CN104250399B

CN104250399B - A kind of polypropene composition and polypropylene knotting packaging film

Info

Publication number: CN104250399B
Application number: CN201310269783.9A
Authority: CN
Inventors: 张师军; 徐萌; 邹浩; 高达利; 徐凯; 王良诗; 郭梅芳; 张丽英; 吕芸
Original assignee: Sinopec Beijing Research Institute of Chemical Industry; China Petroleum and Chemical Corp
Current assignee: Sinopec Beijing Research Institute of Chemical Industry; China Petroleum and Chemical Corp
Priority date: 2013-06-28
Filing date: 2013-06-28
Publication date: 2017-03-01
Anticipated expiration: 2033-06-28
Also published as: CN104250399A

Abstract

The invention provides a kind of polypropene composition and the polypropylene knotting packaging film being made up of this polypropene composition.Described polypropene composition contains polypropylene and kink auxiliary agent；Described polyacrylic molecular weight distributing index is 2.5 5.5, macromolecule hangover indices P I in molecular weight distribution width_HTMore than 1.9；Described kink auxiliary agent is Petropols.The polyacrylic molecular weight distributing index containing in described polypropene composition is narrower and macromolecule hangover index is larger, the polypropene composition enabling to just not only has higher stretch moduluses and tensile strength under relatively low Petropols consumption, also has preferable kink property.

Description

A kind of polypropene composition and polypropylene knotting packaging film

Technical field

The present invention relates to a kind of polypropene composition and a kind of polypropylene knotting packaging film.

Background technology

Kink pack pattern novelty attractive in appearance, is easy to taking of packing material, is commonly used for the bag of confection, chocolate and food etc. Dress.At present, most of producer of China adopts polrvinyl chloride as kink packaging material, but polrvinyl chloride is in recovery and environmental conservation Aspect has some problems, can produce toxic gas, damage health, cause environmental pollution during its burning, many at present European countries forbid the packaging for confection and food etc..Acrylic resin not only has excellent mechanical performance and optical Can, and nontoxic pollution-free, light weight valency are excellent, are therefore widely used in thin film and packaging field, can be used for substituting and gather Application in terms of confection and packaging for foodstuff for the vinyl chloride.

The maximum feature of knotting packaging film is intended to there is preferable kink property, and thin film will be required to be difficult resilience after turning round, and And need thin film to have higher rigidity, thus improve the deflection of packaging so as to have good feel.But polypropylene is in itself A kind of good material of toughness, is easier to resilience, if not treated just cannot use as torsion film.Research shows, by carrying High polyacrylic steric regularity can improve polyacrylic crystal property, makes thin film be easier to obtain good kink performance.With When molecular weight is adjusted, polyacrylic mobility and processing characteristics can also be improved, and the mist degree of thin film, raising can be reduced The glossiness of thin film.

At present, existing polymerization is mainly poly- by adding different external electron donors to control in different polymerization stages The steric regularity of compound.Generally using external electron donor adjust polymer isotacticity method have the characteristics that one common：Carry The addition of high external electron donor is although the isotacticity of polymer can correspondingly improve, but catalyst is to molecular weight regulator Sensitivity has and reduces by a relatively large margin.Therefore, the method adjusting polypropylene isotacticity with external electron donor, usually cannot be simultaneously Obtain preferable steric regularity and molecular weight distribution.

Additionally, prior art can also add Petropols in commercially available casting films sandwich layer HOPP resin, To improve deflection and the kink property of thin film.For example, CN101161706A discloses a kind of knot film, this knot film include to Few one layer of film layer is it is characterised in that at least one layer described film layer contains following component：The polypropylene tree of 45-98 weight % Fat, the antiblocking agent of the Petropols of 2-40 weight %, the antistatic additive of 0-10 weight % and 0-5 weight %；Described polypropylene is general Logical polypropylene, the polypropylene being such as FC801 purchased from the trade mark that oil of SPC produces（Molecular weight distributing index is 7.7, and macromolecule drags Exponential tail is 1.81）, described Petropols can be 100-150 DEG C of hydrogenation saturated oil resin using softening point.Wherein, soften Point refers to the temperature that material softens, i.e. Petropols start temperature during deliquescing.But, during using the method, need to add relatively Many Petropols, generally will more than 15% just can preferable kink property, meet the needs of kink packaging, Petropols Addition less when be difficult to play improve kink property effect.But, on the one hand, Petropols consumption not only can cause greatly thin Film tacky, the performance of acrylic resin can be affected, lead to thin film mechanical performance and heat resistance to decline；On the other hand, oil Resin price is higher, and after a large amount of additions, production cost dramatically increases, and reduces economic benefit.

Content of the invention

The invention aims to overcome existing polypropylene knotting packaging film can not have concurrently higher rigidity, deflection with And the shortcoming of kink property, and a kind of polypropene composition of higher rigidity, deflection and kink property and poly- of can having concurrently is provided Propylene knotting packaging film.

The invention provides a kind of polypropene composition, wherein, this polypropene composition contains polypropylene and kink auxiliary agent； Described polyacrylic molecular weight distributing index is 2.5-5.5, macromolecule hangover indices P I in molecular weight distribution width_HTIt is more than 1.9；Described kink auxiliary agent is Petropols.

Present invention also offers a kind of polypropylene knotting packaging film being made up of described polypropene composition.

The polyacrylic molecular weight distributing index that the present invention provides is narrower, and macromolecule hangover index is larger, so can The polypropene composition obtaining is made just not only to have higher stretch moduluses and tensile strength under relatively low Petropols consumption （That is, there is preferable rigidity and deflection）, also there is preferable kink property.Can be seen that when oil tree from the result of embodiment The content of fat is during below 10 weight portions it becomes possible to make the longitudinal tensile of the polypropylene knotting packaging film obtaining reach More than 1.62GPa, cross directional stretch modulus reaches more than 1.54GPa, and longitudinal tensile strength reaches more than 35.3MPa, cross directional stretch Intensity reaches more than 35.0MPa, and kink angle is maintained at more than 300 °.Speculate its reason it may be possible to due to：On the one hand, molecule The narrower polypropylene of amount profile exponent has broader newton platform area in flow process, and its viscosity fluctuates with shear rate Change is less, and extrusion capacity is easier stability contorting, and can reduce the probability that surface defect occurs in film forming procedure, thus Improve the mechanical property of polypropylene kink packaging material, i.e. rigidity and deflection can be improved.Additionally, in polypropylene kink In the preparation process of packaging film, there is to have a yield point during strain in polypropylene stress, before surrender, recoverable elastic deformation occurs, Occur after surrender to reply plastic deformation, for molecular weight distribution is narrower and macromolecule hangover indices P I_HTHigher polypropylene, Only need to the presence adding a small amount of Petropols just can reduce amorphous region, contribute to making polypropylene reach surrender as early as possible Point, so that polypropylene knotting packaging film only occurs the deformation just no longer resilience of a very little, improves the kink of thin film.Another Aspect, macromolecule hangover indices P I_HTHigher show in polypropylene, there is more significant macromolecular chain tail end.Homogeneous according to polypropylene Nucleation theory, macromolecular chain tail end in crystallization can Preferential Nucleation, make that polyacrylic crystallization temperature raises, crystallization rate adds Hurry up, be conducive to improving rigidity, shorten molding cycle and improve shaping efficiency.In a word, the polypropene composition that the present invention provides was both Solve the little ineffective problem of prior art Petropols addition, prevent thin film excessive because of Petropols addition again And tacky, also reduce the production cost increasing because of a large amount of use of Petropols simultaneously.

A preferred embodiment of the invention, when containing of described polyacrylic isotaxy five unit group [mmmm] When amount is more than 85%, enables to melt polypropylene and there is in flow process broader newton platform area such that it is able to more aobvious Write ground and reduce the probability that surface defect occurs in film forming procedure, and be conducive to improving the crystallization of polypropylene knotting packaging film , so that the stretching of thin film is more uniform, the degree of orientation is higher, thus improving the mechanical property of polypropylene knotting packaging film for property.

A preferred embodiment of the invention, prepares polypropylene using two-stage polymerization method, the first step is relatively low At a temperature of carry out prepolymerization, and second step then improves the temperature of polyreaction, and the polypropylene so enabling to not only has There are narrower molecular weight distribution and larger macromolecule hangover indices P I_HT, also there is higher isotacticity, so that polypropylene is originally Body has higher degree of crystallinity and crystallization regularity, makes only have a small amount of amorphous region in polypropylene, be conducive to rigidity, deflection with And the raising further of kink property.

