DEG C to 50 DEG C, carry out prepolymerization under 0.1-100MPa, obtain the propylene pre-polymer that pre-polymerization multiple is 2-3000 gram of polymkeric substance/gram catalyzer, is preferably 3-2000 gram of polymkeric substance/gram catalyzer, is more preferably 50-300 gram of polymkeric substance/gram catalyzer;
(2) 91-150 DEG C, under 1-6MPa, described propylene pre-polymer and propylene are polymerized.
In the present invention, described pressure all refers to gauge pressure.
Above-mentioned steps (1) and step (2) can carry out batchwise polymerization operation in a reactor, also can carry out successive polymerization operation in different reactors.Such as, in an embodiment of the present invention, step (1) is carried out continuously in vertical stirred tank, and step (2) is carried out continuously in horizontal agitated vessel, that is, in different reactors, carry out successive polymerization.In addition, the reaction of step (1) and step (2) all can be carried out in the gas phase, also can carry out in the liquid phase, as well known to those skilled in the art to this.
According to the present invention, in step (1), described prepolymerized temperature can be-10 DEG C to 50 DEG C, is preferably 0-30 DEG C, is more preferably 10-25 DEG C; Described prepolymerized pressure can be 0.1-100MPa, is preferably 1.0-6.0MPa, is more preferably 1.5-5.5MPa; Described pre-polymerization multiple can be 2-3000 gram of polymkeric substance/gram catalyzer, is preferably 3-2000 gram of polymkeric substance/gram catalyzer, is more preferably 50-300 gram of polymkeric substance/gram catalyzer.Wherein, described " prepolymerization multiple " refers to the weight of prepolymer and the original ratio adding the weight of catalyzer.In addition, described prepolymerization is preferably carried out in the liquid phase, specifically can select the liquid-phase bulk prepolymerization adopting propylene.
According to the present invention, in step (2), the temperature of described polyreaction can be 91-150 DEG C, is preferably 91-110 DEG C; The pressure of described polyreaction can be 1-6MPa, is preferably 2-5MPa.The time of described polyreaction suitably can be selected by needing the polyacrylic molecular size range obtained, such as, need to obtain the larger polypropylene of molecular weight, then can extend the time of polyreaction, need the polypropylene obtaining molecular weight, then can shorten the time of polyreaction.As a rule, the time of described polyreaction can be 0.5-4 hour, is preferably 1-3 hour.In addition, described polymerization is preferably carried out in the gas phase.Particularly, can carry out in gas phase horizontal agitated vessel.Described gas phase horizontal agitated vessel is the horizontal retort removing heat with horizontal type stir shaft, quench liquid, and agitating vane wherein can be one or more in T-shaped, rectangle, oblique oar, gate, wedge shape etc.In the course of the polymerization process, the mixing speed in gas phase horizontal agitated vessel can be 10-150 rev/min.
In addition, in step (2), usually need to add molecular weight regulator (being generally hydrogen) to control the polyacrylic melt mass flow rate obtained.The add-on of described molecular weight regulator reasonably can be selected according to practical situation, in the present invention, the add-on of described molecular weight regulator preferably controls to be as the criterion at 2-5g/10min to make the polyacrylic melt mass flow rate MFR obtained, all can know these those skilled in the art, will repeat no more at this.
According to the present invention, although described Ziegler-Natta catalyst can be the existing various polyacrylic Ziegler-Natta catalyst that is applicable to prepare, but in order to make the polypropylene obtained, there is narrower molecular weight distributing index, higher polymer hangover index, under preferable case, described Ziegler-Natta catalyst contains solids containing titanium catalyst component and alkylaluminium cpd and selectivity and contains external donor compound.
According to the present invention, described solids containing titanium catalyst component can be such as by the catalytic product of alkoxyl magnesium compound, titanium compound and internal electron donor compound.
The general formula of described alkoxyl magnesium compound is preferably as shown in formula II:
Mg (OR 1) 2-m(OR 2) mformula II,
In formula II, R 1and R 2identical or different, and be selected from C independently of one another 1-C 8straight or branched alkyl, 0≤m≤2.Preferably, R 1and R 2be methyl, ethyl, propyl group, sec.-propyl, butyl, isobutyl-, n-hexyl, (2-ethyl) hexyl independently of one another; Particularly preferably, R 1for ethyl, R 2for (2-ethyl) hexyl.M reasonably can select in the scope of 0-2, preferably 0.001≤m≤0.5, further preferably 0.001≤m≤0.25, more preferably 0.001≤m≤0.1.It is emphasized that alkoxyl magnesium represented by general formula, illustrate only the composition content of each alkoxyl group, i.e. mol ratio, and the concrete structure of incomplete representation alkoxy magnesium.Particularly, as in Mg (OEt) (OiPr) only expression alkoxyl magnesium compound, the mol ratio of oxyethyl group and isopropoxy is 1, it both can be mol ratio is the diethoxy magnesium of 1 and the mixture of diisopropoxy magnesium, also can be oxyethyl group isopropoxy magnesium compound, it can also be the mixture of diethoxy magnesium, diisopropoxy magnesium and oxyethyl group isopropoxy magnesium compound, that is, its mixture that can be made up of than the alkoxyl magnesium compound of the various structures being 1 with isopropoxy total mole number oxyethyl group.Wherein, Et represents ethyl, and iPr represents sec.-propyl.
The profile of the present invention to described alkoxyl magnesium compound is not particularly limited, preferably spherical.Further, the median size D50 of described spherical alkoxyl magnesium compound can be 10-150 μm, is preferably 15-100 μm, is more preferably 18-80 μm; Size distribution index SPAN is less than 1.1, is preferably less than 1.05.Wherein, the calculation formula of described size distribution index SPAN is: SPAN=(D90-D10)/D50, and wherein, D90 represents that corresponding to accumulating weight point rate be the particle diameter of 90%, D10 represents that corresponding to accumulating weight point rate be the particle diameter of 10%, and D50 represents that corresponding accumulating weight point rate is the particle diameter of 50%.
According to the present invention, can also containing micro-magnesium halide (as MgI in described solids containing titanium catalyst component 2and/or MgCl 2) or its alcohol adduct, but with the gross weight of the alkoxyl magnesium compound shown in formula (II) and magnesium halide for benchmark, the content of the alkoxyl magnesium compound shown in formula (II) should higher than 90 % by weight, preferably higher than 95 % by weight, more preferably higher than 98 % by weight.
According to the present invention, described alkoxyl magnesium compound can be commercially available, and also can prepare according to existing method.Such as, described alkoxyl magnesium compound can by MAGNESIUM METAL, the alcohol (R corresponding with alkoxyl group 1oH and/or R 2oH) and Mixed bittern agent react under an inert atmosphere and prepare.Wherein, described Mixed bittern agent is the mixture of halogen and halogen compounds.Described halogen can be one or more in iodine, bromine and chlorine.The not limiting example of described halogen compounds is: one or more in magnesium chloride, magnesium bromide, magnesium iodide, Repone K, Potassium Bromide, potassiumiodide, calcium chloride, Calcium Bromide, calcium iodide, mercury chloride, mercuric bromide, red mercury iodide, oxyethyl group magnesium iodide, methoxyl group magnesium iodide, sec.-propyl magnesium iodide, hydrogenchloride, chloroacetyl chloride etc.Mixed bittern agent is particularly preferably the mixture of iodine and magnesium chloride, and further preferably, the weight ratio of iodine and magnesium chloride is 1:0.02-20, is more preferably 1:0.1-10.
According to the present invention, in the preparation process of above-mentioned alkoxyl magnesium compound, in described MAGNESIUM METAL and Mixed bittern agent, the molar ratio of total halogen atom is as be 1:0.0002-0.2, preferably 1:0.001-0.08.The part by weight of the described alcohol corresponding with alkoxyl group and MAGNESIUM METAL, as being 4-50:1, is preferably 6-25:1.R 1oH and R 2the mol ratio Y of OH is 3 (2-g)/g>Y> (2-g)/g, wherein, and 0≤g≤2, preferably 0.001≤g≤0.5, further preferably 0.001≤g≤0.25, more preferably 0.001≤g≤0.1.
