CN104250395B

CN104250395B - Polypropylene composition and polypropylene flat filament and preparation method thereof

Info

Publication number: CN104250395B
Application number: CN201310269009.8A
Authority: CN
Inventors: 高达利; 张师军; 邹浩; 徐萌; 郭梅芳; 王良诗; 于鲁强; 张丽英; 邵静波; 徐凯
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: 2017-04-26
Anticipated expiration: 2033-06-28
Also published as: CN104250395A

Abstract

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

Description

A kind of polypropene composition and polypropylene flat-filament and preparation method thereof

Technical field

The present invention relates to a kind of polypropene composition, polypropylene flat-filament, Yi Zhongju by made by the polypropene composition The preparation method of propylene flat filament and the polypropylene flat-filament prepared by the method.

Background technology

The characteristics of acrylic resin is with its excellent mechanical performance, optical property and excellent light weight valency has obtained widely should With.Particularly polypropylene film, has the advantages that matter is soft, transparency is high due to it, nontoxic, good waterproof performance and high mechanical strength, Many fields such as can be used to packing, be combined, print.

It is in pancake chemical fibre monofilament that flat filament is section, is the stock for producing plastic braid.Flat filament is usual It is made up of polypropylene and/or polyvinyl resin.Wherein, the production process of polypropylene flat-filament is as follows：The tubulose of blow extrusion is thin The flat film of film or T-shaped head extrusion cuts into base silk, and again heated drawing-off carries out simple tension to base silk, finally obtains with certain The polypropylene flat-filament of intensity.The drawing-off of flat filament is the simple tension carried out below its melt temperature, and drawing process is poly- third The orientation process of alkene macromolecular chain and crystalline texture, so that flat filament obtains certain intensity and other physical and mechanical properties.Mesh Before, the polypropylene flat-filament of prior art production, draw ratio is normally controlled in 4-7 times, and stretching ratio is little, and draft temperature is higher, The degree of orientation is not enough, thus the flat filament low intensity for being produced, poor mechanical property, is simply possible to use in the purposes than lower end, such as woven bag, Tarpaulin, geotextiles etc..Improve the mechanical strength of prepared polypropylene flat-filament, it is necessary to improve polypropylene macromolecular chain in flat filament The degree of orientation, while also in time being fixed the micro-structural of orientation, it is to avoid orientation texture occurs to relax, and flat filament can just obtained High mechanical strength.And high intensity, the processing of high modulus polypropylene flat filament are realized, rational processing technology is on the one hand needed, Ensure that polypropylene flat-filament can carry out very powerful stretching, while the stretching production that also cause flat filament has as far as possible high drawing Stretch speed, it is ensured that its economy；On the other hand, the molecular structure for improving acrylic resin raw material is needed, to ensure that it is good that it has While good stretch process, the mechanical strength of flat filament can be further improved.However, existing acrylic resin had been polymerized The isotacticity and molecular weight distribution width aspect of polypropylene molecule structure can not be taken into account in journey, it is impossible to for high-strength polypropylene The production of flat filament.

The content of the invention

The invention aims to overcome the relatively low shortcoming of existing polypropylene flat-filament mechanical strength, and provide a kind of tool There are polypropene composition, polypropylene flat-filament, a kind of polypropylene by made by the polypropene composition of higher force intensity flat The preparation method of silk and the polypropylene flat-filament prepared by the method.

The invention provides a kind of polypropene composition, wherein, the polypropene composition contains polypropylene and nucleator；Institute Polyacrylic molecular weight distributing index is stated for 2.5-5.5, macromolecule hangover indices P I in molecular weight distribution width_HTMore than 1.9.

Present invention also offers one kind polypropylene flat-filament by made by the polypropene composition.

Present invention also offers a kind of preparation method of polypropylene flat-filament, the method is included the Polypropylene compositions logistics Prolong extrusion and obtain flat film, and the flat film is cut into into base silk, then the base silk is carried out into simple tension below 115 DEG C.

Additionally, a kind of present invention also offers polypropylene flat-filament prepared by said method.

The polypropylene flat-filament that polypropene composition provided by the present invention is prepared has higher mechanical strength.From reality The stretch modulus of the polypropylene flat-filament that the result for applying example can be seen that present invention offer can reach more than 8.5GPa, and stretching is disconnected Resistance to spalling can reach more than 856.7MPa.Speculate its reason, it may be possible to due to：On the one hand, the molecule of flat filament pp material Amount profile exponent is narrower, then melt polypropylene has broader newton platform area in flow process, and extrusion capacity is easily stable Control, reduces the possibility that defect occurs in base silk forming process, and is conducive to improving the crystallinity of flat filament so that flat filament Stretching it is more uniform, the flat filament degree of orientation is higher, so as to improve the mechanical property of polypropylene flat-filament, obtain intensity it is higher poly- third Alkene flat filament.Additionally, the polypropylene with narrower molecular weight distribution index and higher macromolecule hangover index can be played into preferably The effect of core agent, so as to dramatically increasing the crystal density of polypropylene flat-filament and promoting fine grain size, improves the drawing of flat filament Stretch processability and mechanical strength.On the other hand, macromolecule hangover indices P I_HTIt is higher to show exist in polypropylene more significantly greatly Strand tail end.It is theoretical according to polypropylene homogeneous nucleation, macromolecular chain tail end in crystallization can Preferential Nucleation, make polyacrylic Crystallization temperature is raised, crystallization rate is accelerated, and is conducive to improving rigidity, is shortened molding cycle and improve shaping efficiency.In a word, this The polypropylene of bright offer is good with the compatibility of filler, beneficial to the dispersed of high levels of filler, coordinates minimal amount of nucleator just The crystal property of polypropylene film can be significantly improved, so as to significantly improve the mechanical strength of film.

A preferred embodiment of the invention, when containing for the polyacrylic isotaxy five unit group [mmmm] When amount is more than 85%, enables to melt polypropylene and there is broader newton platform area in flow process such that it is able to more show Writing ground reduces the possibility that surface defect occurs in film forming procedure, and is conducive to improving the crystallinity of polypropylene flat-filament, makes The stretching for obtaining film is more uniform, and the degree of orientation is higher, so as to improve the mechanical property of polypropylene flat-filament.

A preferred embodiment of the invention, using two-stage polymerization method polypropylene is prepared, and the first step is relatively low At a temperature of carry out prepolymerization, and second step then improves the temperature of polymerisation, the polypropylene for so enabling to have compared with Narrow molecular weight distribution, higher steric regularity and larger macromolecule hangover indices P I_HT, so that polypropylene has in itself Higher crystal property and crystallization regularity so that only have a small amount of amorphous region in polypropylene, be conducive to polypropylene flat-filament power Learn the further raising of intensity.

