CN104250883B

CN104250883B - A kind of polypropylene non-woven fabric and preparation method thereof

Info

Publication number: CN104250883B
Application number: CN201310268371.3A
Authority: CN
Inventors: 徐萌; 张师军; 李�杰; 于鲁强; 郭梅芳; 王良诗; 邹浩; 徐凯; 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: 2017-03-29
Anticipated expiration: 2033-06-28
Also published as: CN104250883A

Abstract

The invention provides the preparation method of a kind of polypropylene non-woven fabric and polypropylene non-woven fabric.In the polypropylene non-woven fabric, polyacrylic molecular weight distributing index is 2.5 5.5, macromolecule hangover indices P I in molecular weight distribution width_HTMore than 1.9.The polypropylene non-woven fabric has higher intensity.

Description

A kind of polypropylene non-woven fabric and preparation method thereof

Technical field

The present invention relates to a kind of polypropylene non-woven fabric and a kind of preparation method of polypropylene non-woven fabric.

Background technology

Polypropylene non-woven fabric has high good, ageing-resistant resistance to elevated temperatures, uvioresistant, elongation percentage, stability height, breathability The advantage such as good, corrosion-resistant, soundproof effect is good, therefore, it is heat insulating material formed which is widely used in garment lining, winter dress（Ski-wear, quilt Son, inner core of sleeping bag etc.）, working clothing, operating coat, protective clothing, Glove suede material.

The technique of production polypropylene non-woven fabric is more, it is for instance possible to use Nonwovens of spunbond production technology prepares poly- third Alkene non-woven fabrics.Detailed process is as follows：The mix homogeneously in agitator by polypropylene and auxiliary agent, and the mixture for obtaining is added crowded Go out machine（Such as double screw extruder）In feeder in, material via feeder enter twin screw in, Jing screw rod melting mixing is equal Even, extruding pelletization, drying obtain non-woven fabrics raw material pellet；Then the non-woven fabrics raw material pellet is added into single screw extrusion machine Middle melting mixing, extrusion, air-flow stretching, cooling and solidifying, lapping are simultaneously reinforced.Wherein, the auxiliary agent is usually antioxidant, halogen-resistant One or more in agent, light stabilizer, heat stabilizer, coloring agent and filler etc..

At present, the polypropylene for producing polypropylene non-woven fabric is typically with peroxide original molecule amount wider distribution is gathered Propylene feedstocks carry out degraded and obtain（The polypropylene for obtaining commonly referred to controls rheology polypropylene）, however, by using this degraded The polypropylene that obtains of method made by polypropylene non-woven fabric intensity it is relatively low.Additionally, on the one hand using for peroxide can increase Plus the cost of product, the peroxide on the other hand remaining may make polypropylene non-woven fabric further degrade, so as to reduce gathering The quality of propylene non-woven fabrics, and the polypropylene non-woven fabric that makes to finally give produces offending taste and limits which in some fields （The such as field such as health care, food）Application.

The content of the invention

The invention aims to the defect for overcoming existing polypropylene non-woven fabric intensity relatively low, and a kind of intensity is provided Higher polypropylene non-woven fabric and a kind of preparation method of polypropylene non-woven fabric.

The invention provides a kind of polypropylene non-woven fabric, wherein, polyacrylic molecular weight distribution in the polypropylene non-woven fabric Index is 2.5-5.5, macromolecule hangover indices P I in molecular weight distribution width_HTMore than 1.9.

Present invention also offers a kind of preparation method of polypropylene non-woven fabric, the method includes melting polypropylene and auxiliary agent Mixing, extrusion, air-flow stretching, cooling and solidifying, lapping are simultaneously reinforced, and the polyacrylic molecular weight distributing index is 2.5-5.5, point Macromolecule hangover indices P I in the son amount dispersion of distribution_HTMore than 1.9.

The polypropylene non-woven fabric that the present invention is provided molecular weight distributing index is narrower and macromolecule hangover index is larger, so The polypropylene non-woven fabric for enabling to has higher intensity.The poly- of present invention offer be can be seen that from the result of embodiment , in more than 82.6MPa, longitudinal fracture intensity is in more than 110.0MPa, transverse breakage elongation for the cross-breaking strength of propylene non-woven fabrics , more than 149%, longitudinal elongation at break rate is more than 160% for rate.Speculate its reason, it may be possible to due to：On the one hand, molecular weight distribution The narrower polypropylene of index has broader newton platform area in flow process, the change that its viscosity fluctuates with shear rate compared with Little, extrusion capacity is easier stability contorting, and can effectively reduce melt of the melt at spinneret orifice and swell phenomenon, reduces melt The probability that rupture and strand surface defect occur.Additionally, molecular weight distributing index is narrower can also to make spinning nozzle pressure stability, Guarantee that the fineness for spraying silk is uniform, fracture of wire drip phenomenon is reduced during non-woven fabrics spinning, and quality is more stable.On the other hand, Macromolecule hangover indices P I_HTIt is higher show polypropylene in there is more significant macromolecular chain tail end.According to polypropylene homogeneous nucleation Theory, macromolecular chain tail end in crystallization can Preferential Nucleation, raise polyacrylic crystallization temperature, crystallization rate is accelerated, have Beneficial to raising rigidity, shorten molding cycle and improve shaping efficiency.