According to the present invention, in the preparation process of above-mentioned alkoxyl magnesium compound, the temperature of described reaction can be such as 30-90 DEG C, is preferably 30-80 DEG C, is more preferably 50-75 DEG C.In actually operating, the discharge of the hydrogen that can be produced by observing response stops judging that reaction terminates.
The shape of the present invention to described MAGNESIUM METAL is not particularly limited, and such as, can be particulate state, silk ribbon shape or Powdered.In order to the median size of the alkoxyl magnesium compound making generation remains in suitable scope, and particle form is excellent, and described MAGNESIUM METAL is preferably the spherical metal magnesium that median size is 10-360 μm, is more preferably the spherical metal magnesium that median size is 50-300 μm.In addition, the surface of the present invention to described MAGNESIUM METAL there is no and limit especially, if but form the tunicles such as oxyhydroxide on the surface of described MAGNESIUM METAL, reaction then can be made slack-off, therefore, under preferable case, the total content >95 % by weight of activated carbon, more preferably >98 % by weight in described MAGNESIUM METAL.
The present invention there is no the water-content in alcohol corresponding with alkoxyl group described in the preparation process at above-mentioned alkoxyl magnesium compound and limits especially, in order to make the alkoxyl magnesium compound obtained, there is more excellent performance, require that moisture content is more few better, water-content in the described alcohol corresponding with alkoxyl group controls at below 1000ppm by usual needs, preferably controls at below 200ppm.
According to the present invention, described inert atmosphere is known to the skilled person, and is preferably nitrogen atmosphere and/or argon atmospher.In addition, the preparation of described alkoxyl magnesium compound is usually using inert solvent as reaction medium.Wherein, described inert solvent can be C 6-C 10alkane or aromatic hydrocarbons at least one, be preferably at least one in hexane, heptane, octane, decane, benzene,toluene,xylene and its derivative etc.
According to the present invention, in the preparation process of above-mentioned alkoxyl magnesium compound, MAGNESIUM METAL, the alcohol corresponding with alkoxyl group, Mixed bittern agent and inert solvent can disposablely drop into, and gradation also can be selected to drop into.Gradation drops into the hydrogen that raw material can prevent instantaneous generation a large amount of, thus prevents the spittle of alcohol or the halogenating agent caused because instantaneous a large amount of hydrogen produces, and considers, preferred this feed way from the angle of safety perspective and reaction homogeneity.The number of times of segmentation can be determined according to the consumption of the scale of reactor and various material.After having reacted, the final product dialkoxy magnesium obtained can kept dry, in inert diluent used when also can be suspended in the titanium-containing catalyst solid ingredient for the preparation of lower step.
According to the present invention, the general formula of described titanium compound is preferably as shown in formula III:
Ti (OR) 4-nx nformula III,
In formula III, R is C 1-C 14aliphatic hydrocarbyl or aromatic hydrocarbyl, X is halogen atom, and n is the integer of 0-4.When n is less than 2, the multiple R existed in formula III can be identical or different.Described halogen atom can be chlorine, bromine or iodine.Particularly, described titanium compound can be selected from least one in four titan-alkoxides, titanium tetrahalide, three halogen titan-alkoxides, dihalo-dialkoxy titanium and single halogen tri-alkoxy titanium.More specifically, described four titan-alkoxides are selected from least one in tetramethoxy titanium, purity titanium tetraethoxide, four positive propoxy titaniums, tetraisopropoxy titanium, four titanium n-butoxide, four isobutoxy titaniums, four cyclohexyloxy titaniums and four phenoxide titaniums; Described titanium tetrahalide is selected from least one in titanium tetrachloride, titanium tetrabromide and titanium tetra iodide; Described three halogen titan-alkoxides are selected from least one in trichloromethoxy titanium, tri-chloroethoxy titanium, trichlorine titanium propanolate, trichlorine titanium n-butoxide and tribromo ethanolato-titanium; Described dihalo-dialkoxy titanium is selected from least one in dichloro dimethoxy titanium, dichlorodiethyl oxygen base titanium, dichloro two positive propoxy titanium, dichloro diisopropoxy titanium and dibromo diethoxy titanium; Described single halogen tri-alkoxy titanium is selected from least one in a chlorine trimethoxy titanium, a chlorine triethoxy titanium, a chlorine three positive propoxy titanium and chlorine three titanium isopropoxide.Described titanium compound is preferably titanium tetrahalide compound, is particularly preferably titanium tetrachloride.
According to the present invention, described internal electron donor compound is preferably the diether compound of general formula as shown in formula IV:
In formula IV, R 1and R 2identical or different, and be selected from C independently of one another 1-C 20the aliphatic hydrocarbyl of straight chain, branching or ring-type; R 3, R 4, R 5, R 6, R 7and R 8identical or different, and be selected from the C of hydrogen, halogen atom, straight or branched independently of one another 1-C 20alkyl, C 3-C 20cycloalkyl, C 6-C 20aryl, C 7-C 20alkaryl and C 7-C 20aralkyl; Optionally, R 3-R 8group between can be linked to be ring by key.Preferably, R 1and R 2identical or different, and be selected from C independently of one another 1-C 6the alkyl of straight or branched; R 5, R 6identical or different, and be selected from C independently of one another 1-C 10the alkyl of straight or branched, C 3-C 10cycloalkyl.
The specific examples of described internal electron donor compound can include but not limited to: 2-sec.-propyl-2-isopentyl-1,3-Propanal dimethyl acetal, 9,9-bis-(methoxymethyl) fluorenes, 2-isobutyl--2-sec.-propyl-1,3-Propanal dimethyl acetal, 2,2-dicyclopentyl dimethoxyl propane, 2,2-phenylbenzene-1,3-Propanal dimethyl acetal, 2-isobutyl--2-sec.-propyl-1,3-Propanal dimethyl acetal, 2,2-bicyclopentyl-1, one or more in 3-Propanal dimethyl acetal, 2,2-diisobutyl-1,3-Propanal dimethyl acetals etc.
According to the present invention, in the preparation process of described solids containing titanium catalyst component, the mol ratio of the magnesium in the titanium in described titanium compound and alkoxyl magnesium compound can be 0.5-100:1; Be preferably 1-50:1.In described internal electron donor compound and alkoxyl magnesium compound, the mol ratio of magnesium can be 0.005-10:1; Be preferably 0.01-1:1.
According to the present invention, the preparation process of described solids containing titanium catalyst component is usually using inert solvent as reaction medium.Wherein, described inert solvent can be selected from C 6-C 10alkane or aromatic hydrocarbons at least one, be preferably at least one in hexane, heptane, octane, decane, benzene,toluene,xylene or derivatives thereof etc., most preferably be toluene.The molar ratio of the magnesium in described inert solvent and alkoxyl magnesium compound, as being 0.5-100:1, is preferably 1-50:1.
According to the present invention, in the preparation process of described solids containing titanium catalyst component, the addition sequence of described alkoxyl magnesium compound, titanium compound, internal electron donor compound and inert solvent is not particularly limited, such as, above-mentioned each component can be made under the existence of inert solvent to mix, also can dilute each composition with inert solvent in advance, and then respective solution is mixed.Number of times for mixing is also not particularly limited, can mixed once, also can mix several times.Particularly, solids containing titanium catalyst component can be prepared according to following several method:
Method one:
1, alkoxyl magnesium carrier compound, internal electron donor and inert solvent are mixed with suspension, the mixture reaction then formed with a part of titanium compound and inert solvent, filter, obtain solid product; 2, the solid product obtained is added in the mixture of another part titanium compound and inert solvent and continue reaction, filter, obtain solid product; 3, the 2nd step reaction 2-4 time is repeated; 4, wash the solid product finally obtained with inert solvent, obtain solids containing titanium catalyst component.Wherein, in preparation process, the amount of the described titanium compound at every turn added can carry out choose reasonable according to the number of times of reaction repeated, such as, and the number of times+2 of repetition the 2nd step that can be 1/n, n be.