Another kind of preferred embodiment of the invention, in the polyacrylic preparation process, when the Ziegler- Natta（Ziegler-Natta）When catalyst preferably comprises external donor compound, can not only make to obtain is polyacrylic Steric regularity is further improved, but also the content of the xylene soluble part in the polypropylene for enabling to is significantly reduced, So as to widen the application of the polypropene composition and polypropylene flat-filament.

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

Specific embodiment

The specific embodiment of the present invention is described in detail below.It should be appreciated that 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 is provided contains polypropylene and nucleator；The polyacrylic molecular weight distributing index For 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。

PI_HTIt is more high, show there is more significant macromolecular chain tail end in polypropylene.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.Stating Mp, Mw, Mz and molecular weight distributing index can pass through gel permeation chromatograph （GPC）It is measured.

The present invention is not particularly limited to the content of polypropylene and nucleator in the polypropene composition, for example, with On the basis of the polypropylene of 100 weight portions, the content of the nucleator can be 0.01-1 weight portions, preferably 0.05-0.5 Weight portion.

According to the present invention, in order that the polypropylene flat-filament prepared by the polypropene composition have it is higher strong Degree, the content of the unit group [mmmm] of the polyacrylic isotaxy five is preferably greater than 85%, further preferably greater than 90%, more excellent Choosing is more than 93%.

According to the present invention, in the polyacrylic preparation process, due to propylene monomer may occur " 2,1 " insertion and/ Or " 1,3 " inserts, the regularity for causing polypropylene molecule chain structure is destroyed, and fusing point is reduced, polyacrylic using temperature so as to affect Degree.The defect sturcture for 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, in order that the polypropylene flat-filament prepared by the polypropene composition have it is higher strong Degree, under preferable case, the polypropylene does not contain the caused position heterogeneous structure of the insertion of propylene 2,1 and 1,3 insertions.Need Bright, " not containing " mentioned here does not refer to and absolutely not contains, and refers to propylene 2, and 1 insertion and 1,3 insertion contents are very It is low, usually less than 0.01%, beyond the Monitoring lower-cut of instrument.

According to the present invention, polyacrylic crystallization temperature Tc is preferably greater than 113 DEG C, more preferably greater than 115 DEG C, such energy Crystal structure after enough making the polypropylene that obtains crystallized is more perfect, so as to improve the mechanical strength of polypropylene flat-filament.

According to the present invention, the content of xylene soluble part is preferably smaller than 4.4 weight % in the polypropylene, further preferably Less than 2.3 weight %, more preferably less than 1.6 weight %.As a rule, xylene soluble content is low, polyacrylic isotacticity compared with Height, therefore rigidity and heat resistance are preferable.Additionally, for some are applied to the polypropylene flat-filament for contacting food, medicine or solvent, Xylene soluble content is lower, then it is transportable go out or be dissolved out or the content of material that extracts is lower, more pacified using upper It is complete reliable.

According to the present invention, the polypropylene is at 230 DEG C, the melt mass flow rate MFR under the effect of 2.16kg load Preferably 2-5g/10min.In the present invention, the melt mass flow rate MFR is carried out according to method specified in ISO1133 Determine, wherein, test temperature is 230 DEG C, and load is 2.16kg.

According to the present invention, the polypropylene can be according to well known to a person skilled in the art various methods be prepared, example Such as, the polypropylene is prepared by the method for 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 for 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, the propylene pre-polymer and propylene are polymerized.

In the present invention, the 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 carry out in device continuous polymerization operation.For example, in an embodiment of the present invention, step（1）It is carried out continuously in vertical stirred tank, And step（2）It is carried out continuously in horizontal agitated vessel, i.e. continuous polymerization is carried out in different reactors.Additionally, step（1） And step（2）Reaction can in the gas phase carry out, can also carry out in the liquid phase, it is as well known to those skilled in the art to this.

According to the present invention, step（1）In, the prepolymerized temperature can be -10 DEG C to 50 DEG C, preferably 0-30 DEG C, More preferably 10-25 DEG C；The prepolymerized pressure can be 0.1-100MPa, preferably 1.0-6.0MPa, more preferably 1.5-5.5MPa；The 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 Measure the weight ratio with original addition catalyst.Additionally, the 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 the polymerisation can be 91-150 DEG C, preferably 91-110 DEG C； The pressure of the polymerisation can be 1-6MPa, preferably 2-5MPa.The time of the polymerisation 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 polymerisation, the polypropylene for obtaining molecular weight is needed, then can shorten the time of polymerisation.As a rule, The time of the polymerisation can be 0.5-4 hours, preferably 1-3 hours.Additionally, the polymerization is preferably entered in the gas phase OK.Specifically, can carry out in gas phase horizontal agitated vessel.The gas phase horizontal agitated vessel is with horizontal type shaft, chilling Liquid removes the horizontal retort of heat, and stirring vane therein can be one or more in T-shaped, 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）Poly- third obtained with control The melt mass flow rate of alkene.The addition of the molecular weight regulator can reasonably be selected according to actual conditions, In the present invention, the addition of the molecular weight regulator is so that the polyacrylic melt mass flow rate MFR for obtaining is preferred Control is defined in 2-5g/10min, can know that here will not be described in great detail to this those skilled in the art.

According to the present invention, although the Ziegler-Natta catalyst can be existing various suitable for preparing poly- third The Ziegler-Natta catalyst of alkene, but in order that to polypropylene there is narrower molecular weight distributing index, higher height Molecule hangover index, under preferable case, the Ziegler-Natta catalyst contains solids containing titanium catalytic component and alkyl aluminum Compound and selectivity contain external donor compound.

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

The formula of the alkoxyl magnesium compound is preferably such as formula（II）It is shown：

Mg(OR¹)_2-m(OR²)_mFormula（II）,

Formula（II）In, R¹And R²It is identical 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- ethyls）Oneself Base；It is particularly preferred that R¹For ethyl, R²For (2- ethyls) hexyl.M can reasonably be selected in the range of 0-2, preferably 0.001≤m≤0.5, more preferably further preferred 0.001≤m≤0.25,0.001≤m≤0.1.It is emphasized that formula Represented alkoxyl magnesium, illustrate only the composition content of each alkoxyl, i.e. mol ratio, not fully represent the concrete of alkoxyl magnesium Structure.Specifically, as Mg (OEt) (OiPr) only represents that ethyoxyl and the mol ratio of isopropoxy are 1 in alkoxyl magnesium compound, It both can be by the mixture, or ethyoxyl isopropyl oxygen of the diethoxy magnesium and diisopropoxy magnesium that mol ratio is 1 Base magnesium compound, can also be the mixture of diethoxy magnesium, diisopropoxy magnesium and ethyoxyl isopropoxy magnesium compound, That is, the alkoxyl magnesium compound group of the various structures that it can be ethyoxyl with isopropoxy total mole number ratio is 1 into mixing Thing.Wherein, Et represents ethyl, and iPr represents isopropyl.