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 in flow process broader newton platform area such that it is able to more show Writing ground reduces the probability that surface defect occurs during polypropylene non-woven fabric is prepared, and is conducive to improving polypropylene non-woven The crystallinity of cloth, so as to improve the mechanical property of polypropylene non-woven fabric.

A preferred embodiment of the invention, prepares polypropylene using two-stage polymerization method, and 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 for so enabling to not only has There are narrower molecular weight distribution and larger macromolecule hangover indices P I_HT, also with higher isotacticity and melt mass flow Speed, so as to further improve the intensity of the polypropylene non-woven fabric.Additionally, the polypropylene for preparing non-woven fabrics is needed with higher Melt mass flow rate and narrower molecular weight distribution, existing method is poly- third using peroxide degradation high molecular Alkene come reach the two requirement, and peroxide non-woven fabrics spin and deposit during, may continue to degraded, cause Non-woven fabrics intensity declines the color that concurrently changes, and peroxide often has offending abnormal smells from the patient, connects in manufacture health care or food Tactile product（Such as mask, operating coat）When, use feeling can be affected.And polypropylene is prepared using said method and need not add peroxidating Thing, can just obtain melt mass flow rate height, the polypropylene of narrow molecular weight distribution, solve the problems, such as that peroxide is remained, Gained non-woven fabrics substantially tasteless, can meet the needs of more areas application.

Additionally, another kind of preferred implementation of the invention, in the polyacrylic preparation process, when described neat Ge Le-Baunatal（Ziegler-Natta）When catalyst preferably comprises external donor compound, poly- third for obtaining can not only be made The further raising of alkene steric regularity, but also the content of xylene soluble part significantly drops in the polypropylene for enabling to Low, the polypropylene non-woven fabric abnormal smells from the patient for obtaining is lower, using safer, so as to widen the application neck of the polypropylene non-woven fabric Domain.

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 described herein concrete Embodiment is merely to illustrate and explains the present invention, is not limited to the present invention.

In the polypropylene non-woven fabric that the present invention is provided, polyacrylic molecular weight distributing index 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.

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

According to the present invention, in order that the polypropylene non-woven fabric has higher intensity, it is described polyacrylic complete with vertical The content of five unit group [mmmm] of structure is more than 85%, preferably greater than 90%, more preferably greater 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 " insertion, cause the regularity of polypropylene molecule chain structure to destroy, 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 non-woven fabric has higher intensity, under preferable case, described poly- third Alkene does not contain the caused position heterogeneous structure of the insertion of propylene 2,1 and 1,3 insertions.It should be noted that mentioned here " do not contain Have " do not refer to, and propylene 2 is referred to, and 1 insertion and 1,3 insertion contents are very low, and usually less than 0.01%, surpass The Monitoring lower-cut of instrument is gone out.

According to the present invention, preferably greater than 113 DEG C of polyacrylic crystallization temperature Tc, 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 significantly more improve the mechanical property of polypropylene non-woven fabric Energy.

According to the present invention, in the 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, polyacrylic isotacticity compared with Height, therefore rigidity and thermostability are preferable.Additionally, being applied to contact the polypropylene non-woven of food, human body, medicine or solvent to some For cloth, xylene soluble content is lower, then it is 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, the polypropylene is at 230 DEG C, the melt mass flow rate MFR under the effect of 2.16kg load Can be 0.01-1000g/10min, preferred 1-1000g/10min, further preferred 1-399g/10min, more preferably 10- 100g/10min.In the present invention, the melt mass flow rate MFR is measured according to method specified in ISO1133, its In, test temperature is 230 DEG C, and load is 2.16kg.

The preparation method of the polypropylene non-woven fabric that the present invention is provided is included polypropylene and auxiliary agent melting mixing, extrusion, gas Stream stretching, cooling and solidifying, lapping are simultaneously reinforced, and the polyacrylic molecular weight distributing index 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.