Method two:
1, alkoxyl magnesium carrier compound, a part of internal electron donor and inert solvent are mixed with suspension, the mixture reaction then formed with a part of titanium compound and inert solvent, filter, obtain solid product; 2, the solid product obtained is added in the mixture formed by the internal electron donor of the titanium compound of another part, inert solvent and remainder and continue reaction, filter, obtain solid product; 3, gained solid product continues to add again continuation reaction in the titanium compound of a part and the mixture of inert solvent, filters, obtains solid product; 4, the 3rd step reaction 2-4 time is repeated; 5, wash the solid product obtained for the last time with inert solvent, obtain solids containing titanium catalyst component.Wherein, in preparation process, the amount of the described titanium compound at every turn added can carry out choose reasonable according to the number of times of reaction repeated, such as, and the number of times+3 of repetition the 3rd step that can be 1/n, n be.
Method three:
1, alkoxyl magnesium carrier compound and inert solvent are mixed with suspension, the mixture reaction then formed with a part of titanium compound and inert solvent, adds internal electron donor compound, continues reaction, filters, obtains solid product; 2, the solid product obtained is added in the mixture of another part titanium compound and inert solvent formation and continue reaction, filter, obtain solid product; 3, the 2nd step reaction 2-4 time is repeated; 4, wash the solid product finally obtained with inert solvent, obtain solids containing titanium catalyst component.Wherein, in preparation process, the amount of the described titanium compound at every turn added can carry out choose reasonable according to the number of times of reaction repeated, such as, and the number of times+2 of repetition the 2nd step that can be 1/n, n be.
Method four:
1, alkoxyl magnesium carrier compound, a part of internal electron donor and inert solvent are mixed with suspension, then the mixture reaction formed with a part of titanium compound and inert solvent, then add the internal electron donor compound of remainder, continue reaction, filter, obtain solid product; 2, the solid product obtained is added in the mixture formed by another part titanium compound and inert solvent and continue reaction, filter, obtain solid product; 3, the 2nd step reaction 2-4 time is repeated; 4, wash the solid product finally obtained with inert solvent, obtain solids containing titanium catalyst component.Wherein, in preparation process, the amount of the described titanium compound at every turn added can carry out choose reasonable according to the number of times of reaction repeated, such as, and the number of times+2 of repetition the 2nd step that can be 1/n, n be.
According to the present invention, in the preparation process of described titanium-containing catalyst solid ingredient, the inert solvent of washing is preferably hexane.The present invention is not particularly limited for the method for washing, preferably adopts the mode such as decant, filtration to carry out.The usage quantity of inert solvent, washing time, washing times are not particularly limited, and such as, relative to the magnesium in 1 mole of described alkoxyl magnesium compound, the consumption for the inert solvent washed can be such as 1-1000 mole, is preferably 10-500 mole.The time of described washing can be such as 1-24 hour, is preferably 6-10 hour.In addition, from the angle of washing homogeneity and detersive efficiency, described washing is preferably carried out under agitation.
According to the present invention, in the preparation process of described solids containing titanium catalyst component, catalytic to alkoxyl magnesium compound, titanium compound, internal electron donor compound and inert solvent condition is generally included: temperature of reaction can be-40 DEG C to 200 DEG C, is preferably-20 DEG C to 150 DEG C; Reaction times can be 1 minute-20 hours, is preferably 5 minutes-8 hours.
According to the present invention, the alkylaluminium cpd in described Ziegler-Natta catalyst such as can such as formula shown in (V):
AlR' px 3-pformula (V),
In formula (V), R' is hydrogen or C 1-C 20alkyl, X is halogen, and p is the integer of 1-3.Particularly, the example of described alkylaluminium cpd can include but not limited to: one or more in triethyl aluminum, tri-propyl aluminum, three n-butylaluminum, triisobutyl aluminium, tri-n-octylaluminium, a hydrogen diethyl aluminum, a hydrogen diisobutyl aluminum, aluminium diethyl monochloride, a chloro-di-isobutyl aluminum, sesquialter ethylmercury chloride aluminium and ethyl aluminum dichloride, is preferably triethyl aluminum and/or triisobutyl aluminium.
According to the present invention, in described Ziegler-Natta catalyst, described external electron donor can optionally add.The present inventor finds, after adding external electron donor, can reduce the content of xylene soluble part in polypropylene.
Described external donor compound can be that the routine of this area is selected, and is preferably the silicoorganic compound of general formula as shown in formula I:
R 1'' m''r 2'' n''si (OR 3'') 4-m''-n''formula I,
In formula I, R 1''and R 2''identical or different, and be halogen, hydrogen atom, C independently of one another 1-C 20alkyl, C 3-C 20cycloalkyl, C 6-C 20aryl or C 1-C 20haloalkyl; R 3''for C 1-C 20alkyl, C 3-C 20cycloalkyl, C 6-C 20aryl or C 1-C 20haloalkyl; M'' and n'' is the integer of 0-3 independently of one another, and m''+n''<4.The object lesson of described silicoorganic compound can include but not limited to: trimethylmethoxysilane, diisopropyl dimethoxy silane, second, isobutyl dimethoxy silane, isopropyl butyldimethoxysilane, di-t-butyl dimethoxysilane, tertbutyl methyl dimethoxysilane, t-butylethyl dimethoxysilane, tertiary butyl propyldimethoxy-silane, ter /-butylisopropyl dimethoxysilane, Cyclohexyl Methyl Dimethoxysilane, Dicyclohexyldimethoxysilane, cyclohexyl-t-butyldimethoxysilane, cyclopentyl-methyl dimethoxysilane, cyclopentyl ethyl dimethoxysilane, dicyclopentyl dimethoxyl silane, cyclopentyl cyclohexyl dimethoxysilane, two (2-methylcyclopentyl) dimethoxysilane, dimethoxydiphenylsilane, diphenyl diethoxy silane, phenyl triethoxysilane, methyltrimethoxy silane, Union carbide A-162, ethyl trimethoxy silane, propyl trimethoxy silicane, propyl-triethoxysilicane, isopropyltri-methoxysilane, isopro-pyltriethoxysilane, butyl trimethoxy silane, butyl triethoxyl silane, trimethoxysilane, isobutyl triethoxy silane, amyltrimethoxysilane, isopentyl Trimethoxy silane, cyclopentyl-trimethoxy-silane, cyclohexyl trimethoxy silane, dimethoxydiphenylsilane, diphenyl diethoxy silane, phenyltrimethoxysila,e, phenyl triethoxysilane, n-propyl Trimethoxy silane, vinyltrimethoxy silane, vinyltriethoxysilane, tetramethoxy-silicane, tetraethoxysilane, four butoxy silanes etc.These silicoorganic compound can individually use, and also two or more can be combinationally used.Preferably, described silicoorganic compound are selected from one or more in dicyclopentyl dimethoxyl silane, diisopropyl dimethoxy silane, second, isobutyl dimethoxy silane, Cyclohexyl Methyl Dimethoxysilane, dimethoxydiphenylsilane, methyl-t-butyldimethoxysilane, tetraethoxysilane, propyl-triethoxysilicane and isobutyl triethoxy silane.
According to the present invention, in the preparation process of described Ziegler-Natta catalyst, the molar ratio of the titanium in the aluminium in described alkylaluminium cpd and described solids containing titanium catalyst component is as being 20-500:1; Be preferably 50-500:1; Be more preferably 50-100:1.The molar ratio of the silicon of the aluminium in described alkylaluminium cpd and described external donor compound is as being 0.1-500:1, preferred 1-200:1, more preferably 3-100:1.