According to another kind of preferred implementation of the present invention, in described polyacrylic preparation process, when described Ziegler- Baunatal（Ziegler-Natta）When catalyst preferably comprises external donor compound, the polypropylene obtaining can not only be made to stand The raising further of structure regularity, but also in the polypropylene enabling to, the content of xylene soluble part significantly reduces, from And widened described polypropene composition and the application of polypropylene knotting packaging film.

Other features and advantages of the present invention will be described in detail in subsequent specific embodiment part.

Specific embodiment

Hereinafter the specific embodiment of the present invention is described in detail.It should be appreciated that it is described herein concrete Embodiment is merely to illustrate and explains the present invention, is not limited to the present invention.

The polypropene composition that the present invention provides contains polypropylene and kink auxiliary agent；Described polyacrylic molecular weight distribution refers to Number is 2.5-5.5, preferably 3.0-4.9；Macromolecule hangover indices P I in molecular weight distribution width_HTMore than 1.9, preferably greater than 2.1；Described kink auxiliary agent is Petropols.

PI_HTMore high, show in polypropylene, there is more significant macromolecular chain tail end.Described macromolecule hangover indices P I_HT It is calculated as follows：PI_HT=10⁵× (Mz/Mp)/Mw, wherein, Mp is peak molecular weight, and Mw is weight average molecular weight, Mz For Z-average molecular weight, unit is g/mol.Described Mp, Mw, Mz and molecular weight distributing index can pass through chromatograph of gel permeation （GPC）It is measured.

The present invention is not particularly limited to the content of the polypropylene in described polypropene composition and kink auxiliary agent, example As, on the basis of the described polypropylene of 100 weight portions, the content of described kink auxiliary agent can be 5-10 weight portion.

According to the present invention, so that the polypropylene knotting packaging film being prepared by described polypropene composition has more High intensity, the content of described polyacrylic isotaxy five unit group [mmmm] is preferably greater than 85%, further preferably greater than 90%, more preferably greater than 93%.

According to the present invention, in described polyacrylic preparation process, due to propylene monomer it may happen that " 2,1 " insertion and/ Or " 1,3 " insertion, lead to the regularity of polypropylene molecule chain structure to destroy, fusing point reduces, thus affecting polyacrylic use temperature Degree.The defect sturcture so causing is collectively referred to here in as position heterogeneous structure（regio-irregularity）.Isotactic polypropylene The structural formula of position heterogeneous structure is schematically as follows：

Head-header structure that " 2,1 " insertion causes（Erythro form）

Head-header structure that " 2,1 " insertion causes（Soviet Union's formula）

The position heterogeneous structure that " 1,3 " insertion causes

According to the present invention, so that the polypropylene knotting packaging film being prepared by described polypropene composition has more High intensity, under preferable case, described polypropylene does not contain the position heterogeneous structure caused by propylene 2,1 insertion and 1,3 insertions. It should be noted that " not containing " mentioned here does not refer to absolutely not contain, and refer to propylene 2,1 insertion and 1,3 insertions contain Amount is very low, and usually less than 0.01%, beyond the Monitoring lower-cut of instrument.

According to the present invention, preferably greater than 115 DEG C of described polyacrylic crystallization temperature Tc, more preferably greater than 120 DEG C, such energy Crystal structure after enough making the polypropylene that obtains crystallized is more perfect, thus significantly more improving the power of polypropylene knotting packaging film Learn performance.

According to the present invention, in described polypropylene, the content of xylene soluble part is preferably smaller than 4.4 weight %, further preferably Less than 2.3 weight %, more preferably less than 1.6 weight %.As a rule, xylene soluble content is low, and polyacrylic isotacticity is relatively Height, therefore rigidity and thermostability are preferable.Additionally, to some polypropylene kink packagings being applied to contact food, medicine or solvent For film, xylene soluble content is lower, then transportable go out or be dissolved out or the content of material that extracts is lower, using upper Safer reliability.

According to the present invention, described polypropylene is at 230 DEG C, 2.16kg load effect under melt mass flow rate MFR Particularly preferably 5-10g/10min.In the present invention, described melt mass flow rate MFR is according to method specified in ISO1133 It is measured, wherein, test temperature is 230 DEG C, load is 2.16kg.

According to the present invention, described polypropylene can be according to well known to a person skilled in the art various method prepares, example As described polypropylene is prepared by the method comprising the following steps：

（1）In Ziegler-Natta catalyst（Ziegler-Natta）In the presence of catalyst, by propylene at -10 DEG C to 50 DEG C, carry out prepolymerization under 0.1-100MPa, obtain pre-polymerization multiple and be 2-3000 gram of polymer/gram catalyst, be preferably 3-2000 The propylene pre-polymer of gram polymer/gram catalyst, more preferably 50-300 gram of polymer/gram catalyst；

（2）Under 91-150 DEG C, 1-6MPa, described propylene pre-polymer and propylene are polymerized.

In the present invention, described pressure refers both to gauge pressure.

Above-mentioned steps（1）And step（2）Batchwise polymerization operation can be carried out in a reactor it is also possible to different anti- Answer and in device, carry out continuous polymerization operation.For example, in an embodiment of the present invention, step（1）Vertical stirred tank is carried out continuously, And step（2）Horizontal agitated vessel is carried out continuously, i.e. carry out continuous polymerization in different reactors.Additionally, step（1） And step（2）Reaction all can carry out in the gas phase, can also carry out in the liquid phase, as well known to those skilled in the art to this.

According to the present invention, step（1）In, described prepolymerized temperature can be -10 DEG C to 50 DEG C, preferably 0-30 DEG C, More preferably 10-25 DEG C；Described prepolymerized pressure can be 0.1-100MPa, preferably 1.0-6.0MPa, more preferably 1.5-5.5MPa；Described pre-polymerization multiple can be 2-3000 gram of polymer/gram catalyst, preferably 3-2000 gram polymer/gram Catalyst, more preferably 50-300 gram polymer/gram catalyst.Wherein, described " prepolymerization multiple " refers to the weight of prepolymer Amount and the original weight ratio adding catalyst.Additionally, described prepolymerization is preferably carried out in the liquid phase, specifically may be selected to adopt third The liquid-phase bulk prepolymerization of alkene.

According to the present invention, step（2）In, the temperature of described polyreaction can be 91-150 DEG C, preferably 91-110 DEG C； The pressure of described polyreaction can be 1-6MPa, preferably 2-5MPa.The time of described polyreaction can be by needing To polyacrylic molecular size range suitably selected, for example, it is desired to obtain the larger polypropylene of molecular weight, then can extend The time of polyreaction, need to obtain the polypropylene of molecular weight, then can shorten the time of polyreaction.As a rule, The time of described polyreaction can be 0.5-4 hour, preferably 1-3 hour.Additionally, described polymerization is preferably entered in the gas phase OK.Specifically, can carry out in gas phase horizontal agitated vessel.Described gas phase horizontal agitated vessel is with horizontal type shaft, chilling Liquid removes the horizontal retort of heat, and stirring vane therein can be T-shaped, one or more of rectangle, oblique oar, gate, wedge shape etc..? In polymerization process, the speed of agitator in gas phase horizontal agitated vessel can be 10-150 rev/min.

Additionally, in step（2）In, it usually needs add molecular weight regulator（Generally hydrogen）To control poly- third obtaining The melt mass flow rate of alkene.The addition of described molecular weight regulator reasonably can be selected according to practical situation, In the present invention, the addition of described molecular weight regulator is so that the polyacrylic melt mass flow rate MFR obtaining is preferred Control and be defined in 5-10g/10min, all being known, here will not be described in great detail to this those skilled in the art.

According to the present invention, although described Ziegler-Natta catalyst can prepare polypropylene for existing various being applied to Ziegler-Natta catalyst, but so as to polypropylene there is narrower molecular weight distributing index, higher high score Son hangover index, under preferable case, described Ziegler-Natta catalyst contains solids containing titanium catalytic component and alkyl calorize Compound and selectivity contain external donor compound.

According to the present invention, described solids containing titanium catalytic component can be for example by alkoxyl magnesium compound, titanium compound The catalytic product with internal electron donor compound.