The present invention is not particularly limited to the profile of the alkoxyl magnesium compound, preferably spherical.Further, institute Average grain diameter D50 for stating spherical alkoxyl magnesium compound can be for 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 the particle diameter distribution index SPAN For：SPAN=（D90-D10）/ D50, wherein, D90 is represented corresponding to the particle diameter that accumulating weight point rate is 90%, D10 represent corresponding to Accumulating weight point rate is 10% particle diameter, and D50 represents the particle diameter that correspondence accumulating weight point rate is 50%.

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

According to the present invention, the alkoxyl magnesium compound can be commercially available, it is also possible to according to existing method system It is standby to obtain.For example, the alkoxyl magnesium compound can be by magnesium metal alcohol (R corresponding with alkoxyl¹OH and/or R²OH it is) and mixed Conjunction halogenating agent reacts prepare under an inert atmosphere.Wherein, the mixing halogenating agent is the mixing of halogen and halogen compounds Thing.The halogen can be one or more in iodine, bromine and chlorine.The not limiting example of the halogen compounds is：Chlorination Magnesium, magnesium bromide, magnesium iodide, potassium chloride, KBr, KI, calcium chloride, calcium bromide, calcium iodide, mercury chloride, mercuric bromide, iodate One or more in mercury, ethyoxyl magnesium iodide, methoxyl group magnesium iodide, isopropyl magnesium iodide, hydrogen chloride, chloracetyl chloride etc..It is mixed The mixture that halogenating agent is particularly preferably iodine and magnesium chloride is closed, it is further preferred that the weight ratio of iodine and magnesium chloride is 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, the magnesium metal with mix in halogenating agent The molar ratio of total halogen atom such as can be 1: 0.0002-0.2, preferably 1: 0.001-0.08.It is described corresponding with alkoxyl Alcohol such as can be 4-50: 1, preferably 6-25: 1 with the part by weight of magnesium metal.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 the reaction for example can be 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 the magnesium metal, can be graininess, silk ribbon shape or powder for example Last shape.In order that the average grain diameter of the alkoxyl magnesium compound for generating is maintained in suitable scope, and particle shape is excellent, institute It is 10-360 μm of spherical metal magnesium to state magnesium metal and be preferably average grain diameter, and more preferably average grain diameter is spherical for 50-300 μm Magnesium metal.In addition, the present invention has no to the surface of the magnesium metal especially limit, but if in the surface shape of the 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 the magnesium metal 95 weight %, more preferably weight % of ＞ 98.

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, in order that the alkoxyl magnesium compound for arriving has more excellent performance, it is desirable to which moisture is fewer It is better, it usually needs water content in the alcohol corresponding with alkoxyl is controlled in below 1000ppm, 200ppm is preferably controlled in Below.

According to the present invention, the inert atmosphere is known to the skilled person, preferably blanket of nitrogen and/or argon atmospher. Additionally, the preparation of the alkoxyl magnesium compound is generally using atent solvent as reaction medium.Wherein, the atent solvent can be with For C₆-C₁₀Alkane or aromatic hydrocarbons at least one, preferably hexane, heptane, octane, decane, benzene,toluene,xylene and its At least one in derivative 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.By several times input raw material can be prevented wink When produce substantial amounts of hydrogen, so as to prevent the spittle of the alcohol or halogenating agent for producing and causing due to instantaneous substantial amounts of hydrogen, from peace From the point of view of full property angle and reaction uniformity, preferred this feed way.The number of times of segmentation can be according to the rule of reactor The consumption of mould and various materials is determining.After the completion of reaction, the end product dialkoxy magnesium for obtaining can also may be used with kept dry To be suspended in in inert diluent used during the titanium-containing catalyst solid constituent for preparing lower step.

According to the present invention, the formula of the titanium compound is preferably such as formula（Ⅲ）It is shown：

Ti(OR)_4-nX_nFormula（Ⅲ）,

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

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

Formula（Ⅳ）In, R₁And R₂It is identical or different, and it is each independently selected from C₁-C₂₀Straight chain, branched or ring-type aliphatic hydrocarbon Base；R₃、R₄、R₅、R₆、R₇And R₈It is identical 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 R₂It is identical or different, and it is each independently selected from C₁-C₆The alkyl of straight or branched；R₅、R₆It is identical or not Together, and it is each independently selected from C₁-C₁₀The alkyl of straight or branched, C₃-C₁₀Cycloalkyl.

The instantiation of the internal electron donor compound can be including but not limited to：2- isopropyl -2- isopentyl -1,3- Dimethoxy propane, 9,9- bis-（Methoxy）Fluorenes, 2- isobutyl group -2- isopropyl -1,3- dimethoxy propanes, the rings of 2,2- bis- Dicyclopentyldimetoxy propane, 2,2- diphenyl -1,3- dimethoxy propanes, 2- isobutyl group -2- isopropyl -1,3- dimethoxys third One kind or many in alkane, 2,2- bicyclopentyl -1,3- dimethoxy propanes, 2,2- diisobutyl -1,3- dimethoxy propanes etc. Kind.

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

According to the present invention, the preparation process of the solids containing titanium catalytic component is generally situated between using atent solvent as reaction Matter.Wherein, the 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.The atent solvent and alkane The molar ratio of the magnesium in epoxide magnesium compound such as can be 0.5-100：1, preferably 1-50：1.

According to the present invention, in the preparation process of the solids containing titanium catalytic component, the alkoxyl magnesium compound, titanium The addition sequence of compound, internal electron donor compound and atent solvent is not particularly limited, for example, can be in atent solvent In the presence of be well mixed above-mentioned each component, it is also possible to dilute each composition with atent solvent in advance, then again will be respective molten Liquid is well mixed.For the number of times of 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 into suspension, then with a part The mixture reaction that titanium compound and atent solvent are formed, filters, and obtains solid product；2nd, the solid product for obtaining is added another Continue to react in the mixture of a part of titanium compound and atent solvent, filter, obtain solid product；3rd, the reaction of the 2nd step is repeated 2-4 time；4th, the solid product for finally obtaining is washed with atent solvent, solids containing titanium catalytic component is obtained.Wherein, preparation process In, the amount of the titanium compound for adding every time can carry out reasonable selection according to the number of times for repeating reaction, can be 1/ for example N, n are the number of times+2 for repeating the 2nd step.