According to the present invention, the kind of described filler is known to the skilled person, such as, can be median be 0.05-40 μm, be preferably the mineral filler of 0.1-20 μm.Particularly, the example of described filler includes but not limited to: one or more in calcium carbonate, clay, silica, alumina, barium sulfate, calcium sulfate, talcum, magnesium sulfate, titanium dioxide, zeolite, Tai-Ace S 150, diatomite, magnesiumcarbonate, kaolin, calcium oxide and magnesium oxide, is preferably calcium carbonate and/or titanium dioxide.Wherein, described calcium carbonate can select light calcium carbonate of the prior art and/or nano-calcium carbonate.The median of described light calcium carbonate is 0.5-15 μm, is preferably 0.6-10 μm.The median of described nano-calcium carbonate is 0.1-0.6 μm, is preferably 0.1-0.3 μm.Described filler to be particularly preferably median the be nano-calcium carbonate of 0.1-0.3 μm.
Described nano-calcium carbonate can improve the processing characteristics of polypropene composition, improves its rheological, dimensional stability, heat-resistant stability etc., can also play enhancing, toughness reinforcing effect.Special in BiOriented Polypropylene Films, nano-calcium carbonate fine size and evenly, film uniform ground more can be made, and nano-calcium carbonate has high opacity, high brightness, addition can be changed as required to improve whiteness and the opacity of film.In addition, the high-expansion of nano-calcium carbonate, can also play and reduce film loose density, improves the effect of imitative writing property of paper film.
Described nano-calcium carbonate can be commercially available, and also can prepare according to existing method.Such as, described nano-calcium carbonate can be prepared by following industrial production process: at certain density Ca (OH) 2suspension in pass into carbon dioxide and carry out carbonization, wherein, by Ca (OH) 2the temperature of suspension, the flow of carbon dioxide control the nucleation rate of calcium carbonate nucleus; In carbonization to after forming certain nucleus number, be converted into crystal growth by nucleus formation control and control, now add the growth velocity that morphology regulation additives controls each crystal face, thus reach morphology controllable; Continue carbonization and add the calcite nano particle that dispersion agent adjustment particle surface electric charge obtains Monodispersed to terminal.
According to the present invention, the kind of described nucleator is known to the skilled person, and such as, can be Sorbitol Nucleator and/or aryl phosphoric acids salt nucleator.
The specific examples of described Sorbitol Nucleator can include but not limited to: 1, 3:2, 4-bis-(α-tolylene)-D-glucitol, 1, 3:2, 4-bis-(4-methylbenzene subunit)-D-glucitol, 1, 3:2, 4-bis-(3, 4-dimethylbenzylidene)-D-glucitol, 1, 3:2, 4-bis-(4-ethylbenzene methylene radical)-D-glucitol, two-1, 3:2, 4-(4 '-propyl group benzylidene)-1-allyl sorbitol, two-1, 3:2, 4-(4 '-ethylbenzylidene)-1-allyl sorbitol, two-1, 3:2, 4-(4 '-propoxy-benzylidene)-1-allyl sorbitol, two-1, 3:2, 4-(4 '-propyl group benzylidene)-1-propyl group sorbyl alcohol, two-1, 3:2, 4-(4 '-propoxy-benzylidene)-1-propyl group sorbyl alcohol.Described Sorbitol Nucleator is preferably 1,3:2,4-bis-(3,4-dimethylbenzylidene)-D-glucitol is (as can purchased from American Milliken Co., the trade mark is Millad3988) and/or two-1,3:2,4-(4 '-propyl group benzylidene)-1-propyl group sorbyl alcohol (disclosed in CN101484458A, can purchased from American Milliken Co., the trade mark is NX8000), be particularly preferably two-1,3:2,4-(4 '-propyl group benzylidene)-1-propyl group sorbyl alcohol.
The specific examples of described aryl phosphoric acids salt nucleator can include but not limited to: 2,2 '-methylene radical-bis-(4,6-di-tert-butyl-phenyl) sodium phosphate, 2,2 '-ethidine-bis-(4,6-di-tert-butyl-phenyl) sodium phosphate, 2,2 '-methylene radical-bis-(4,6-di-tert-butyl-phenyl) Trilithium phosphate, 2,2 '-ethidine-bis-(4,6-di-tert-butyl-phenyl) Trilithium phosphate, 2,2 '-ethidine-bis-(4-sec.-propyl-6-di-tert-butyl-phenyl) sodium phosphate, 2,2 '-methylene radical-bis-(4-methyl-6-di-tert-butyl-phenyl) Trilithium phosphate, 2,2 '-methylene radical-bis-(4-ethyl-6-di-tert-butyl-phenyl) Trilithium phosphate, two [2,2 '-thiobis (4-methyl-6-di-tert-butyl-phenyl) calcium phosphate], two [2,2 '-thiobis (4-ethyl-6-di-tert-butyl-phenyl) calcium phosphate], two [2,2 '-thiobis (4,6-di-tert-butyl-phenyl) calcium phosphate], two [2,2 '-thiobis (4,6-di-tert-butyl-phenyl) trimagnesium phosphate], two [2,2 '-thiobis (the tertiary octyl phenyl of 4,6-bis-) trimagnesium phosphate], 2,2 '-Ding pitches base-bis-(4,6-3,5-dimethylphenyl) sodium phosphate, 2,2 '-tertiary octyl group methylene radical-bis-(4,6-3,5-dimethylphenyl) sodium phosphate, 2,2 '-tertiary octyl group methylene radical-bis-(4,6-di-tert-butyl-phenyl) sodium phosphate, two [2,2 '-methylene radical-bis-(4,6-di-tert-butyl-phenyl) calcium phosphate], two [2,2 '-methylene radical-bis-(4,6-di-tert-butyl-phenyl) trimagnesium phosphate], two [2,2 '-methylene radical-bis-(4,6-di-tert-butyl-phenyl) barium phosphate], 2,2 '-methylene radical-bis-(4-methyl-6-tert butyl phenyl) sodium phosphate, 2,2 '-methylene radical-bis-(4-ethyl-6-tert-butyl-phenyl) sodium phosphate, two [4,4 '-dimethyl-6,6 '-di-t-butyl-2,2 '-xenyl) calcium phosphate], 2,2 '-ethidine-bis-(the m-butyl of 4--6-tert-butyl-phenyl) sodium phosphate, 2,2 '-methylene radical-bis-(4,6-3,5-dimethylphenyl) sodium phosphate, 2,2 '-methylene radical-bis-(4,6-diethyl phenyl) sodium phosphate, 2,2 '-ethidine-bis-(4,6-di-tert-butyl-phenyl) potassiumphosphate, two [2,2 '-ethidine-bis-(4,6-di-tert-butyl-phenyl) calcium phosphate], two [2,2 '-ethidine-bis-(4,6-di-tert-butyl-phenyl) trimagnesium phosphate], two [2,2 '-ethidine-bis-(4,6-di-tert-butyl-phenyl) barium phosphate], hydroxyl-bis-[2,2 '-ethidine-bis-(4,6-di-tert-butyl-phenyl) aluminum phosphate], three pairs [2,2 '-ethidine-bis-(4,6-di-tert-butyl-phenyl) aluminum phosphate], hydroxyl-bis-[2,4,8,10-tetra-(1,1 '-dimethyl ethyl)-6-hydroxyl-12H-dibenzo [d, g] dioxy phospha eight ring-6-oxygen] closes aluminium.Described aryl phosphoric acids salt nucleator is preferably 2,2 '-methylene radical-bis-(4,6-di-tert-butyl-phenyl) sodium phosphate, hydroxyl-bis-[2,2 '-ethidine-bis-(4,6-di-tert-butyl-phenyl) aluminum phosphate] and hydroxyl-bis-[2,4,8,10-tetra-(1,1 '-dimethyl ethyl)-6-hydroxyl-12H-dibenzo [d, g] dioxy phospha eight ring-6-oxygen] close in aluminium one or more.Described aryl phosphoric acids salt nucleator can be commercially available, such as, can be ADK NA-11(2 purchased from Japanese rising sun electrification company, the trade mark, 2 '-methylene radical-bis-(4,6-di-tert-butyl-phenyl) sodium phosphate salt) and/or ADK NA-21(main component be: hydroxyl-bis-[2,4,8,10-tetra-(1,1 '-dimethyl ethyl)-6-hydroxyl-12H-dibenzo [d, g] dioxy phospha eight ring-6-oxygen] close aluminium) aryl phosphoric acids salt nucleator.