The formula of described alkoxyl magnesium compound is preferably as formula（Ⅱ）Shown：

Mg(OR¹)_2-m(OR²)_mFormula（Ⅱ）,

Formula（Ⅱ）In, R¹And R²Identical or different, and it is each independently selected from C₁-C₈Straight or branched alkyl, 0≤m≤ 2.Preferably, R¹And R²Be each independently methyl, ethyl, propyl group, isopropyl, butyl, isobutyl group, n-hexyl,（2- ethyl）Oneself Base；It is particularly preferred that R¹For ethyl, R²For (2- ethyl) hexyl.M reasonably can be selected in the range of 0-2, preferably 0.001≤m≤0.5, further preferred 0.001≤m≤0.25, more preferably 0.001≤m≤0.1.It is emphasized that formula Represented alkoxyl magnesium, illustrate only the composition content of each alkoxyl, i.e. mol ratio, and incomplete representation alkoxy magnesium is concrete Structure.Specifically, as Mg (OEt) (OiPr) only represents that in alkoxyl magnesium compound, ethyoxyl and the mol ratio of isopropoxy are 1, The mixture of the diethoxy magnesium that it both can be is 1 by mol ratio and diisopropoxy magnesium or ethyoxyl isopropyl oxygen Base magnesium compound, can also be the mixture of diethoxy magnesium, diisopropoxy magnesium and ethyoxyl isopropoxy magnesium compound, That is, it can be the mixing of the alkoxyl magnesium compound composition with isopropoxy total mole number than the various structures for 1 for the ethyoxyl Thing.Wherein, Et represents ethyl, and iPr represents isopropyl.

The present invention is not particularly limited to the profile of described alkoxyl magnesium compound, preferably spherical.Further, institute Mean diameter D50 stating spherical alkoxyl magnesium compound can be 10-150 μm, preferably 15-100 μm, more preferably 18- 80μm；Particle diameter distribution index SPAN is less than 1.1, preferably smaller than 1.05.Wherein, the computing formula of described particle diameter distribution index SPAN For：SPAN=（D90-D10）/ D50, wherein, the particle diameter that it is 90% corresponding to accumulating weight point rate that D90 represents, D10 represent corresponding to Accumulating weight point rate is 10% particle diameter, and D50 represents the particle diameter that corresponding accumulating weight point rate is 50%.

According to the present invention, micro magnesium halide in described solids containing titanium catalytic component, can also be contained（As MgI₂And/or MgCl₂）Or its alcohol adduct, but with formula（II）On the basis of the gross weight of shown alkoxyl magnesium compound and magnesium halide, formula（II） The content of shown alkoxyl magnesium compound should be higher than that 90 weight %, preferably above 95 weight %, more preferably higher than 98 weight %.

According to the present invention, described alkoxyl magnesium compound can be commercially available it is also possible to according to existing method system Standby obtain.For example, described alkoxyl magnesium compound can be by magnesium metal alcohol corresponding with alkoxyl（R¹OH and/or R²OH）With mixed Conjunction halogenating agent reacts under an inert atmosphere and prepares.Wherein, described mixing halogenating agent is the mixing of halogen and halogen compounds Thing.Described halogen can be one or more of iodine, bromine and chlorine.The not limiting example of described halogen compounds is：Chlorination Magnesium, magnesium bromide, magnesium iodide, potassium chloride, potassium bromide, potassium iodide, calcium chloride, calcium bromide, calcium iodide, mercuric chloride, mercuric bromide, iodate One or more of hydrargyrum, ethyoxyl magnesium iodide, methoxyl group magnesium iodide, isopropyl magnesium iodide, hydrogen chloride, chloracetyl chloride etc..Mixed Close the mixture that halogenating agent is particularly preferably iodine and magnesium chloride, it is further preferred that the weight of iodine and magnesium chloride ratio is for 1：0.02- 20, more preferably 1：0.1-10.

According to the present invention, in the preparation process of above-mentioned alkoxyl magnesium compound, described magnesium metal with mix in halogenating agent The molar ratio of total halogen atom is as being 1：0.0002-0.2, preferably 1：0.001-0.08.Described corresponding with alkoxyl Alcohol can be such as 4-50 with the part by weight of magnesium metal：1, preferably 6-25：1.R¹OH and R²Mol ratio Y of OH is 3 (2-g)/g> Y>(2-g)/g, wherein, 0≤g≤2, preferably 0.001≤g≤0.5, further preferred 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 for example 30-90 DEG C, preferably 30-80 DEG C, more preferably 50-75 DEG C.In practical operation, the hydrogen that can be produced by observing response Discharge stop judging that reaction terminates.

The present invention is not particularly limited to the shape of described magnesium metal, for example, it is possible to be graininess, silk ribbon shape or powder Last shape.In order that the mean diameter of the alkoxyl magnesium compound generating is maintained in suitable scope, and particle shape is excellent, institute State magnesium metal and be preferably the spherical metal magnesium that mean diameter is 10-360 μm, more preferably mean diameter is spherical for 50-300 μm Magnesium metal.In addition, the present invention has no to the surface of described magnesium metal especially limiting, but if the surface shape in described magnesium metal The envelopes such as hydrate, then can make reaction slack-off, it is therefore preferable that in the case of, the total content of activated carbon in described magnesium metal>95 Weight %, more preferably>98 weight %.

The present invention contains to the water in alcohol corresponding with alkoxyl described in the preparation process in above-mentioned alkoxyl magnesium compound Amount has no and especially limits so as to alkoxyl magnesium compound there is more excellent performance it is desirable to moisture is fewer Better, it usually needs to control water content in described alcohol corresponding with alkoxyl in below 1000ppm, be preferably controlled in 200ppm Below.

According to the present invention, described inert atmosphere is known to the skilled person, preferably blanket of nitrogen and/or argon atmospher. Additionally, the preparation of described alkoxyl magnesium compound is generally using atent solvent as reaction medium.Wherein, described atent solvent is permissible For C₆-C₁₀Alkane or aromatic hydrocarbons at least one, preferably hexane, heptane, octane, decane, benzene,toluene,xylene and its At least one in derivant etc..

According to the present invention, in the preparation process of above-mentioned alkoxyl magnesium compound, magnesium metal alcohol corresponding with alkoxyl, Mixing halogenating agent and atent solvent can disposably put into it is also possible to select to put into by several times.Putting into raw material by several times can prevent wink When produce substantial amounts of hydrogen, thus preventing the spittle due to alcohol that instantaneously substantial amounts of hydrogen produces and causes or halogenating agent, from peace From the point of view of full property angle and reaction uniformity, preferably this feed way.The number of times of segmentation can be according to the rule of reactor The consumption of mould and various material is determining.After the completion of reaction, the end product dialkoxy magnesium obtaining can also may be used with kept dry To be suspended in inert diluent used during the titanium-containing catalyst solid constituent for preparing lower step.

According to the present invention, the formula of described titanium compound is preferably as formula（Ⅲ）Shown：

Ti(OR)_4-nX_nFormula（Ⅲ）,

Formula（Ⅲ）In, R is C₁-C₁₄Aliphatic hydrocarbyl or aromatic hydrocarbyl, X be halogen atom, n be 0-4 integer.When n is 2 When following, formula（Ⅲ）Present in multiple R can be identical or different.Described halogen atom can be chlorine, bromine or iodine.Specifically, Described titanium compound can be selected from tetraalkoxy titanium, titanium tetrahalide, three alkyl groups in the halogenalkoxy titaniums, dihalo- dialkoxy titanium and single halogen three alkane At least one in epoxide titanium.More specifically, described tetraalkoxy titanium be selected from titanium tetramethoxide, purity titanium tetraethoxide, four positive third In epoxide titanium, tetraisopropoxy titanium, four titanium n-butoxide, four isobutoxy titaniums, four cyclohexyloxy titaniums and four phenoxide titaniums extremely Few one kind；Described titanium tetrahalide is selected from least one in titanium tetrachloride, titanium tetrabromide and titanium tetra iodide；Described three alkyl groups in the halogenalkoxy Titanium is selected from trichloromethoxy titanium, tri-chloroethoxy titanium, trichlorine titanium propanolate, trichlorine titanium n-butoxide and tribromo ethanolato-titanium At least one；Described dihalo- dialkoxy titanium is selected from dichloro dimethoxy titanium, dichlorodiethyl epoxide titanium, dichloro two positive propoxy At least one in titanium, dichloro diisopropoxy titanium and dibromo diethoxy titanium；Described single halogen tri-alkoxy titanium is selected from a chlorine three At least one in methoxyl group titanium, a chlorine triethoxy titanium, a chlorine three positive propoxy titanium and a chlorine three titanium isopropoxide.Described titanium Compound is preferably titanium tetrahalide compound, particularly preferably titanium tetrachloride.