Method two：

1st, alkoxyl magnesium carrier compound, a part of internal electron donor and atent solvent are configured to into suspension, Ran Houyu The mixture reaction that a part of titanium compound and atent solvent are formed, filters, and obtains solid product；2nd, by the solid product for obtaining Add in the mixture 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 titanium compound and atent solvent a part of again Continue to react in thing, filter, obtain solid product；4th, repeat the 3rd step to react 2-4 time；5th, last time is washed with atent solvent The solid product for obtaining, obtains solids containing titanium catalytic component.Wherein, in preparation process, the titanium compound for adding every time Amount can according to repeat reaction number of times carry out reasonable selection, for example, can 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 into suspension, then with a part of titanium compound and lazy Property solvent formed mixture reaction, add internal electron donor compound, continue react, filter, obtain solid product；2nd, incite somebody to action To solid product add and continue to react in the mixture that another part titanium compound and atent solvent formed, filter, consolidate Body product；3rd, repeat the 2nd step to react 2-4 time；4th, the solid product for finally obtaining is washed with atent solvent, solids containing titanium is obtained and is urged Agent component.Wherein, in preparation process, the amount of the titanium compound for adding every time can be carried out according to the number of times for repeating reaction Reasonable selection, can be 1/n for example, and n is the number of times+2 for repeating the 2nd step.

Method four：

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

According to the present invention, in the preparation process of the 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, relative in 1 mole of alkoxyl magnesium compound Magnesium, the consumption for the atent solvent of washing for example can be 1-1000 mole, preferably 10-500 mole.The washing when Between for example can be 1-24 hours, preferably 6-10 hours.Additionally, from washing homogeneity and the angle of detersive efficiency, institute Stating washing is preferably carried out under agitation.

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

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

AlR'_pX_3-pFormula（Ⅴ）,

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

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

The 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''It is identical or different, and it is each independently halogen, hydrogen atom, C₁-C₂₀Alkyl, C₃- C₂₀Cycloalkyl, C₆-C₂₀Aryl or C₁-C₂₀Haloalkyl；R^3''For C₁-C₂₀Alkyl, C₃-C₂₀Cycloalkyl, C₆-C₂₀ Aryl or C₁-C₂₀Haloalkyl；M'' and n'' are each independently the integer of 0-3, and m''+n''<4.The organosilicon The specific example of compound can be including but not limited to：Trimethylmethoxysilane, diisopropyl dimethoxy silane, two isobutyls Base dimethoxysilane, isopropyl butyldimethoxysilane, di-t-butyl dimethoxysilane, tertbutyl methyl dimethoxy Base silane, t-butylethyl dimethoxysilane, tert-butyl group propyldimethoxy-silane, ter /-butylisopropyl dimethoxy silicon Alkane, Cyclohexyl Methyl Dimethoxysilane, Dicyclohexyldimethoxysilane, cyclohexyl-t-butyldimethoxysilane, ring penta Ylmethyl dimethoxysilane, cyclopentyl ethyl dimethoxysilane, dicyclopentyl dimethoxyl silane, cyclopentyl cyclohexyl two It is methoxy silane, double（2- methylcyclopentyls）Dimethoxysilane, dimethoxydiphenylsilane, diphenyl diethoxy silicon Alkane, phenyl triethoxysilane, MTMS, MTES, ethyl trimethoxy silane, propyl group three Methoxy silane, propyl-triethoxysilicane, isopropyltri-methoxysilane, isopro-pyltriethoxysilane, butyl trimethoxy Base silane, butyl triethoxysilane, trimethoxysilane, isobutyl triethoxy silane, amyl group trimethoxy silicon Alkane, isopentyl trimethoxy silane, cyclopentyl-trimethoxy-silane, cyclohexyl trimethoxy silane, diphenyl dimethoxy silicon Alkane, diphenyl diethoxy silane, phenyltrimethoxysila,e, phenyl triethoxysilane, n-propyl trimethoxy silane, second Thiazolinyl trimethoxy silane, VTES, tetramethoxy-silicane, tetraethoxysilane, four butoxy silanes etc.. These organo-silicon compound can be used individually, it is also possible to be applied in combination two or more.Preferably, it is described to have Organic silicon compound selected from dicyclopentyl dimethoxyl silane, diisopropyl dimethoxy silane, second, isobutyl dimethoxy silane, Cyclohexyl Methyl Dimethoxysilane, dimethoxydiphenylsilane, methyl-t-butyldimethoxysilane, tetraethoxy-silicane One or more in alkane, propyl-triethoxysilicane and isobutyl triethoxy silane.

According to the present invention, in the preparation process of the Ziegler-Natta catalyst, in the alkyl aluminum compound The molar ratio of the titanium in aluminium and the solids containing titanium catalytic component such as can be 20-500：1；Preferably 50-500：1；More Preferably 50-100：1.Aluminium in the alkyl aluminum compound such as may be used with the molar ratio of the silicon of the external donor compound Think 0.1-500：1, preferred 1-200：1, more preferably 3-100：1.

According to the present invention, the species of the nucleator is known to the skilled person, for example, can for glucitols into Core agent and/or aryl phosphoric acids salt nucleator.

The instantiation of the Sorbitol Nucleator can be including but not limited to：1,3:2,4- bis-（Benzylidene）-D- Sorbierite, 1,3:2,4- bis-（4- methylbenzene subunits）- D-glucitol, 1,3:2,4- bis-（3,4- dimethylbenzylidenes）- D- mountains Pears alcohol, 1,3:2,4- bis-（4- ethyl benzylidenes）- D-glucitol, double -1,3:2,4-（4 '-propyl group benzal）- 1- pi-allyls Sorbierite, double -1,3:2,4-（4 '-ethylbenzylidene）- 1- allyl sorbitols, double -1,3:2,4-（4 '-propoxyl group benzal Base）- 1- allyl sorbitols, double -1,3:2,4-（4 '-propyl group benzal）- 1- propyl group sorbierites, double -1,3:2,4-（4 '-the third Epoxide benzal）- 1- propyl group sorbierites.The Sorbitol Nucleator is preferably 1,3:2,4- bis-（3,4- dimethyl benzene methylenes Base）- D-glucitol（Milliken Co. of the U.S. can be such as purchased from, the trade mark is Millad3988）And/or double -1,3:2,4-（4 '-the third Base benzal）- 1- propyl group sorbierites（As disclosed in CN101484458A, Milliken Co. of the U.S. can be purchased from, the trade mark is NX8000）, particularly preferably double -1,3:2,4-（4 '-propyl group benzal）- 1- propyl group sorbierites.