According to the present invention, according to the needs that reality uses, described polypropene composition can also contain other auxiliary agent.Other auxiliary agent described can be such as at least one in oxidation inhibitor, halogen-resistant agent, photostabilizer, thermo-stabilizer, tinting material, filler, slipping agent, antisticking agent, static inhibitor etc.In addition, with the described polypropylene of 100 weight parts for benchmark, the consumption of other auxiliary agent described can be 0.05-0.3 weight part, is preferably 0.15-0.25 weight part.
Present invention also offers a kind of polypropylene film be made up of described polypropene composition.
The main improvements of polypropylene film provided by the invention are that the polypropene composition that have employed other auxiliary agent contained containing specific polypropylene, filler, nucleator and selectivity is as raw materials for production, and concrete preparation process can be same as the prior art.
Particularly, each component in described polypropene composition is mixed in high speed agitator, and the material after mixing is added the even also extruding pelletization of melting mixing in twin screw extruder, dry.Processing temperature remains between 170-250 DEG C, finally obtains polypropene composition pellet.Then described polypropene composition pellet is joined in casting apparatus and carry out extruding curtain coating slab.Wherein, curtain coating slab head can be single or multiple lift structure composite head.Extrusion temperature can be 190-280 DEG C, and casting roller temperature can be 10-95 DEG C.And then the raw material sheet material through extruding flow casting molding is carried out drawing and forming in film two-way stretch equipment.Wherein, described drawing and forming can adopt Synchronos method drawing process (namely simultaneously carrying out film longitudinally (MD) and laterally (TD) stretching), also can adopt method of fractional steps drawing process (namely first carry out film longitudinally (MD) stretch, after carry out film laterally (TD) stretch).
The concrete operations of Synchronos method drawing process are as follows: raw material sheet material, after abundant preheating, carries out the synchro-draw in MD and TD direction, and wherein MD stretching ratio can be 2-7 times, and TD stretching ratio can be 4-12 times, and draft temperature can be 110-180 DEG C.Can be unannealed after film stretching is shaping, also can carry out anneal, through cutting edge and rolling, obtain the BOPP film that thickness is 5-150 μm.
The concrete operations of method of fractional steps drawing process are as follows: raw material sheet material, after abundant preheating, first carries out the stretching in MD direction, and stretching ratio can be 2-7 times, and draft temperature can be 80-160 DEG C; Then carry out the stretching in TD direction, stretching ratio can be 4-12 times, and draft temperature can be 140-180 DEG C.Can be unannealed after film stretching is shaping, also can carry out anneal, and through cutting edge and rolling, obtain the BOPP film that thickness is 5-150 μm.
In addition, described polypropene composition not only may be used for the BiOriented Polypropylene Films preparing individual layer, can also for the preparation of Multi-layer biaxial tension polypropylene film.At least one deck in Multi-layer biaxial tension polypropylene film contains described polypropene composition, and other layer of raw material can be homo-polypropylene, ethylene-propylene copolymer, propylene and other alpha olefin copolymer etc., will repeat no more at this.
Below will be described the present invention by embodiment.
In following examples and comparative example, propylene and hydrogen are polymerization-grade, through dehydration, deoxidation treatment.
In following examples and comparative example, polypropylene film adopts the KaroVI type film stretching experimental machine of Bruckner company and adopts step drawing technique to be prepared.
In following examples and comparative example:
1, molecular weight distributing index Mw/Mn, peak molecular weight Mp, the model that weight-average molecular weight Mw and Z-average molecular weight Mz adopts Polymer Laboratories company of Britain to produce is that the gel permeation chromatograph of PL-GPC220 measures in conjunction with IR5 type infrared detector, wherein, chromatographic column in gel permeation chromatograph is Plgel10 μm of MIXED-B post of 3 series connection, solvent and moving phase are 1, 2, 4-trichlorobenzene is (containing the oxidation inhibitor 2 of 0.3g/1000mL, 6-ditertbutylparacresol), column temperature is 150 DEG C, flow velocity is 1.0mL/min, adopt PL company to produce EasiCal PS-l Narrow distribution polystyrene standard specimen and carry out universal calibration.
Polymer hangover indices P I hT(1) calculates according to the following formula:
PI HT=10 5×(Mz/Mp)/Mw （1）。
2, the assay of isotaxy five unit group [mmmm]:
Due to 13in C-NMR spectrum, the stereoregular information that the methyl carbon district that chemical shift is 19.5-22.5ppm can provide resolving power higher, obtain the content of triad isotactic, an isotactic-rule, an a rule-rule, therefore, use this district measuring result and according to formula (2) calculate isotaxy five unit group [mmmm] content:
[ mmmm ] % = 100 &times; [ mmmm ] [ mm ] + [ mr ] + [ rr ] - - - ( 2 )
Wherein, [mm], [mr], [rr] are respectively triad isotactic, an isotactic-rule, an a rule-content of advising.
Adopt the model of Switzerland Bruker company be polyacrylic nuclear-magnetism carbon spectrum under the nuclear magnetic resonance spectrometer (NMR) of AVANCE III measures 400MHz ( 13c-NMR), wherein, solvent is deuterated orthodichlorobenzene, and sample concentration is 250mg sample/2.5mL solvent.For preventing sample oxidative degradation in dissolving and data acquisition, add the 2,6 di tert butyl 4 methyl phenol oxidation inhibitor (being called for short BHT) of 2mg in the sample to which.140 DEG C of dissolved samples, gather 13c-NMR, probe temperature 125 DEG C, detecting head specification 10 millimeters, 90 ° of pulses, sampling time AQ is 5 seconds, and time of lag, D1 was 1 second, scanning times 6000 times.Spectrum peak identification is concrete with reference to reference: (1) Hansen E W, Redford K.Nuclear Magnetic Resonance Spectroscopy of Polypropylene Homopolymers.In:Karger-Kocsis J, ed.Polypropylene:A-Z Reference.Dordrecht:Kluwer Publishers, 1999:540-544; (2) Zambelli A, Macromelecules Vol8, No5,1975:687-688.
3, propylene 2, the mensuration of 1 insertion and the position heterogeneous structure content caused by 1,3 insertions:
Pass through 13c-NMR analyzes and calculates the content that " 2,1 " inserts and " 1,3 " insert according to the following formula:
Wherein, the locus of the carbon atom that α α, α β, α δ three kinds of representing that different inserted mode causes are different, carbon atom represents when being α α position that inserted mode is normal " head-tail " mode, be " 2; 1 when carbon atom is α β position " insert, for " 1,3 " insert when carbon atom is α δ position.
13the test conditions of C-NMR is identical with 2, the identification at spectrum peak and data processing concrete reference reference: (1) Grassi A, Zambelli A.Macromolecules, 1988,21:617-622; (2) Tsutsui T, Ishimaru N, Mizuno A, et al.Polymer, 1989,30:1350-1356.