According to the present invention, described internal electron donor compound is preferably formula such as formula（Ⅳ）Shown diether compound：

Formula（Ⅳ）,

Formula（Ⅳ）In, R₁And R₂Identical or different, and it is each independently selected from C₁-C₂₀Straight chain, the aliphatic hydrocarbon of branched or ring-type Base；R₃、R₄、R₅、R₆、R₇And R₈Identical or different, and it is each independently selected from the C of hydrogen, halogen atom, straight or branched₁-C₂₀Alkane Base, C₃-C₂₀Cycloalkyl, C₆-C₂₀Aryl, C₇-C₂₀Alkaryl and C₇-C₂₀Aralkyl；Optionally, R₃-R₈Group between can be bonded into Ring.Preferably, R₁And R₂Identical or different, and it is each independently selected from C₁-C₆The alkyl of straight or branched；R₅、R₆Identical or not With, and it is each independently selected from C₁-C₁₀The alkyl of straight or branched, C₃-C₁₀Cycloalkyl.

The instantiation of described internal electron donor compound can include but is not limited to：2- isopropyl -2- isopentyl -1,3- Dimethoxy propane, 9,9- bis-（Methoxy）Fluorenes, 2- isobutyl group -2- isopropyl -1,3- dimethoxy propane, 2,2- bicyclo- Dicyclopentyldimetoxy propane, 2,2- diphenyl -1,3- dimethoxy propane, 2- isobutyl group -2- isopropyl -1,3- dimethoxy third One of alkane, 2,2- bicyclopentyl -1,3- dimethoxy propane, 2,2- diisobutyl -1,3- dimethoxy propane etc. or many Kind.

According to the present invention, in the preparation process of described solids containing titanium catalytic component, titanium in described titanium compound with The mol ratio of the magnesium in alkoxyl magnesium compound can be 0.5-100：1；It is preferably 1-50：1.Described internal electron donor compound Mol ratio with magnesium in alkoxyl magnesium compound can be 0.005-10：1；It is preferably 0.01-1：1.

According to the present invention, the preparation process of described solids containing titanium catalytic component is generally situated between using atent solvent as reaction Matter.Wherein, described atent solvent can be selected from C₆-C₁₀Alkane or aromatic hydrocarbons at least one, preferably hexane, heptane, pungent At least one in alkane, decane, benzene,toluene,xylene or derivatives thereof etc., most preferably toluene.Described atent solvent and alkane The molar ratio of the magnesium in epoxide magnesium compound is as being 0.5-100：1, preferably 1-50：1.

According to the present invention, in the preparation process of described solids containing titanium catalytic component, described alkoxyl magnesium compound, titanium The addition sequence of compound, internal electron donor compound and atent solvent is not particularly limited, for example, it is possible in atent solvent In the presence of make above-mentioned each component mix homogeneously it is also possible in advance with atent solvent dilute each composition, then again will be respective molten Liquid mix homogeneously.Number of times for mixing is also not particularly limited, can be with mixed once it is also possible to mix several times.Specifically Ground, can prepare solids containing titanium catalytic component according to following several method：

Method one：

1st, alkoxyl magnesium carrier compound, internal electron donor and atent solvent are configured to suspension, then with a part Titanium compound and the mixture reaction of atent solvent formation, filter, obtain solid product；2nd, the solid product obtaining is added separately Continue reaction in the mixture of a part of titanium compound and atent solvent, filter, obtain solid product；3rd, repeat the 2nd step reaction 2-4 time；4th, wash, with atent solvent, the solid product finally obtaining, obtain solids containing titanium catalytic component.Wherein, preparation process In, the amount of the described titanium compound adding every time can carry out reasonable selection according to the number of times repeating to react, for example, it is possible to be 1/ N, n are the number of times+2 repeating the 2nd step.

Method two：

1st, alkoxyl magnesium carrier compound, a part of internal electron donor and atent solvent are configured to suspension, Ran Houyu A part of titanium compound and the mixture reaction of atent solvent formation, filter, obtain solid product；2nd, by the solid product obtaining Add in the mixture being formed by the internal electron donor of the titanium compound, atent solvent and remainder of another part and continue instead Should, filter, obtain solid product；3rd, gained solid product continuously adds the mixing of the titanium compound of a part and atent solvent again Continue reaction in thing, filter, obtain solid product；4th, repeat the 3rd step to react 2-4 time；5th, washed for the last time with atent solvent The solid product obtaining, obtains solids containing titanium catalytic component.Wherein, in preparation process, the described titanium compound of addition every time Amount can according to repeat react number of times carry out reasonable selection, for example, it is possible to be 1/n, n be repeat the 3rd step number of times+3.

Method three：

1st, alkoxyl magnesium carrier compound and atent solvent are configured to suspension, then with a part of titanium compound and lazy Property solvent formed mixture reaction, add internal electron donor compound, continue reaction, filter, obtain solid product；2nd, incite somebody to action To solid product add in the mixture that another part titanium compound and atent solvent formed and continue reaction, filter, consolidate Body product；3rd, repeat the 2nd step to react 2-4 time；4th, wash, with atent solvent, the solid product finally obtaining, obtain solids containing titanium and urge Agent component.Wherein, in preparation process, the amount of the described titanium compound adding every time can be carried out according to the number of times repeating to react Reasonable selection, for example, it is possible to be 1/n, n is the number of times+2 repeating the 2nd step.

Method four：

1st, alkoxyl magnesium carrier compound, a part of internal electron donor and atent solvent are configured to suspension, Ran Houyu A part of titanium compound and the mixture reaction of atent solvent formation, add the internal electron donor compound of remainder, continue Continuous reaction, filters, obtains solid product；2nd, the solid product obtaining is added by another part titanium compound and atent solvent shape Continue reaction in the mixture becoming, filter, obtain solid product；3rd, repeat the 2nd step to react 2-4 time；4th, washed with atent solvent The solid product finally obtaining, obtains solids containing titanium catalytic component.Wherein, in preparation process, the described titanizing of addition every time The amount of compound can according to repeat react number of times carry out reasonable selection, for example, it is possible to be 1/n, n be repeat the 2nd step number of times+ 2.

According to the present invention, in the preparation process of described catalyst solid constituent, the atent solvent of washing is preferably oneself Alkane.The present invention is not particularly limited for the method for washing, it is preferred to use the mode such as decantation, filtration is carried out.Atent solvent Usage amount, wash time, washing times are not particularly limited, for example, with respect in 1 mole of described alkoxyl magnesium compound Magnesium, the consumption for the atent solvent of washing for example can be 1-1000 mole, preferably 10-500 mole.Described washing when Between can be for example 1-24 hour, preferably 6-10 hour.Additionally, from the angle of washing homogeneity and detersive efficiency, institute State washing preferably to carry out under agitation.

According to the present invention, in the preparation process of described solids containing titanium catalytic component, by alkoxyl magnesium compound, titanizing Compound, internal electron donor compound and the catalytic condition of atent solvent generally include：Reaction temperature can for -40 DEG C extremely 200 DEG C, preferably -20 DEG C to 150 DEG C；Response time can be 1 minute -20 hours, preferably 5 minutes -8 hours.

According to the present invention, the alkyl aluminum compound in described Ziegler-Natta catalyst for example can be as formula（Ⅴ）Institute Show：

AlR′_pX_3-pFormula（Ⅴ）,

Formula（Ⅴ）In, R ' is hydrogen or C₁-C₂₀Alkyl, X be halogen, p be 1-3 integer.Specifically, described alkyl calorize The example of compound can include but is not limited to：Triethyl aluminum, tri-propyl aluminum, three n-butylaluminum, triisobutyl aluminium, three n-octyls Aluminum, a hydrogen diethyl aluminum, a hydrogen diisobutyl aluminum, aluminium diethyl monochloride, a chloro-di-isobutyl aluminum, sesquialter ethylmercury chloride aluminum and two One or more of chloroethyl aluminum, preferably triethyl aluminum and/or triisobutyl aluminium.

According to the present invention, in described Ziegler-Natta catalyst, described external electron donor can optionally add Enter.It was found by the inventors of the present invention that the content of xylene soluble part in polypropylene after addition external electron donor, can be reduced.