The instantiation of the aryl phosphoric acids salt nucleator can be including but not limited to：2,2 '-methylene-bis-（4,6- Di-tert-butyl-phenyl）Sodium phosphate, 2,2 '-ethidine-bis-（4,6- di-tert-butyl-phenyls）Sodium phosphate, 2,2 '-methylene-bis-（4, 6- di-tert-butyl-phenyls）Lithium phosphate, 2,2 '-ethidine-bis-（4,6- di-tert-butyl-phenyls）Lithium phosphate, 2,2 '-ethidine-bis- （4- isopropyl -6- di-tert-butyl-phenyls）Sodium phosphate, 2,2 '-methylene-bis-（4- methyl -6- di-tert-butyl-phenyls）Lithium phosphate, 2,2 '-methylene-bis-（4- ethyl -6- di-tert-butyl-phenyls）Lithium phosphate, double [2,2 '-thiobis（4- methyl -6- di-t-butyls Phenyl）Calcium phosphate], double [2,2 '-thiobis（4- ethyl -6- di-tert-butyl-phenyls）Calcium phosphate], double [2,2 '-thiobis（4,6- Di-tert-butyl-phenyl）Calcium phosphate], double [2,2 '-thiobis（4,6- di-tert-butyl-phenyls）Magnesium phosphate], double [2,2 '-thiobis （The t-octyl phenyl of 4,6- bis-）Magnesium phosphate], 2,2 '-butane-bis-（4,6- 3,5-dimethylphenyls）Sodium phosphate, 2,2 '-t-octyl are sub- Methyl-bis-（4,6- 3,5-dimethylphenyls）Sodium phosphate, 2,2 '-t-octyl methylene-bis-（4,6- di-tert-butyl-phenyls）It is sodium phosphate, double [2,2 '-methylene-bis-（4,6- di-tert-butyl-phenyls）Calcium phosphate], double [2,2 '-methylene-bis-（4,6- di-tert-butyl-phenyls） Magnesium phosphate], double [2,2 '-methylene-bis-（4,6- di-tert-butyl-phenyls）Barium phosphate], 2,2 '-methylene-bis-（4- methyl-6-terts Butyl phenyl）Sodium phosphate, 2,2 '-methylene-bis-（4- ethyl -6- tert-butyl-phenyls）Sodium phosphate, it is double [4,4 '-dimethyl -6, 6 '-di-t-butyl -2,2 '-xenyl）Calcium phosphate], 2,2 '-ethidine-bis-（M- butyl -6- the tert-butyl-phenyls of 4-）Sodium phosphate, 2,2 '-methylene-bis-（4,6- 3,5-dimethylphenyls）Sodium phosphate, 2,2 '-methylene-bis-（4,6- diethyl phenyls）Sodium phosphate, 2, 2 '-ethidine-bis-（4,6- di-tert-butyl-phenyls）Potassium phosphate, double [2,2 '-ethidines-bis-（4,6- di-tert-butyl-phenyls）Phosphoric acid Calcium], double [2,2 '-ethidines-bis-（4,6- di-tert-butyl-phenyls）Magnesium phosphate], double [2,2 '-ethidines-bis-（4,6- di-t-butyls Phenyl）Barium phosphate], hydroxyl-bis- [2,2 '-ethidine-bis-（4,6- di-tert-butyl-phenyls）Aluminum phosphate], three pairs of [2,2 '-ethylidenes Base-bis-（4,6- di-tert-butyl-phenyls）Aluminum phosphate], hydroxyl-bis- [2,4,8,10- tetra-（1,1 '-dimethyl ethyl）- 6- hydroxyls- Ring -6- the oxygen of 12H- dibenzo [d, g] dioxy phospha eight] close aluminium.The aryl phosphoric acids salt nucleator is preferably 2,2 '-methylene Base-bis-（4,6- di-tert-butyl-phenyls）Sodium phosphate, hydroxyl-bis- [2,2 '-ethidines-bis-（4,6- di-tert-butyl-phenyls）Aluminum phosphate] With hydroxyl-bis- [2,4,8,10- tetra-（1,1 '-dimethyl ethyl）Ring-the 6- of -6- hydroxyl -12H- dibenzo [d, g] dioxies phospha eight Oxygen] close aluminium in one or more.The aryl phosphoric acids salt nucleator can be commercially available, and for example, can be purchased from day This rising sun electrification company, the trade mark are ADK NA-11（2,2 '-methylene-bis-（4,6- di-tert-butyl-phenyls）Sodium ascorbyl phosphate）And/or ADK NA-21（Main component is：Hydroxyl-bis- [2,4,8,10- tetra-（1,1 '-dimethyl ethyl）- 6- hydroxyl -12H- dibenzo Ring -6- the oxygen of [d, g] dioxy phospha eight] close aluminium）Aryl phosphoric acids salt nucleator.

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

The preparation method of the polypropylene flat-filament that the present invention is provided includes being put down above-mentioned polypropene composition curtain coating extrusion Film, and the flat film is cut into into base silk, then the base silk is preferably unidirectionally drawn below 115 DEG C at 80-110 DEG C Stretch.

Specifically, the preparation method of the polypropylene flat-filament includes mixing granulator, three steps of curtain coating extrusion and drawing and forming Suddenly：

（1）Mixing granulator：

Each component in the polypropene composition is well mixed in high speed agitator, and by the thing after being well mixed Material adds melting mixing in double screw extruder uniform and extruding pelletization, drying.Processing temperature is maintained between 170-250 DEG C, Finally obtain polypropene composition pellet.（2）Curtain coating extrusion：

By step（1）The polypropene composition pellet for obtaining is added in casting apparatus carries out extrusion curtain coating, and by T-shaped Diaphragm head is molded melt diaphragm, after Jing chill rolls, wind bath or the mode such as water-bath carry out cooling and shaping, form flat film processed, flat film The base silk with one fixed width is made after cleaved.Wherein, casting machine extrusion temperature can be 190-280 DEG C, be cast roller temperature Degree can be 5-35 DEG C, and flat film thickness can be 100-800 μm, and the base silk width after cutting can be 0.5-5cm.Also, root Need according to final products, it can be single or multiple lift structure composite head to be cast T-shaped diaphragm head.During using MULTILAYER COMPOSITE head Flat film upper and lower superficial layer can adopt low melting point pp material carry out it is multi-layer co-extruded prepare composite polypropylene flat filament, can So that prepared polypropylene flat-filament has good heat sealability and Thermoadhesive.

（3）Drawing and forming：

By step（2）The base silk for obtaining carries out simple tension below 115 DEG C, preferably at 80-110 DEG C, after Jing determine The steps such as type, cooling make polypropylene flat-filament.