4, the mensuration of TREF analysis mode solubles content: adopt the TREF-300 type analysis instrument of Poly CHAR company to measure, concrete grammar is as follows: take trichlorobenzene (TCB) solvent that 80mg sample 40mL is added with 0.3 % by weight BHT and dissolve 60min at 150 DEG C, make sample fully dissolve formation homogeneous solution; Get the above-mentioned solution of 20mL and enter post, be cooled to 35 DEG C with 0.2 DEG C/min speed, make sample in temperature-fall period according to crystallizing power size gradually crystallization be deposited on post; Be warming up to 140 DEG C with 1.0 DEG C/min again stablize 10min at 35 DEG C after and carry out drip washing.The flow velocity controlling solvent pump in drip washing is 0.5mL/min, and sample dissolution is constantly drenched by solvent, the record pouring effluent of sample and the relation of temperature.TREF analysis mode solubles content is designated as by drenching effluent percentage composition at 35 DEG C.
5, the mensuration of Tc Tc: the DIAMOND type DSC adopting PE company to produce measures, and wherein, correct instrument with indium metal and zinc standard specimen, sample quality is about 5mg, and atmosphere is nitrogen, and airshed is 20mL/min.By sample with the ramp to 210 of 10 DEG C/min DEG C and constant temperature 5min to eliminate thermal history, and then be cooled to 50 DEG C with the speed of 10 DEG C/min, record crystallization exotherm, temperature corresponding for the peak value of crystallization exotherm is designated as Tc Tc.
6, xylene soluble content measures according to the method specified in ASTM D5492-98.
7, melt mass flow rate MFR measures according to the method specified in ISO1133, and wherein, probe temperature is 230 DEG C, and load is 2.16kg.
8, the titanium atom content in solids containing titanium catalyst component and Ziegler-Natta catalyst adopts 721 spectrophotometers purchased from An Hemeng (Tianjin) development in science and technology company limited to measure.The particle diameter of alkoxyl magnesium compound and Ziegler-Natta catalyst and size distribution index adopt Malvern Mastersizer TM2000 laser particle analyzer to measure, wherein, adopt normal hexane as dispersion agent, size distribution index SPAN=(D90-D10)/D50.The mensuration of the m value in alkoxyl magnesium compound: get 0.1 gram of alkoxyl magnesium compound, adding 10mL concentration is 1.2mol/L aqueous hydrochloric acid, shaking makes it decompose in 24 hours, gas chromatograph (purchased from Alan Analytical Instrument Co., Ltd, model is GC-7960) is adopted to measure ethanol wherein and 2-Ethylhexyl Alcohol content and be calculated as follows m value:
m = 2 ( w 1 &times; 46.07 ) w 2 &times; 130.23 + w 1 &times; 46.07
Wherein, w1 is 2-Ethylhexyl Alcohol quality, and w2 is ethanol quality.
In Ziegler-Natta catalyst, the content of internal electron donor adopts Waters600E liquid chromatograph to measure.
9, the mechanical strength of polypropylene film is tested according to GB/T1040.3-2006.
Embodiment 1
This embodiment is for illustration of polypropene composition provided by the invention and polypropylene film and preparation method thereof.
(1) polyacrylic preparation:
The preparation of A, solids containing titanium catalyst component: after fully replacing the 16L voltage-resistant reactor with agitator with nitrogen, then in reactor, add 10L ethanol, the 2-Ethylhexyl Alcohol of 300mL, 11.2g iodine, 8g magnesium chloride and 640g magnesium powder and be uniformly mixed, while stirring, system is made to be warming up to 75 DEG C of back flow reaction, until no longer including stopped reaction till hydrogen is discharged.By obtain reaction product 3L washing with alcohol, filtration, drying, obtain dialkoxy magnesium, its median size D50 is 30.2 μm, and size distribution index SPAN is 0.81, m is 0.015.Get the above-mentioned dialkoxy magnesium of 650g, 3250mL toluene, 65mL 2-sec.-propyl-2-isopentyl-1,3-Propanal dimethyl acetal be mixed with suspension.Repeating in the withstand voltage reactor of 16L of replacing through high pure nitrogen, add 2600mL toluene and 3900mL titanium tetrachloride, be warming up to 80 DEG C, then the suspension prepared added in still, constant temperature 1 hour at 80 DEG C, add the 2-sec.-propyl-2-isopentyl-1 of 65mL, 3-Propanal dimethyl acetal, is slowly warming up to 110 DEG C, then constant temperature 2 hours, press filtration, obtains solid product.Above-mentioned solid product is added in the mixed solution of 5070mL toluene and 3380mL titanium tetrachloride, and 110 DEG C of stir process 1 hour, re-treatment like this 3 times, press filtration, and the solid product hexane (through processed) obtained is washed 4 times, each consumption is 600mL, and press filtration, drying obtain solids containing titanium catalyst component.Wherein, the content of titanium atom is the content of 4.1 % by weight, 2-sec.-propyl-2-isopentyl-1,3-Propanal dimethyl acetals is 11.9 % by weight.
B, testing apparatus:
Device adopts continuous autoclave pre-polymerization and horizontal retort gas phase series polymerizations technique.Prepolymerization reactor is the vertical mixing Fu of jacketed cooling, and volume is 5 liters, and agitating vane is the oblique oar of turbine type, and stirring velocity is 500 revs/min; Horizontal pneumatic phase reactor is Horizontal stirring Fu, and volume is 0.2 cubic metre, and stirring rake is T-shaped oblique blade, and angle of inclination is 10 degree, and stirring velocity is 100 revs/min.
C, test conditions:
(1) step prepolymerization: reaction pressure is 2.5MPa, temperature of reaction is 10 DEG C, and the reaction times is 12 minutes; Solids containing titanium catalyst component and triethyl aluminum inlet amount are respectively 0.4g/ hour and 0.058 mol/hr, and propylene feed amount is 10 kgs/hour, obtain the propylene pre-polymer that pre-polymerization multiple is 100 grams of polymkeric substance/gram catalyzer;
(2) step vapour phase polymerization: temperature of reaction is 98 DEG C, reaction pressure is 2.3MPa, reaction times is 60 minutes, the propylene pre-polymer that step (1) obtains is passed in Horizontal stirring Fu continuously, the inlet amount simultaneously controlling propylene is 30 kgs/hour, and makes hydrogen/propylene molar ratio in reaction gas phase be 0.0003.
Carried out 48 hours long run tests according to above-mentioned condition, device stable operation, the polypropylene obtained is carried out analytical test, and acquired results is as shown in table 1.
(2) preparation of polypropene composition:
(concrete consumption is as shown in table 2 for polypropylene, filler, nucleator and the oxidation inhibitor that will be obtained by step (1), wherein, filler to be median the be nano-calcium carbonate of 0.1 μm, nucleator is ADK NA-21, oxidation inhibitor is four [methyl-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester (be called for short 1010)) add in agitator and mix, then the material mixed is joined W & P company in the feeder of twin screw extruder, material enters in twin screw via feeder, even through screw rod melting mixing, extruding pelletization, and dry, in the course of processing, the temperature of screw rod controls, between 170-230 DEG C, to obtain polypropene composition pellet.
(3) preparation of polypropylene film:
The polypropene composition pellet that step (2) obtains is added in hot-air oven and carries out drying, and the model added by dried polypropene composition pellet purchased from Labtech company of Sweden is carry out curtain coating slab in the curtain coating extrusion equipment of LCR400, and the Karo IV type film two-way stretch experimental machine of German Br ü ckner company the polypropylene slab obtained is adopted to carry out two-way stretch.Particularly, slab put in the stretching clamp of film two-way stretch experimental machine, the two-way step drawing technique that after adopting first MD to stretch, TD stretches forms BOPP film, and each step process condition is as follows: MD preheating temperature 150 DEG C, MD draft temperature 150 DEG C, MD stretching ratio 5 times; TD preheating temperature 172 DEG C, TD draft temperature 165 DEG C, TD stretching ratio 7 times, obtain the polypropylene film that mean thickness is 20 microns, its performance is as shown in table 3.