Described external donor compound can be the conventional selection of this area, preferably formula such as formula（Ⅰ）Shown has Organic silicon compound：

R^1″ _m″R^2″ _n″Si(OR^3″)_4-m″-n″Formula（Ⅰ）,

Formula（Ⅰ）In, R^1″And R^2″Identical or different, and it is each independently halogen, hydrogen atom, C₁-C₂₀Alkyl, C₃-C₂₀ Cycloalkyl, C₆-C₂₀Aryl or C₁-C₂₀Haloalkyl；R^3″For C₁-C₂₀Alkyl, C₃-C₂₀Cycloalkyl, C₆-C₂₀Virtue Base or C₁-C₂₀Haloalkyl；M " and n " is each independently the integer of 0-3, and m "+n "<4.Described organo-silicon compound Specific example can include but is not limited to：Trimethylmethoxysilane, diisopropyl dimethoxy silane, diisobutyl dimethoxy Base silane, isopropyl butyldimethoxysilane, di-t-butyl dimethoxysilane, tertbutyl methyl dimethoxysilane, T-butylethyl dimethoxysilane, tert-butyl group propyldimethoxy-silane, ter /-butylisopropyl dimethoxysilane, cyclohexyl Methyl dimethoxysilane, Dicyclohexyldimethoxysilane, cyclohexyl-t-butyldimethoxysilane, cyclopentyl-methyl two Methoxy silane, cyclopentyl ethyl dimethoxysilane, dicyclopentyl dimethoxyl silane, cyclopentyl cyclohexyl dimethoxy silicon Alkane, double（2- methylcyclopentyl）Dimethoxysilane, dimethoxydiphenylsilane, diphenyl diethoxy silane, phenyl three Ethoxysilane, MTMS, MTES, ethyl trimethoxy silane, propyl trimethoxy silicon Alkane, propyl-triethoxysilicane, isopropyltri-methoxysilane, isopro-pyltriethoxysilane, butyl trimethoxy silane, fourth Ethyl triethoxy silicane alkane, trimethoxysilane, isobutyl triethoxy silane, amyltrimethoxysilane, isopentyl Trimethoxy silane, cyclopentyl-trimethoxy-silane, cyclohexyl trimethoxy silane, dimethoxydiphenylsilane, diphenyl Diethoxy silane, phenyltrimethoxysila,e, phenyl triethoxysilane, n-pro-pyl trimethoxy silane, vinyl front three TMOS, VTES, tetramethoxy-silicane, tetraethoxysilane, four butoxy silanes etc..These are organic Silicon compound can be individually using it is also possible to be applied in combination two or more.Preferably, described organosilicon compound Thing is selected from dicyclopentyl dimethoxyl silane, diisopropyl dimethoxy silane, second, isobutyl dimethoxy silane, cyclohexyl first Base dimethoxysilane, dimethoxydiphenylsilane, methyl-t-butyldimethoxysilane, tetraethoxysilane, propyl group three One or more of Ethoxysilane and isobutyl triethoxy silane.

According to the present invention, in the preparation process of described Ziegler-Natta catalyst, in described alkyl aluminum compound The molar ratio of the titanium in aluminum and described solids containing titanium catalytic component is as being 20-500：1；It is preferably 50-500：1；More It is preferably 50-100：1.The molar ratio of the silicon of the aluminum in described alkyl aluminum compound and described external donor compound such as can Think 0.1-500：1, preferably 1-200：1, more preferably 3-100：1.

According to the present invention, described kink auxiliary agent is the Petropols of not polar functionalities.Described Petropols refer to oil The aggregated resin-like thing obtaining of the mixture such as the alkene of fraction, alkadienes, cycloolefins, styrene derivative and heterocyclic compound Matter.Under preferable case, described Petropols are the C in petroleum cracking side-product₅Fraction and/or C₉Fraction through pre-treatment, polymerization, A kind of thermoplastic resin of the technique productions such as distillation, its softening point is 100-150 DEG C.Wherein, softening point refers to what material softened Temperature, i.e. Petropols start temperature during deliquescing.Petropols after carrying out hydrotreating, can make its color from yellow to Light yellow become colorless, therefore preferably C₅And/or C₉Hydrogenated petroleum resin, most preferably Cyclopeutadiene type resin or with it Resin as the higher alkene of key component.Described Petropols can be commercially available, for example, it is possible to be purchased from The C of Exxonmobil company₅Petropols and/or C₉Petropols.

According to the present invention, according to actually used needs, described polypropene composition can also contain other auxiliary agents.Described Other auxiliary agents can be for example antioxidant, halogen-resistant agent, light stabilizer, heat stabilizer, coloring agent, filler, slipping agent, anti-stick At least one in agent, antistatic additive etc..Additionally, on the basis of the described polypropylene of 100 weight portions, the use of described other auxiliary agent Amount can be 0.05-0.3 weight portion, preferably 0.15-0.25 weight portion.

The present invention provide polypropylene knotting packaging film mainly the improvement is that employ containing specific polypropylene, The polypropene composition of auxiliary agent that kink auxiliary agent and selectivity contain as raw materials for production, and concrete preparation process can with existing There is technology identical.

Specifically, by each component in described polypropene composition in high speed agitator mix homogeneously, and will mix all Material after even adds melting mixing in double screw extruder uniform and extruding pelletization, dries.Processing temperature is maintained at 170-230 Between DEG C, finally obtain polypropene composition pellet.Above-mentioned polypropene composition pellet is added in extruder, controls extrusion Casting temperature is 170-230 DEG C, and curtain coating roll temperature is 10-50 DEG C, and material, after extruding dies outflow, passes sequentially through curtain coating Roller, carry-over pinch rolls, then through cutting edge and winding, obtain polypropylene knotting packaging film.

Additionally, described polypropene composition can be not only used for preparing the cast film of monolayer, can be also used for preparation many Layer cast film, single or multiple lift biaxially oriented film.At least one of which in multi-layer compound film contains described Polypropylene compositions Thing, and other layer raw material can be HOPP, ethylene-propylene copolymer, propylene and other alpha olefin copolymers etc., here will no longer Repeat.

Hereinafter will be described the present invention by embodiment.

In following examples and comparative example, propylene and hydrogen are polymer grade, through dehydration, deoxidation treatment.

In following examples and comparative example：

1st, molecular weight distributing index Mw/Mn, peak molecular weight Mp, weight average molecular weight Mw and Z-average molecular weight Mz adopt Britain The chromatograph of gel permeation of model PL-GPC220 that Polymer Laboratories company produces combines the infrared inspection of IR5 type Survey device to measure, wherein, the chromatographic column in chromatograph of gel permeation is Plgel10 μm of MIXED-B post, solvent and the stream of 3 series connection Move and be mutually 1,2,4- trichloro-benzenes（Antioxidant DBPC 2,6 ditertiary butyl p cresol containing 0.3g/1000mL）, column temperature be 150 DEG C, stream Speed is 1.0mL/min, produces EasiCal PS-1 Narrow distribution polystyrene standard specimen using PL company and carries out universal calibration.

Macromolecule hangover indices P I_HTAccording to the following formula（1）It is calculated：

PI_HT=10⁵×(Mz/Mp)/Mw （1）.

2nd, the assay of isotaxy five unit group [mmmm]：

Due to¹³In C-NMR spectrum, the methyl carbon area for 19.5-22.5ppm for the chemical shift can provide resolution higher Stereoregular information, obtains triad isotactic, an isotactic-rule, the content of an a rule-rule, therefore, using the measurement knot in this area Really and according to formula（2）Calculate the content of isotaxy five unit group [mmmm]：

Wherein, [mm], [mr], [rr] are respectively triad isotactic, an isotactic-rule, the content of an a rule-rule.

Nuclear magnetic resonance chemical analyser using the model AVANCE III of Bruker company of Switzerland（NMR）Measure under 400MHz Polyacrylic nuclear-magnetism carbon spectrum（¹³C-NMR）, wherein, solvent is deuterated o-dichlorohenzene, and sample concentration is that 250mg sample/2.5mL is molten Agent.For preventing sample oxidative degradation in dissolving and data acquisition, add 2, the 6- di-t-butyl -4- of 2mg in the sample Methylphenol antioxidant（Abbreviation BHT）.140 DEG C of dissolved samples, collection¹³C-NMR, 125 DEG C of test temperature, detecting head specification 10 milli Rice, 90 ° of pulses, sampling time AQ is 5 seconds, and time delay, D1 was 1 second, scanning times 6000 times.Spectral peak is assert referring in particular to ginseng Examine document：（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.