According to the present invention, during drawing and forming, the multiplying power of simple tension is preferably above 10 times, more preferably 15- 25 times；Rate of extension is not less than 50%/s, preferably 50-100%/s.Drawing and forming can be stretched, can also adopted using single order Second order is stretched.Base silk is disposably stretched to setting multiplying power by the single order stretching, and now draft temperature need to generally be less than 115 DEG C, preferably 80-110 DEG C.The second order stretching is first to be pre-stretched at high temperature, carries out succeeding stretch at low temperature afterwards Setting multiplying power is reached, wherein, pre-stretching multiplying power is preferably 2-5 times, and pre-stretch temperature is preferably 125-150 DEG C；Succeeding stretch times Rate is preferably 10-15 times, and succeeding stretch temperature is preferably 80-110 DEG C.

Additionally, present invention also offers the polypropylene flat-filament prepared by said method.

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, polypropylene flat-filament adopts the two-way drawing of Karo VI type films of Bruckner company Stretch experimental machine and be prepared using simple tension technique.

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 gel permeation chromatograph of model PL-GPC220 of Polymer Laboratories companies production combines the infrared inspection of IR5 types Survey device to determine, wherein, the chromatographic column in gel permeation chromatograph is Plgel10 μm of MIXED-B post of 3 series connection, solvent and stream Dynamic phase is 1,2,4- trichloro-benzenes（Antioxidant DBPC 2,6 ditertiary butyl p cresol containing 0.3g/1000mL）, column temperature is 150 DEG C, stream Speed is 1.0mL/min, and using PL companies production EasiCal PS-1 Narrow distribution polystyrenes standard specimens universal calibration is carried out.

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 the unit group [mmmm] of isotaxy five：

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

Wherein, [mm], [mr], [rr] are respectively a three unit group isotactics, isotactic-rule, the content of an a rule-rule.

Using the nuclear magnetic resonance chemical analyser of the model AVANCE III of Bruker companies of Switzerland（NMR）Under determining 400MHz Polyacrylic nuclear-magnetism carbon spectrum（¹³C-NMR）, wherein, solvent is deuterated o-dichlorohenzene, and sample concentration is that 250mg samples/2.5mL is molten Agent.To prevent sample oxidative degradation in dissolving and data acquisition, 2, the 6- di-t-butyl -4- of 2mg are added in the sample Methylphenol antioxidant（Abbreviation BHT）.140 DEG C of dissolved samples, collection¹³C-NMR, 125 DEG C of test temperature, the milli of detecting head specification 10 Rice, 90 ° of pulses, sampling time AQ is 5 seconds, and time delay D1 is 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 measure of the position heterogeneous structure content that propylene 2,1 is inserted and 1,3 insertions are caused：

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

Wherein, α α, α β, α δ represent the locus of three kinds of different carbon atoms caused by different inserted modes, carbon atom For α α positions when represent inserted mode for normal " head-tail " mode, be " 2,1 " insertion when carbon atom is α β positions, carbon atom is α δ It is " 1,3 " insertion during position.

¹³The experimental condition of C-NMR is identical with 2, and the fixed sum data of recognizing of spectral peak is processed referring in particular to bibliography：（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 measure of TREF analytic types solubles content：Carried out using the TREF-300 type analysis instrument of Poly CHAR companies Determine, concrete grammar is as follows：Weigh trichloro-benzenes of the 80mg samples 40mL added with 0.3 weight %BHT（TCB）Solvent is at 150 DEG C Dissolving 60min, makes sample fully dissolve to form homogeneous solution；Take the above-mentioned solution of 20mL and 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；It is stable at 35 DEG C Being warming up to 140 DEG C with 1.0 DEG C/min again after 10min carries out drip washing.The flow velocity that solvent pump is controlled in drip washing is 0.5mL/min, molten Solution sample constantly drenches by solvent, records the relation for drenching thing and temperature of sample.Thing percentage composition will be drenched at 35 DEG C to be designated as TREF analytic type solubles contents.

5th, the measure of crystallization temperature Tc：DIAMOND types DSC produced using PE companies are measured, wherein, with indium metal Instrument is corrected with zinc standard specimen, sample quality is about 5mg, atmosphere is nitrogen, and throughput is 20mL/min.By sample with 10 DEG C/ramp of min to 210 DEG C and constant temperature 5min to eliminate thermal history, then with the speed of 10 DEG C/min be cooled to 50 again DEG C, crystallization exotherm is recorded, the corresponding temperature of the peak value of crystallization exotherm is designated as into 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, 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 being purchased from An He alliances 721 spectrophotometers of (Tianjin) development in science and technology Co., Ltd are measured.Alkoxyl magnesium compound and Ziegler-Natta are urged The particle diameter and particle diameter distribution index of agent is measured using Malvern Mastersizer TM2000 laser particle analyzers, Wherein, using n-hexane as dispersant, particle diameter distribution index SPAN=（D90-D10）/D50.M in alkoxyl magnesium compound The measure of value：0.1 gram of alkoxyl magnesium compound is taken, adds 10mL concentration to be 1.2mol/L aqueous hydrochloric acid solutions, concussion makes for 24 hours Its decomposition, using gas chromatograph（Purchased from Alan Analytical Instrument Co., Ltd, model GC-7960）To ethanol therein and 2- Ethyl hexanol content is measured and is calculated as follows m values：

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

The content of internal electron donor is surveyed using Waters600E liquid chromatographs in Ziegler-Natta catalyst It is fixed.

9th, the mechanical property of polypropylene flat-filament（Including tensile strength, stretch modulus and fracture norminal strain）According to GB/ T1040.3-2006 is tested.

Embodiment 1

The embodiment is used to illustrate polypropene composition and polypropylene flat-filament of present invention offer and preparation method thereof.