Embodiment 2
This embodiment is for illustration of polypropene composition provided by the invention and polypropylene film and preparation method thereof.
(1) polyacrylic preparation:
The preparation of A, solids containing titanium catalyst component: (with embodiment 1);
B, testing apparatus: (with embodiment 1);
C, test conditions:
(1) step prepolymerization: reaction pressure is 2.5MPa, temperature of reaction is 10 DEG C, and the reaction times is 12 minutes; Solids containing titanium catalyst component and triethyl aluminum inlet amount are respectively 0.4g/ hour and 0.058 mol/hr, and propylene feed amount is 10 kgs/hour, obtain the propylene pre-polymer that pre-polymerization multiple is 100 grams of polymkeric substance/gram catalyzer;
(2) step vapour phase polymerization: temperature of reaction is 91 DEG C, reaction pressure is 2.3MPa, reaction times is 60 minutes, the propylene pre-polymer that step (1) obtains is passed in Horizontal stirring Fu continuously, the inlet amount simultaneously controlling propylene is 30 kgs/hour, and makes hydrogen/propylene molar ratio in reaction gas phase be 0.0005.
Carried out 48 hours long run tests according to above-mentioned condition, device stable operation, the polypropylene obtained is carried out analytical test, and acquired results is as shown in table 1.
(2) polypropene composition preparation:
(concrete consumption is as shown in table 2 for polypropylene, filler, nucleator and the oxidation inhibitor that will be obtained by step (1), wherein, filler to be median the be nano-calcium carbonate of 0.3 μm, nucleator is ADK NA-21, oxidation inhibitor is 1010) add in agitator and mix, then the material mixed is joined W & P company in the feeder of twin screw extruder, material enters in twin screw via feeder, even through screw rod melting mixing, extruding pelletization, and dry, in the course of processing, the temperature of screw rod controls, between 170-230 DEG C, to obtain polypropene composition pellet.
(3) preparation of polypropylene film:
With embodiment 1, obtain the polypropylene film that mean thickness is 20 microns, its performance is as shown in table 3.
Embodiment 3
This embodiment is for illustration of polypropene composition provided by the invention and polypropylene film and preparation method thereof.
(1) polyacrylic preparation:
The preparation of A, solids containing titanium catalyst component: (with embodiment 1);
B, testing apparatus: (with embodiment 1);
C, test conditions:
(1) step prepolymerization: reaction pressure is 2.5MPa, temperature of reaction is 10 DEG C, and the reaction times is 12 minutes; Solids containing titanium catalyst component, triethyl aluminum and dicyclopentyl dimethoxyl silane (DCPDMS, being commonly called as D-Donor) inlet amount is respectively 1.1g/ hour, 0.051 mol/hr and 0.0082 mol/hr, Al/Si mol ratio is 6.2, propylene feed amount is 10 kgs/hour, obtains the propylene pre-polymer that pre-polymerization multiple is 150 grams of polymkeric substance/gram catalyzer;
(2) step vapour phase polymerization: temperature of reaction is 98 DEG C, reaction pressure is 2.3MPa, reaction times is 60 minutes, the propylene pre-polymer that step (1) obtains is passed in Horizontal stirring Fu continuously, the inlet amount simultaneously controlling propylene is 30 kgs/hour, and makes hydrogen/propylene molar ratio in reaction gas phase be 0.0005.
Carried out 48 hours long run tests according to above-mentioned condition, device stable operation, the polypropylene obtained is carried out analytical test, and acquired results is as shown in table 1.
(2) preparation of polypropene composition:
(concrete consumption is as shown in table 2 for polypropylene, filler, nucleator and the oxidation inhibitor that will be obtained by step (1), wherein, filler to be median the be titanium dioxide of 15 μm, nucleator is ADK NA-21, oxidation inhibitor is 1010) add in agitator and mix, then the material mixed is joined W & P company in the feeder of twin screw extruder, material enters in twin screw via feeder, even through screw rod melting mixing, extruding pelletization, and dry, in the course of processing, the temperature of screw rod controls, between 170-230 DEG C, to obtain polypropene composition pellet.
(3) preparation of polypropylene film:
With embodiment 1, obtain the polypropylene film that mean thickness is 20 microns, its performance is as shown in table 3.
Embodiment 4
This embodiment is for illustration of polypropene composition provided by the invention and polypropylene film and preparation method thereof.
(1) polyacrylic preparation:
The preparation of A, solids containing titanium catalyst component: (with embodiment 1);
B, testing apparatus: (with embodiment 1);
C, test conditions:
(1) step prepolymerization: reaction pressure is 2.5MPa, temperature of reaction is 10 DEG C, and the reaction times is 12 minutes; Solids containing titanium catalyst component, triethyl aluminum and second, isobutyl dimethoxy silane (DIBDMS, being commonly called as B-Donor) inlet amount is respectively 1.0g/ hour, 0.054 mol/hr and 0.0087 mol/hr, Al/Si mol ratio is 6.2, propylene feed amount is 10 kgs/hour, obtains the propylene pre-polymer that pre-polymerization multiple is 200 grams of polymkeric substance/gram catalyzer;
(2) step vapour phase polymerization: temperature of reaction is 91 DEG C, reaction pressure is 2.3MPa, reaction times is 60 minutes, the propylene pre-polymer that step (1) obtains is passed in Horizontal stirring Fu continuously, the inlet amount simultaneously controlling propylene is 30 kgs/hour, and makes hydrogen/propylene molar ratio in gas phase be 0.0014.
Carried out 48 hours long run tests according to above-mentioned condition, device stable operation, the polypropylene obtained is carried out analytical test, and acquired results is as shown in table 1.
(2) polypropene composition preparation:
(concrete consumption is as shown in table 2 for polypropylene, filler, nucleator and the oxidation inhibitor that will be obtained by step (1), wherein, filler to be median the be light calcium carbonate of 10 μm, nucleator is the trade mark produced by Milliken Co. of the U.S. is the nucleator of NX8000, oxidation inhibitor is 1010) add in agitator and mix, then the material mixed is joined W & P company in the feeder of twin screw extruder, material enters in twin screw via feeder, even through screw rod melting mixing, extruding pelletization, and dry, in the course of processing, the temperature of screw rod controls, between 170-230 DEG C, to obtain polypropene composition pellet.
(3) preparation of polypropylene film:
With embodiment 1, obtain the polypropylene film that mean thickness is 20 microns, its performance is as shown in table 3.
Comparative example 1
This comparative example is for illustration of the polypropene composition and polypropylene film and preparation method thereof of reference.
The preparation of polypropylene, polypropene composition and polypropylene film is carried out according to the method for embodiment 1, unlike, it is that (molecular weight distributing index is 5.7 for the polypropylene of FS3011E that polypropylene adopts purchased from the trade mark of TPC company of Singapore, polymer hangover index is 1.85) substitute, obtain reference polypropylene, reference polypropylene composition and reference polypropylene film.Wherein, the performance of reference polypropylene is as shown in table 1, and the consumption of reference polypropylene composition is as shown in table 2, and the performance of reference polypropylene film is as shown in table 3.
Comparative example 2
This comparative example is for illustration of the polypropene composition and polypropylene film and preparation method thereof of reference.
The preparation of polypropylene, polypropene composition and polypropylene film is carried out according to the method for embodiment 2, unlike, it is that (molecular weight distributing index is 5.7 for the polypropylene of FS3011E that polypropylene adopts purchased from the trade mark of TPC company of Singapore, polymer hangover index is 1.85) substitute, obtain reference polypropylene, reference polypropylene composition and reference polypropylene film.Wherein, the performance of reference polypropylene is as shown in table 1, and the consumption of reference polypropylene composition is as shown in table 2, and the performance of reference polypropylene film is as shown in table 3.