3rd, the mensure of the position heterogeneous structure content that propylene 2,1 inserts and 1,3 insertions are caused：

Pass through¹³C-NMR analyzes and calculates the content that " 2,1 " insertion and " 1,3 " are inserted according to the following formula：

α α, α β, α δ represent the locus of three kinds of different carbon atoms that different inserted modes lead to, and carbon atom is α α position When represent that inserted mode is normal " head-tail " mode, carbon atom is that carbon atom is to be during α δ position for " 2,1 " insertion during α β position " 1,3 " insert.

¹³The experimental condition of C-NMR is identical with 2, and the identification data of spectral peak is processed referring in particular to list of references：（1） Grassi A, Zambelli A.Macromolecules, 1988,21：617-622；（2）Tsutsui T, Ishimaru N, Mizuno A, et al.Polymer, 1989,30：1350-1356.

4th, the mensure of TREF analytical type solubles content：TREF-300 type analysis instrument using Poly CHAR company is carried out Measure, concrete grammar is as follows：Weigh the trichloro-benzenes added with 0.3 weight %BHT for the 80mg sample 40mL（TCB）Solvent is at 150 DEG C Dissolving 60min, makes sample fully dissolve formation homogeneous solution；Take the above-mentioned solution of 20mL to enter post, be cooled to 0.2 DEG C/min speed 35 DEG C, make sample gradually crystallize precipitation according to crystallizing power size in temperature-fall period and be deposited on post；Stable at 35 DEG C It is warming up to 140 DEG C with 1.0 DEG C/min again after 10min and carry out drip washing.The flow velocity controlling solvent pump in drip washing is 0.5mL/min, molten Solution sample constantly is drenched by solvent, and the pouring of record sample goes out the relation of thing and temperature.It is designated as drenching thing percentage composition at 35 DEG C TREF analytical type solubles content.

5th, the mensure of crystallization temperature Tc：It is measured using DIAMOND type DSC that PE company produces, wherein, with indium metal With zinc standard specimen, instrument is corrected, sample quality is about 5mg, atmosphere is nitrogen, throughput is 20mL/min.By sample with 10 DEG C/then the ramp of min be cooled to 50 with the speed of 10 DEG C/min to 210 DEG C and constant temperature 5min to eliminate thermal history again DEG C, record crystallization exotherm, corresponding for the peak value of crystallization exotherm temperature is designated as crystallization temperature Tc.

6th, xylene soluble content is measured according to method specified in ASTM D5492-98.

7th, melt mass flow rate MFR is measured according to method specified in ISO1133, and wherein, test temperature is 230 DEG C, load is 2.16kg.

8th, the titanium atom content in solids containing titanium catalytic component and Ziegler-Natta catalyst is using purchased from An He alliance 721 spectrophotometers of (Tianjin) development in science and technology company limited are measured.Alkoxyl magnesium compound and Ziegler-Natta urge The particle diameter of agent and particle diameter distribution index are surveyed using Malvern Mastersizer TM 2000 laser particle analyzer Fixed, wherein, using normal hexane as dispersant, particle diameter distribution index SPAN=（D90-D10）/D50.In alkoxyl magnesium compound M value mensure：Take 0.1 gram of alkoxyl magnesium compound, addition 10mL concentration is 1.2mol/L aqueous hydrochloric acid solution, shakes 24 hours It is made to decompose, using gas chromatograph（Purchased from Alan Analytical Instrument Co., Ltd, model GC-7960）To ethanol therein and 2-Ethylhexyl Alcohol content is measured and is calculated as follows m value：

Wherein, w1 is 2-Ethylhexyl Alcohol quality, and w2 is ethanol quality.

In Ziegler-Natta catalyst, the content of internal electron donor is surveyed using Waters600E chromatograph of liquid Fixed.

9th, heat distortion temperature is according to ASTM D648-2007 standard testing.

10th, the mechanical property of polypropylene knotting packaging film is tested according to GB/T1040.3-2006.

11st, the test of polypropylene knotting packaging film kink angle：Cut the polypropylene knotting packaging film of one piece of 10 × 10cm, Wrap into confection, with handss, candy paper end is twisted together 360 ° in transverse direction, remaining angle after observation resilience.

12nd, the mist degree of polypropylene knotting packaging film is tested according to method specified in GB/T2410.

13rd, the glossiness of polypropylene knotting packaging film is tested according to method specified in ASTMD2457-08.

Embodiment 1

This embodiment is used for polypropene composition and polypropylene knotting packaging film and its preparation side that the present invention provides is described Method.

（1）Polyacrylic preparation：

A, the preparation of solids containing titanium catalytic component：It is sufficiently displaced from after the 16L voltage-resistant reactor with agitator with nitrogen, Then add 10L ethanol, the 2-Ethylhexyl Alcohol of 300mL, 11.2g iodine, 8g magnesium chloride and 640g magnesium powder toward in reactor and stir Mix homogeneously, makes system be warming up to 75 DEG C of back flow reaction while stirring, stopped reaction till no longer having hydrogen to discharge. By the product obtaining 3L washing with alcohol, filtration, it is dried, obtains dialkoxy magnesium, its mean diameter D50 is 30.2 μm, Particle diameter distribution index SPAN is 0.81, m is 0.015.Take 650g above-mentioned dialkoxy magnesium, 3250mL toluene, the 2- isopropyl of 65mL Base -2- isopentyl -1,3- dimethoxy propane is configured to suspension.In the pressure reaction of 16L repeating to replace through high pure nitrogen In kettle, add 2600mL toluene and 3900mL titanium tetrachloride, be warming up to 80 DEG C, then the suspension preparing is added in kettle, Constant temperature 1 hour at 80 DEG C, adds 2- isopropyl -2- isopentyl -1 of 65mL, 3- dimethoxy propane, is to slowly warm up to 110 DEG C, then constant temperature 2 hours, filter pressing, obtain solid product.Above-mentioned solid product is added 5070mL toluene and 3380mL titanium tetrachloride Mixed liquor in, and in 110 DEG C of stir process 1 hour, so repeat to process 3 times, filter pressing, and will the solid product that obtain with oneself Alkane（Through processed）Washing 4 times, each consumption is 600mL, and filter pressing, drying obtain final product solids containing titanium catalytic component.Its In, the content of titanium atom is 4.1 weight %, 2- isopropyl -2- isopentyl -1, and the content of 3- dimethoxy propane is 11.9 weights Amount %.

B, assay device：

Device adopts continuous autoclave pre-polymerization and horizontal retort gas phase series polymerizations technique.Prepolymerization reactor cools down for jacketed Vertical mixing, volume is 5 liters, and stirrer paddle is the oblique oar of turbine type, and mixing speed is 500 revs/min；Horizontal Gas-phase reactor For Horizontal stirring, volume is 0.2 cubic metre, and stirring paddle is T-shaped oblique blade, and angle of inclination is 10 degree, and mixing speed is 100 Rev/min.

C, experimental condition：

The（1）Step prepolymerization：Reaction pressure is 2.5MPa, and reaction temperature is 10 DEG C, and the response time is 12 minutes；Titaniferous is solid Body catalyst component and triethyl aluminum inlet amount are respectively 0.4g/ hour and 0.058 mol/hr, and propylene feed amount is 10 public affairs Jin/hour, obtains the propylene pre-polymer that pre-polymerization multiple is 100 grams of polymer/gram catalyst；

The（2）Step gas-phase polymerization：Reaction temperature is 98 DEG C, and reaction pressure is 2.3MPa, and the response time is 60 minutes, will walk Suddenly（1）The propylene pre-polymer obtaining continuously is passed through in Horizontal stirring, controls the inlet amount of propylene to be 30 kgs/hour simultaneously, And make hydrogen/propylene molar ratio in reaction gas phase be 0.001.

Carry out 48 hours long run tests, device stable operation according to above-mentioned condition, the polypropylene obtaining has been analyzed Test, acquired results are as shown in table 1.