（1）Polyacrylic preparation：

The preparation of A, solids containing titanium catalytic component：It is sufficiently displaced from after the 16L voltage-resistant reactors with agitator with nitrogen, Then 10L ethanol, the 2-Ethylhexyl Alcohol of 300mL, 11.2g iodine, 8g magnesium chlorides and 640g magnesium powders are added toward reactor and is stirred Being well mixed, make system be warming up to 75 DEG C of back flow reactions while stirring, until there is no longer till hydrogen is discharged reaction is stopped. The product for obtaining washed, filtered with 3L ethanol, is dried, obtaining dialkoxy magnesium, its average grain diameter D50 is 30.2 μm, Particle diameter distribution index SPAN is 0.015 for 0.81, m.Take the above-mentioned dialkoxy magnesium of 650g, 3250mL toluene, the 2- isopropyls of 65mL Base -2- isopentyl -1,3- dimethoxy propanes are configured to suspension.In the pressure reactions of 16L for repeating displacement through high pure nitrogen In kettle, 2600mL toluene and 3900mL titanium tetrachlorides are added, are warming up to 80 DEG C, then the suspension for preparing is added in kettle, Constant temperature 1 hour at 80 DEG C, adds 2- isopropyl -2- isopentyl -1 of 65mL, 3- dimethoxy propanes to be to slowly warm up to 110 DEG C, then constant temperature 2 hours, press filtration obtains solid product.Above-mentioned solid product is added into 5070mL toluene and 3380mL titanium tetrachlorides Mixed liquor in, and in 110 DEG C of stir process 1 hour, so repeat to process 3 times, press filtration, and the solid product for obtaining is used into oneself Alkane（Through processed）Washing 4 times, each consumption is 600mL, and press filtration, 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 propanes is 11.9 weights Amount %.

B, experimental rig：

Device is using continuous autoclave pre-polymerization and horizontal retort gas phase series polymerizations technique.Prepolymerization reactor is jacketed cooling Vertical mixing Fu, 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 Fu, volume is 0.2 cubic metre, and 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 reaction time is 12 minutes；Titaniferous is consolidated Body catalyst component and triethyl aluminum inlet amount are respectively 0.4g/ hours and 0.058 mol/hr, and propylene feed amount is 10 public 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 reaction time is 60 minutes, will be walked Suddenly（1）The propylene pre-polymer for obtaining continuously is passed through in Horizontal stirring Fu, while the inlet amount for controlling propylene is 30 kgs/hour, And make hydrogen/propylene molar ratio in reaction gas phase be 0.0003.

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

（2）The preparation of polypropene composition：

Will be by step（1）Obtained polypropylene, nucleator and antioxidant（Concrete species and consumption are as shown in table 2, its In, nucleator be ADK NA-11, antioxidant be four [methyl-（3,5- di-tert-butyl-hydroxy phenyls）Propionic acid] pentaerythritol ester （Referred to as 1010））Add and be well mixed in agitator, then the material for mixing is added to into W＆P companiesTwin-screw extrusion In the feeder of machine, material is entered in twin-screw via feeder, and Jing screw rods melting mixing is uniform, extruding pelletization, drying, processing During screw rod temperature control between 170-230 DEG C, obtain polypropene composition pellet.

（3）The preparation of polypropylene flat-filament：

By step（2）The polypropene composition pellet for obtaining is added and is dried in hot-air oven, and will be dried poly- Propylene compositions pellet adds to be purchased from the curtain coating extrusion equipment of model LCR400 of Labtech companies of Sweden carries out curtain coating casting Piece, obtains flat film, and the flat film is cut into into base silk, and then the base silk for obtaining is adopted the Karo of Br ü ckner companies of Germany IV type film biaxial tension experimental machines are stretched.Specifically, base silk is put into the stretching folder of film biaxial tension experimental machine In tool, it is preheated after carry out simple tension, wherein, drawing and forming using single order stretch, draft temperature be 100 DEG C, stretching ratio For 15 times, rate of extension is 50%/s, obtains the polypropylene flat-filament that average thickness is 30 μm, width is 3mm, its performance such as institute of table 3 Show.

Embodiment 2

（1）Polyacrylic preparation：

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

B, experimental rig：（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 reaction time is 60 minutes, will be walked Suddenly（1）The propylene pre-polymer for obtaining continuously is passed through in Horizontal stirring Fu, while the inlet amount for controlling propylene is 30 kgs/hour, And make hydrogen/propylene molar ratio in reaction gas phase be 0.0005.

（2）It is prepared by polypropene composition：

With embodiment 1, except for the difference that, the consumption of nucleator is 0.05 weight portion.

（3）The preparation of polypropylene flat-filament：

With embodiment 1, except for the difference that, draft temperature is 80 DEG C, and stretching ratio is 18 times, and rate of extension is 100%/s, is obtained To average thickness be 30 μm, width for 3mm polypropylene flat-filament, its performance is as shown in table 3.

Embodiment 3

（1）Polyacrylic preparation：

B, experimental rig：（With embodiment 1）；

C, experimental condition：

The（1）Step prepolymerization：Reaction pressure is 2.5MPa, and reaction temperature is 10 DEG C, and the reaction time is 12 minutes；Titaniferous is consolidated Body catalyst component, triethyl aluminum and dicyclopentyl dimethoxyl silane（DCPDMS, is commonly called as D-Donor）Inlet amount is respectively 1.1g/ hours, 0.051 mol/hr and 0.0082 mol/hr, Al/Si mol ratios are 6.2, and propylene feed amount is 10 public 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 reaction time is 60 minutes, will be walked Suddenly（1）The propylene pre-polymer for obtaining continuously is passed through in Horizontal stirring Fu, while the inlet amount for controlling propylene is 30 kgs/hour, And make hydrogen/propylene molar ratio in reaction gas phase be 0.0005.

（2）The preparation of polypropene composition：

With embodiment 1, except for the difference that, the consumption of nucleator is 0.1 weight portion.

（3）The preparation of polypropylene flat-filament：

With embodiment 1, except for the difference that, drawing and forming is stretched using second order, wherein, the temperature of pre-stretching is 125 DEG C, prestretching Multiplying power is stretched for 5 times；Succeeding stretch temperature is 100 DEG C, and succeeding stretch multiplying power is 15 times, and rate of extension is 50%/s, obtains average The polypropylene flat-filament that thickness is 30 μm, width is 3mm, its performance is as shown in table 3.

Embodiment 4

（1）Polyacrylic preparation：

B, experimental rig：（With embodiment 1）；

C, experimental condition：

The（1）Step prepolymerization：Reaction pressure is 2.5MPa, and reaction temperature is 10 DEG C, and the reaction time is 12 minutes；Titaniferous is consolidated Body catalyst component, triethyl aluminum and second, isobutyl dimethoxy silane (DIBDMS is commonly called as B-Donor) inlet amount are respectively 1.0g/ hours, 0.054 mol/hr and 0.0087 mol/hr, Al/Si mol ratios are 6.2, and propylene feed amount is 10 public 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 reaction time is 60 minutes, will be walked Suddenly（1）The propylene pre-polymer for obtaining continuously is passed through in Horizontal stirring Fu, while the inlet amount for controlling propylene is 30 kgs/hour, And make hydrogen/propylene molar ratio in reaction gas phase be 0.0014.

（2）It is prepared by polypropene composition：

With embodiment 1, except for the difference that, nucleator is with the trade mark produced by Milliken Co. of the U.S. of 0.5 weight portion The nucleator of NX8000 is substituted.