Comparative example 3
This comparative example is for illustration of the polypropene composition and polypropylene film and preparation method thereof of reference.
The preparation of polypropylene, polypropene composition and polypropylene film is carried out according to the method for embodiment 3, unlike, in described polyacrylic preparation process, the temperature of reaction of (2) step is 66 DEG C, and the mol ratio making hydrogen and propylene in reaction gas phase is 0.002, obtain reference polypropylene, reference polypropylene composition and reference polypropylene film.Wherein, the performance of reference polypropylene is as shown in table 1, and the consumption of reference polypropylene composition is as shown in table 2, and the performance of reference polypropylene film is as shown in table 3.
Comparative example 4
This comparative example is for illustration of the polypropene composition and polypropylene film and preparation method thereof of reference.
(1) polyacrylic preparation:
The preparation of A, solids containing titanium catalyst component: (with embodiment 1);
B, testing apparatus: (with embodiment 1);
C, test conditions:
Polypropylene, without prepolymerization, directly joins in horizontal agitated vessel.Polymeric reaction temperature is 98 DEG C, reaction pressure is 2.3MPa, reaction times is 60 minutes, solids containing titanium catalyst component and triethyl aluminum inlet amount are respectively 0.4g/ hour and 0.058 mol/hr, the inlet amount of propylene is 30 kgs/hour, and makes hydrogen/propylene molar ratio in reaction gas phase be 0.01.
Carried out 48 hours long run tests according to above-mentioned condition, found that, polymer active is too low, and cannot obtain polypropylene, acquired results is as shown in table 1.
(2) polypropene composition preparation:
Cannot prepare.
(3) preparation of polypropylene film:
Cannot prepare.
Table 1
Numbering Embodiment 1 Embodiment 2 Embodiment 3 Embodiment 4 Comparative example 1 Comparative example 2 Comparative example 3 Comparative example 4
External electron donor Nothing Nothing D Donor B Donor -- -- D Donor Nothing
Pre-polymerization temperature, DEG C 10 10 10 10 -- -- 10 Not pre-polymerization
The pre-polymerization time, min 12 12 12 12 -- -- 12 -
Polymerization temperature, DEG C 98 91 98 91 -- -- 66 98
Hydrogen/propylene molar ratio in Gas-phase reactor 0.0003 0.0005 0.0005 0.0014 --- --- 0.002 0.01
Polymerization activity, KgPP/gCat.h 33 45 28 35 -- -- 50 3
Mw，10 4g/mol 39.9 39.7 41.5 33.3 38.1 38.1 37.6 -
Molecular weight distributing index Mw/Mn 4.4 3.8 4.3 4.1 5.7 5.7 7.0 -
PI HT 2.39 2.35 2.40 2.31 1.85 1.85 2.02 -
Isotaxy five unit group [mmmm] content, % 93.9 93.7 94.6 95.0 87.8 87.8 92.1 -
Propylene 2,1 inserts and/or 1,3 insertion content, % 0 0 0 0 0 0 0 -
Solubles content (TREF analysis mode), wt% 3.05 3.11 1.85 1.60 3.8 3.8 2.9 -
Xylene soluble content, wt% 2.09 2.13 1.56 1.42 3.8 3.8 3.4 -
Melt mass flow rate, g/10min 3.0 3.0 2.0 5.0 3.0 3.0 2.0 -
Tc，℃ 120.1 119.5 121.8 122.4 106.8 106.8 117.2 -
[0194]table 2
Table 3
As can be seen from the above results, the longitudinal tensile of polypropylene film provided by the invention can reach more than 3.49GPa, cross directional stretch modulus can reach more than 5.32GPa, and longitudinal fracture intensity can reach more than 72MPa, and cross-breaking strength can reach more than 105MPa.That is, the polypropylene film prepared by polypropene composition provided by the invention has higher mechanical strength.
In addition, as can be seen from the contrast of embodiment 1 and comparative example 1, embodiment 2 and comparative example 2, with adopt commercially available polypropylene to be compared with the polypropylene film for preparing of raw material, adopt polypropylene provided by the invention to be that the modulus of the polypropylene film that raw material prepares is higher, tensile break strength is larger.Can conclude thus, adopt that molecular weight distribution provided by the invention is narrower, polymer hangover indices P I hTlarger polypropylene can play the effect of filler and nucleator better, obtains the polypropylene film that mechanical strength is higher.
More than describe the preferred embodiment of the present invention in detail; but the present invention is not limited to the detail in above-mentioned embodiment, within the scope of technical conceive of the present invention; can carry out multiple simple variant to technical scheme of the present invention, these simple variant all belong to protection scope of the present invention.
It should be noted that in addition, each the concrete technical characteristic described in above-mentioned embodiment, in reconcilable situation, can be combined by any suitable mode.In order to avoid unnecessary repetition, the present invention illustrates no longer separately to various possible array mode.
In addition, also can carry out arbitrary combination between various different embodiment of the present invention, as long as it is without prejudice to thought of the present invention, it should be considered as content disclosed in this invention equally.

Claims (12)

1. a polypropene composition, is characterized in that, this polypropene composition contains polypropylene, filler and nucleator; Described polyacrylic molecular weight distributing index is 2.5-5.5, the polymer hangover indices P I in molecular weight distribution width hTbe greater than 1.9.
2. polypropene composition according to claim 1, wherein, with the described polypropylene of 100 weight parts for benchmark, the content of described filler is 10-85 weight part, and the content of described nucleator is 0.01-0.5 weight part.
3. polypropene composition according to claim 1, wherein, the content of described polyacrylic isotaxy five unit group [mmmm] is greater than 85%, is preferably greater than 90%, more preferably greater than 93%.
4. polypropene composition according to claim 1, wherein, the position heterogeneous structure caused by described polypropylene does not insert containing propylene 2,1 insertion and 1,3.
5. according to the polypropene composition in claim 1-4 described in any one, wherein, described polyacrylic Tc Tc is greater than 113 DEG C, is preferably greater than 115 DEG C.
6. according to the polypropene composition in claim 1-4 described in any one, wherein, in described polypropylene, the content of xylene soluble part is less than 4.4 % by weight, is preferably less than 2.3 % by weight, is more preferably less than 1.6 % by weight.
7. according to the polypropene composition in claim 1-4 described in any one, wherein, the melt mass flow rate MFR of described polypropylene at 230 DEG C, under the effect of 2.16kg load is 2-5g/10min.
8. according to the polypropene composition in claim 1-4 described in any one, wherein, described polypropylene is prepared by the method comprised the following steps:
(1) under Ziegler-Natta catalyst exists, by propylene-10 DEG C to 50 DEG C, carry out prepolymerization under 0.1-100MPa, obtain the propylene pre-polymer that pre-polymerization multiple is 2-3000 gram of polymkeric substance/gram catalyzer, is preferably 3-2000 gram of polymkeric substance/gram catalyzer, is more preferably 50-300 gram of polymkeric substance/gram catalyzer;
(2) 91-150 DEG C, under 1-6MPa, described propylene pre-polymer and propylene are polymerized.
9. polypropene composition according to claim 1 and 2, wherein, described filler is selected from one or more in calcium carbonate, clay, silica, alumina, barium sulfate, calcium sulfate, talcum, magnesium sulfate, titanium dioxide, zeolite, Tai-Ace S 150, diatomite, magnesiumcarbonate, kaolin, calcium oxide and magnesium oxide.
10. polypropene composition according to claim 9, wherein, described filler to be median the be nano-calcium carbonate of 0.1-0.3 μm.
11. polypropene compositions according to claim 1 and 2, wherein, described nucleator is Sorbitol Nucleator and/or aryl phosphoric acids salt nucleator.
12. polypropylene films be made up of the polypropene composition in claim 1-11 described in any one.
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