（2）The preparation of polypropene composition：

Will be by step（1）Prepared polypropylene, kink auxiliary agent and antioxidant（Concrete species and consumption are as shown in table 2, its In, described kink auxiliary agent is the C purchased from Exxonmobil company₅Petropols）Add mix homogeneously in agitator, then will mix Good material adds in the feeder of WP25 double screw extruder, and material enters in twin screw via feeder, through screw rod melting Mix homogeneously, extruding pelletization, dry, in the course of processing, the temperature control of screw rod, between 170-230 DEG C, obtains Polypropylene compositions Thing pellet.

（3）The preparation of polypropylene knotting packaging film：

By step（2）It is dried in the polypropene composition pellet addition hot-air oven obtaining, and will be dried poly- The addition of propylene compositions pellet is squeezed purchased from carrying out melting in the curtain coating extrusion equipment of model LCR400 of Labtech company of Sweden Go out, then through casting roller flow casting molding, each zone temperatures of extruder control respectively 220 DEG C, 240 DEG C, 240 DEG C, 240 DEG C, 240 DEG C, at 240 DEG C, head temperature controls at 240 DEG C draping area temperature control, and casting roller temperature control, at 25 DEG C, forms averagely thick Spend the polypropylene knotting packaging film for 25 microns, its performance is as shown in table 3.

Embodiment 2

（1）Polyacrylic preparation：

A, the preparation of solids containing titanium catalytic component：（With embodiment 1）；

B, assay device：（With embodiment 1）；

C, experimental condition：

The（2）Step gas-phase polymerization：Reaction temperature is 91 DEG C, and reaction pressure is 2.3MPa, and the response time is 60 minutes, will walk Suddenly（1）The propylene pre-polymer obtaining continuously is passed through in Horizontal stirring, controls the inlet amount of propylene to be 30 kgs/hour simultaneously, And make hydrogen/propylene molar ratio in reaction gas phase be 0.001.

（2）Prepared by polypropene composition：

Will be by step（1）Prepared polypropylene, kink auxiliary agent and antioxidant（Concrete species and consumption are as shown in table 2, its In, described kink auxiliary agent is the C purchased from Exxonmobil company₉Petropols）Add mix homogeneously in agitator, then will mix Good material adds in the feeder of WP25 double screw extruder, and material enters in twin screw via feeder, through screw rod melting Mix homogeneously, extruding pelletization, dry, in the course of processing, the temperature control of screw rod, between 170-230 DEG C, obtains Polypropylene compositions Thing pellet.

（3）The preparation of polypropylene knotting packaging film：

By step（2）It is dried in the polypropene composition pellet addition hot-air oven obtaining, and will be dried poly- The addition of propylene compositions pellet is squeezed purchased from carrying out melting in the curtain coating extrusion equipment of model LCR400 of Labtech company of Sweden Go out, then through casting roller flow casting molding, each zone temperatures of extruder control respectively 210 DEG C, 230 DEG C, 230 DEG C, 230 DEG C, 230 DEG C, at 230 DEG C, head temperature controls at 230 DEG C draping area temperature control, and casting roller temperature control, at 25 DEG C, forms averagely thick Spend the polypropylene knotting packaging film for 25 microns, its performance is as shown in table 3.

Embodiment 3

（1）Polyacrylic preparation：

B, assay device：（With embodiment 1）；

C, experimental condition：

The（1）Step prepolymerization：Reaction pressure is 2.5MPa, and reaction temperature is 10 DEG C, and the response time is 12 minutes；Titaniferous is solid Body catalyst component, triethyl aluminum and dicyclopentyl dimethoxyl silane（DCPDMS, is 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, and propylene feed amount is 10 public affairs Jin/hour, obtains the propylene pre-polymer that pre-polymerization multiple is 150 grams of polymer/gram catalyst；

The（2）Step gas-phase polymerization：Reaction temperature is 98 DEG C, and reaction pressure is 2.3MPa, and the response time is 60 minutes, will walk Suddenly（1）The propylene pre-polymer obtaining continuously is passed through in Horizontal stirring, controls the inlet amount of propylene to be 30 kgs/hour simultaneously, And make hydrogen/propylene molar ratio in reaction gas phase be 0.002.

（2）The preparation of polypropene composition：

With embodiment 1, except for the difference that, described polypropylene is with by step（1）The polypropylene obtaining substitutes, and obtains polypropylene group Compound pellet.

（3）The preparation of polypropylene knotting packaging film：

By step（2）It is dried in the polypropene composition pellet addition hot-air oven obtaining, and will be dried poly- The addition of propylene compositions pellet is squeezed purchased from carrying out melting in the curtain coating extrusion equipment of model LCR400 of Labtech company of Sweden Go out, and through casting roller flow casting molding, each zone temperatures of extruder control respectively 190 DEG C, 210 DEG C, 220 DEG C, 220 DEG C, 220 DEG C, at 220 DEG C, head temperature controls at 220 DEG C draping area temperature control, and casting roller temperature control, at 25 DEG C, forms averagely thick Spend the polypropylene knotting packaging film for 25 microns, its performance is as shown in table 3.

Embodiment 4

（1）Polyacrylic preparation：

B, assay device：（With embodiment 1）；

C, experimental condition：

The（1）Step prepolymerization：Reaction pressure is 2.5MPa, and reaction temperature is 10 DEG C, and the response time is 12 minutes；Titaniferous is solid Body catalyst component, triethyl aluminum and second, isobutyl dimethoxy silane（DIBDMS, is 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, and propylene feed amount is 10 public affairs Jin/hour, obtains the propylene pre-polymer that pre-polymerization multiple is 200 grams of polymer/gram catalyst；

The（2）Step gas-phase polymerization：Reaction temperature is 91 DEG C, and reaction pressure is 2.3MPa, and the response time is 60 minutes, will walk Suddenly（1）The propylene pre-polymer obtaining continuously is passed through in Horizontal stirring, controls the inlet amount of propylene to be 30 kgs/hour simultaneously, And make hydrogen/propylene molar ratio in reaction gas phase be 0.003.

（2）Prepared by polypropene composition：

（3）The preparation of polypropylene knotting packaging film：

By step（2）It is dried in the polypropene composition pellet addition hot-air oven obtaining, and will be dried poly- The addition of propylene compositions pellet is squeezed purchased from carrying out melting in the curtain coating extrusion equipment of model LCR400 of Labtech company of Sweden Go out, then through casting roller flow casting molding, each zone temperatures of extruder control respectively 190 DEG C, 210 DEG C, 220 DEG C, 220 DEG C, 220 DEG C, at 220 DEG C, head temperature controls at 220 DEG C draping area temperature control, and casting roller temperature control, at 25 DEG C, forms averagely thick Spend the polypropylene knotting packaging film for 25 microns, its performance is as shown in table 3.

Comparative example 1

This comparative example is used for polypropene composition and polypropylene knotting packaging film of reference and preparation method thereof are described.

Method according to embodiment 1 carries out the preparation of polypropylene, polypropene composition and polypropylene knotting packaging film, no With, in described polyacrylic preparation process, the（2）The reaction temperature of step is 66 DEG C, and make in reaction gas phase hydrogen with The mol ratio of propylene is 0.004, obtains reference polypropylene, reference polypropylene compositionss and reference polypropylene knotting packaging film.Its In, as shown in table 1, the composition of reference polypropylene compositionss and consumption are as shown in table 2, reference polypropylene for the performance of reference polypropylene The performance of knotting packaging film is as shown in table 3.

Comparative example 2

Method according to embodiment 3 carries out the preparation of polypropylene, polypropene composition and polypropylene knotting packaging film, no With, in described polyacrylic preparation process, the（2）The reaction temperature of step is 66 DEG C, and make in reaction gas phase hydrogen with The mol ratio of propylene is 0.01, obtains reference polypropylene, reference polypropylene compositionss and reference polypropylene knotting packaging film.Its In, as shown in table 1, the composition of reference polypropylene compositionss and consumption are as shown in table 2, reference polypropylene for the performance of reference polypropylene The performance of knotting packaging film is as shown in table 3.

Comparative example 3

（1）Polyacrylic preparation：

B, assay device：（With embodiment 1）；

C, experimental condition：

Polypropylene, without prepolymerization, is added directly in horizontal agitated vessel.Polymeric reaction temperature is 98 DEG C, reaction pressure For 2.3MPa, the response time is 60 minutes, solids containing titanium catalytic component and triethyl aluminum inlet amount be 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 0.005.

Carried out 48 hours long run tests according to above-mentioned condition, it was found that polymer active too low it is impossible to obtain poly- third Alkene, acquired results are as shown in table 1.