（3）The preparation of polypropylene flat-filament：

With embodiment 1, except for the difference that, draft temperature is 100 DEG C, and stretching ratio is 15 times, and rate of extension is 50%/s, is obtained To average thickness be 30 μm, width for 3mm polypropylene flat-filament, its performance is as shown in table 3.

Comparative example 1

The comparative example is used to illustrate polypropene composition and polypropylene flat-filament of reference and preparation method thereof.

Method according to embodiment 1 carries out the preparation of polypropylene, polypropene composition and polypropylene flat-filament, different It is that polypropylene adopts the polypropylene purchased from the trade mark of TPC companies of Singapore for FS3011E（Molecular weight distributing index is 5.7, high Molecule hangover index is 1.85）Substitute, obtain reference polypropylene, reference polypropylene composition and reference polypropylene flat filament.Wherein, As shown in table 1, as shown in table 2, reference polypropylene is flat for the composition and consumption of reference polypropylene composition for the performance of reference polypropylene The performance of silk is as shown in table 3.

Comparative example 2

Method according to embodiment 2 carries out the preparation of polypropylene, polypropene composition and polypropylene flat-filament, different It is that polypropylene adopts the polypropylene purchased from the trade mark of TPC companies of Singapore for FS3011E（Molecular weight distributing index is 5.7, high Molecule hangover index is 1.85）Substitute, obtain reference polypropylene, reference polypropylene composition.Wherein, the performance of reference polypropylene As shown in table 1, the composition and consumption of reference polypropylene composition are as shown in table 2.By the polypropene composition according to embodiment 2 Method prepares polypropylene flat-filament, finds in preparation process, and occur the phenomenon of fracture of wire under this process conditions, the polypropylene is flat The preparation method and technology condition of silk is with embodiment 2.Find in preparation process, occur the situation of fracture of wire under this process conditions, Flat filament cannot drawing and forming.

Comparative example 3

Method according to embodiment 3 carries out the preparation of polypropylene, polypropene composition and polypropylene flat-filament, different It is, in the polyacrylic preparation process, the（2）The reaction temperature of step is 66 DEG C, and makes hydrogen and propylene in reaction gas phase Mol ratio be 0.002, obtain reference polypropylene, reference polypropylene composition and reference polypropylene flat filament.Wherein, reference poly- third As shown in table 1, the composition and consumption of reference polypropylene composition is as shown in table 2, the performance of reference polypropylene flat filament for the performance of alkene As shown in table 3.

Comparative example 4

（1）Polyacrylic preparation：

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

B, experimental rig（With embodiment 1）；

C, experimental condition：

Polypropylene without prepolymerization, in being added directly into horizontal agitated vessel.Polymeric reaction temperature is 98 DEG C, reaction pressure For 2.3MPa, the reaction time is 60 minutes.Solids containing titanium catalytic component and triethyl aluminum inlet amount be respectively 0.4g/ hours 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.

48 hours long run tests are carried out according to above-mentioned condition, has as a result been found, polymer active is too low, it is impossible to obtained poly- third Alkene, acquired results are as shown in table 1.

（2）It is prepared by polypropene composition：

Cannot prepare.

（3）The preparation of polypropylene flat-filament：

Cannot prepare.

Table 1

Project	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
									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,1O⁴g/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	-
Unit group [mmmm] content of isotaxy five, %	93.9	93.7	94.6	95.0	87.8	87.8	92.1	-
									The insertion of propylene 2,1 and/or 1,3 insertion contents, %	0	0	0	0	0	0	0	-
Solubles content (TREF analytic types), 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, DEG C	120.1	119.5	121.8	122.4	106.8	106.8	117.2	-

Table 2

Table 3

As can be seen from the above results, the present invention provide polypropylene flat-filament stretch modulus can reach 8.5GPa with On, tensile break strength can reach more than 856.7MPa, i.e. with higher mechanical strength.

Additionally, from the contrast of embodiment 1 and comparative example 1, embodiment 2 and comparative example 2 as can be seen that and being gathered using commercially available Propylene is compared for the polypropylene flat-filament that raw material is prepared, adopt the present invention offer polypropylene prepare for raw material poly- third Alkene flat filament has higher mechanical strength, and the drawing and forming performance of flat filament is more preferable.

The preferred embodiment of the present invention described in detail above, but, the present invention is not limited in above-mentioned embodiment Detail, the present invention range of the technology design in, various simple variants can be carried out to technical scheme, this A little simple variants 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 it is various can The combination of energy is no longer separately illustrated.

Additionally, can also be combined between a variety of embodiments of the present invention, as long as it is without prejudice to this The thought of invention, it should equally be considered as content disclosed in this invention.

Claims

1. a kind of polypropene composition, it is characterised in that the polypropene composition contains polypropylene and nucleator；The polypropylene Molecular weight distributing index be 2.5-5.5, in molecular weight distribution width macromolecule hangover indices P I_HTMore than 1.9；The high score Son 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, Mz is Z-average molecular weight, and unit is g/mol；

The polypropylene is prepared by the method for comprising the following steps：

(1) in the presence of Ziegler-Natta catalyst, propylene is carried out under -10 DEG C to 50 DEG C, 0.1-100MPa prepolymerization, 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, the propylene pre-polymer and propylene are polymerized.

2. polypropene composition according to claim 1, wherein, it is described on the basis of the polypropylene of 100 weight portions The content of nucleator is 0.01-1 weight portions.

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

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

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

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

7. the polypropene composition according to any one in claim 1-6, wherein, polyacrylic crystallization temperature Tc More than 113 DEG C.

8. polypropene composition according to claim 7, wherein, polyacrylic crystallization temperature Tc is more than 115 DEG C.

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

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

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

12. polypropene compositions according to any one in claim 1-6, wherein, the polypropylene at 230 DEG C, Melt mass flow rate MFR under the effect of 2.16kg load is 2-5g/10min.

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

Polypropylene flat-filament made by 15. polypropene compositions by described in any one in claim 1-14.

A kind of 16. preparation methods of polypropylene flat-filament, the method is included poly- third described in any one in claim 1-14 Ene compositions curtain coating extrusion obtains flat film, and the flat film is cut into into base silk, then the base silk is carried out into list below 115 DEG C To stretching.

17. preparation methods according to claim 16, wherein, the multiplying power of the simple tension is higher than 10 times；Rate of extension It is not less than 50%/s.

18. preparation methods according to claim 17, wherein, the multiplying power of the simple tension is 15-25 times.

19. preparation methods according to claim 17, wherein, the rate of extension is 50-100%/s.

The polypropylene flat-filament that 20. methods by described in any one in claim 16-19 are prepared.