（2）Prepared by polypropene composition：Cannot prepare.

（3）The preparation of polypropylene knotting packaging film：Cannot prepare.

Comparative example 4

Method according to embodiment 4 carries out the preparation of polypropylene, polypropene composition and polypropylene knotting packaging film, no With polypropylene is the polypropylene of FC801 using the trade mark producing purchased from oil of SPC（Molecular weight distributing index is 7.7, high Molecule hangover index is 1.81）Substitute, obtain reference polypropylene, reference polypropylene compositionss and reference polypropylene kink packaging Film.Wherein, as shown in table 1, the composition of reference polypropylene compositionss and consumption are as shown in table 2, reference for the performance of reference polypropylene The performance of polypropylene knotting packaging film is as shown in table 3.

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	No	No	D Donor	B Donor	No	D Donor	No	--
Pre-polymerization temperature, DEG C	10	10	10	10	10	10	Not pre-polymerization	--
									The pre-polymerization time, min	12	12	12	12	12	12	-	--
Polymerization temperature, DEG C	98	91	98	91	66	66	98	--
									Hydrogen/propylene molar ratio in Gas-phase reactor	0.001	0.001	0.002	0.003	0.004	0.01	0.005	--
Polymerization activity, KgPP/gCat.h	33	45	28	35	50	40	3.0	--
									Mw, 10⁴g/mol	33.7	32.0	31.5	30.3	31.8	31.2	-	31.9
Molecular weight distributing index Mw/Mn	4.3	4.8	4.6	4.5	6.3	6.7	-	7.7
									PI_HT	2.95	2.93	2.9	3.01	2.68	2.77	-	1.81
Isotaxy five unit group [mmmm] %	93.6	93.8	94.4	95.0	93.0	92.3	-	93.2
									Propylene 2,1 inserts and/or 1,3 contents inserted	0	0	0	0	0	0	-	0
Solubles content（TREF analytical type）, wt%	2.55	2.05	1.50	1.39	3.41	2.38	-	2.85
									Xylene soluble content, wt%	2.09	1.83	1.56	1.43	3.76	2.55	-	2.31
Melt mass flow rate, g/10min	5.2	7.6	8.1	9.6	7.8	8.8	-	8.3
									Tc, DEG C	118.2	120.2	121.8	122.4	116.0	116.6	-	115.2

Table 2

Table 3

As can be seen from the above results, when the content of Petropols is when below 10 weight portions it becomes possible to make obtain to gather The longitudinal tensile of propylene knotting packaging film reaches more than 1.62GPa, and cross directional stretch modulus reaches more than 1.54GPa, longitudinally Tensile strength reaches more than 35.3MPa, and transverse tensile strength reaches more than 35.0MPa, and kink angle is maintained at more than 300 °.By This can be seen that present invention offer polyacrylic molecular weight distributing index is narrower and macromolecule hangover index is larger, such energy The polypropene composition obtaining enough is made just not only to have higher stretch moduluses under relatively low Petropols consumption and stretch strong Degree（That is, there is preferable rigidity and deflection）, also there is preferable kink property.

Additionally, can be seen that in the same torsion of addition with comparative example 1, embodiment 3 and the contrast of comparative example 2 from embodiment 1 After knot auxiliary agent and antioxidant, the polyacrylic knotting packaging film providing containing the present invention has more preferable mechanical property, kink property Energy and optical property.Can be seen that from the contrast of embodiment 4 and comparative example 4 and adding same kink auxiliary agent and antioxidant Afterwards, the polyacrylic knotting packaging film providing containing the present invention has preferably than containing commercially available polyacrylic knotting packaging film Combination property, i.e. the polypropylene of the present invention is particularly suited for preparing knotting packaging film.

The preferred embodiment of the present invention described in detail above, but, the present invention is not limited in above-mentioned embodiment Detail, in the range of the technology design of the present invention, multiple simple variant can be carried out to technical scheme, this A little simple variant belong to protection scope of the present invention.

It is further to note that each particular technique feature described in above-mentioned specific embodiment, in not lance In the case of shield, can be combined by any suitable means.In order to avoid unnecessary repetition, the present invention to various can The compound mode of energy no longer separately illustrates.

Additionally, combination in any can also be carried out between the various different embodiment of the present invention, as long as it is without prejudice to this The thought of invention, it equally should be considered as content disclosed in this invention.

Claims

1. a kind of polypropene composition is it is characterised in that this polypropene composition contains polypropylene and kink auxiliary agent；Described poly- third The molecular weight distributing index of alkene is 2.5-5.5, macromolecule hangover indices P I in molecular weight distribution width_HTMore than 1.9；Described torsion Knot auxiliary agent is Petropols；Described macromolecule hangover indices P I_HTIt is calculated as follows：PI_HT=10⁵×(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 polypropylene is prepared by the method comprising the following steps：

(1) in the presence of Ziegler-Natta catalyst, propylene is carried out prepolymerization under -10 DEG C to 50 DEG C, 0.1-100MPa, Obtain the propylene pre-polymer that pre-polymerization multiple is 2-3000 gram of polymer/gram catalyst；

(2) under 91-150 DEG C, 1-6MPa, described propylene pre-polymer and propylene are polymerized.

2. polypropene composition according to claim 1, wherein, on the basis of the described polypropylene of 100 weight portions, described The content of kink auxiliary agent is 5-10 weight portion.

3. polypropene composition according to claim 1, wherein, described polyacrylic isotaxy five unit group [mmmm] Content be more than 85%.

4. polypropene composition according to claim 3, wherein, described polyacrylic isotaxy five unit group [mmmm] Content be more than 90%.

5. polypropene composition according to claim 4, wherein, described polyacrylic isotaxy five unit group [mmmm] Content be more than 93%.

6. polypropene composition according to claim 1, wherein, described polypropylene does not contain propylene 2,1 insertion and 1,3 and inserts Enter caused position heterogeneous structure.

7. the polypropene composition according to any one in claim 1-6, wherein, described polyacrylic crystallization temperature Tc More than 115 DEG C.

8. polypropene composition according to claim 7, wherein, described polyacrylic crystallization temperature Tc is more than 120 DEG C.

9. the polypropene composition according to any one in claim 1-6, wherein, xylene soluble in described polypropylene The content of thing is less than 4.4 weight %.

10. polypropene composition according to claim 9, wherein, in described polypropylene, the content of xylene soluble part is little In 2.3 weight %.

11. polypropene compositions according to claim 10, wherein, in described polypropylene, the content of xylene soluble part is little In 1.6 weight %.

12. polypropene compositions according to any one in claim 1-6, wherein, described polypropylene at 230 DEG C, Melt mass flow rate MFR under the effect of 2.16kg load is 5-10g/10min.

13. polypropene compositions according to claim 1, wherein, the pre-polymerization multiple of the propylene pre-polymer that step (1) obtains For 3-2000 gram of polymer/gram catalyst.

14. polypropene compositions according to claim 13, wherein, the pre-polymerization times of the propylene pre-polymer that step (1) obtains Number is 50-300 gram of polymer/gram catalyst.

15. polypropene compositions according to claim 1, wherein, described Ziegler-Natta catalyst contains solids containing titanium Catalytic component and alkyl aluminum compound and selectivity contain external donor compound.

16. polypropene compositions according to claim 15, wherein, solids containing titanium catalytic component is by alkoxyl magnesium Compound, titanium compound and the catalytic product of internal electron donor compound.

17. polypropene compositions according to claim 15, wherein, described external donor compound is formula such as formula (I) organo-silicon compound shown in：

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 it is each independently halogen, hydrogen atom, C₁-C₂₀Alkyl, C₃-C₂₀Ring Alkyl, C₆-C₂₀Aryl or C₁-C₂₀Haloalkyl；R^3”For C₁-C₂₀Alkyl, C₃-C₂₀Cycloalkyl, C₆-C₂₀Aryl or C₁-C₂₀Haloalkyl；M " and n " is each independently the integer of 0-3, and m "+n "<4.

18. polypropene compositions according to any one in claim 1-6, wherein, described Petropols are C₅And/or C₉Hydrogenated petroleum resin.

19. polypropene compositions according to claim 18, wherein, the softening point of described Petropols is 100-150 DEG C.

20. polypropene compositions according to claim 18, wherein, described Petropols are Cyclopeutadiene type resins.

The polypropylene knotting packaging film that 21. polypropene compositions described in any one in claim 1-20 are made.