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- Continuous polymerization operation is carried out in answering device.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 carry out in the gas phase, 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 and the original weight ratio for adding 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 polyreaction can be 91-150 DEG C, preferably 91-110 DEG C； The pressure of the polyreaction can be 1-6MPa, preferably 2-5MPa.The time of the 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 the polyreaction 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 reacting kettle.The gas phase horizontal reacting kettle 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 reacting kettle 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 be reasonably selected according to practical situation, In the present invention, the addition of the molecular weight regulator is so that the polyacrylic melt mass flow rate MFR controls for obtaining In 0.01-1000g/10min, 1-1000g/10min is preferably controlled in, further preferably control is in 1-399g/10min, more excellent Selected control system is defined in 10-100g/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 can for example 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 be reasonably 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, and not fully representation alkoxy magnesium is concrete Structure.Specifically, as Mg (OEt) (OiPr) only represents that ethyoxyl and the mol ratio of isopropoxy are 1 in alkoxyl magnesium compound, It can both 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, it can be ethyoxyl with the alkoxyl magnesium compound group of the various structures that 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 Mean 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 in the solids containing titanium catalytic component, can also be contained（Such 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 %, 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 under an inert atmosphere and prepares.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, potassium bromide, potassium iodide, calcium chloride, calcium bromide, calcium iodide, mercuric chloride, mercuric bromide, iodate One or more in hydrargyrum, 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 can such as be 1：0.0002-0.2, preferably 1：0.001-0.08.It is described corresponding with alkoxyl Alcohol can such as be 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 the reaction can for example 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, for example, can be graininess, silk ribbon shape or powder Last shape.In order that the mean diameter of the alkoxyl magnesium compound for generating is maintained in suitable scope, and particle shape is excellent, institute Stating magnesium metal and mean diameter being preferably for 10-360 μm of spherical metal magnesium, more preferably mean diameter is spherical for 50-300 μm Magnesium metal.In addition, the present invention is had 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>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, 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 to be controlled in below 1000ppm, be preferably controlled in 200ppm 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 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 disposably can put into, it is also possible to select to put into by several times.Input raw material can be prevented wink by several times When produce substantial amounts of hydrogen, so as to the alcohol that prevents from producing and causing due to instantaneous substantial amounts of hydrogen or the spittle of halogenating agent, 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 Prepared in inert diluent used during the titanium-containing catalyst solid constituent of lower step with being suspended in.

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, integers of the n for 0-4.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, three alkane of dihalo- dialkoxy titanium and single halogen 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, two positive propoxy of dichloro 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, three positive propoxy titanium of a chlorine and three titanium isopropoxide of a chlorine.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-C₂₀The aliphatic hydrocarbon of straight chain, branched or ring-type 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 can be including but not limited to：2- isopropyl -2- isopentyl -1,3- dimethoxies Base propane, 9,9- bis-（Methoxy）Fluorenes, 2- isobutyl group -2- isopropyl -1,3- dimethoxy propanes, 2,2- bicyclopentyls two Methoxy propane, 2,2- diphenyl -1,3- dimethoxy propanes, 2- isobutyl group -2- isopropyl -1,3- dimethoxy propanes, 2, One or more in 2- bicyclopentyl -1,3- dimethoxy propanes, 2,2- diisobutyl -1,3- dimethoxy propanes etc..

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 Mol ratio with magnesium in alkoxyl magnesium compound can be 0.005-10：1；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 can such as 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 make above-mentioned each component mix homogeneously, it is also possible in advance dilute each composition with atent solvent, then again will be respective molten Liquid mix homogeneously.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, obtains solid product；2nd, the solid product for obtaining is added another Continue reaction in the mixture of a part of titanium compound and atent solvent, filter, obtain solid product；3rd, repeat the reaction of the 2nd step 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, for example, can be 1/ 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, obtains solid product；2nd, by the solid product for obtaining Continue anti-in adding the mixture formed by the internal electron donor of the titanium compound, atent solvent and remainder of another part Should, filter, obtain solid product；3rd, gained solid product continuously adds the mixing of titanium compound and atent solvent a part of again Continue reaction 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 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, 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, for example, can be 1/n, 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, obtains solid product；2nd, the solid product for obtaining is added by another part titanium compound and atent solvent shape Into mixture in continue reaction, 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 can for example be 1-1000 mole, preferably 10-500 mole.The washing when Between can for example 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；Response 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, integers of the p for 1-3.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 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 in chloroethyl aluminum, preferably triethyl aluminum and/or triisobutyl aluminium.

According to the present invention, in the Ziegler-Natta catalyst, the external electron donor optionally can add Enter.It was found by the inventors of the present invention that after adding 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-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.The organo-silicon compound Specific example can be including but 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 It is alkane, double（2- methylcyclopentyls）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 individually can be used, it is also possible to be applied in combination two or more.Preferably, the 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 in Ethoxysilane 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 aluminum and the solids containing titanium catalytic component can such as be 20-500: 1；Preferably 50-500: 1；More Preferably 50-100: 1.The silicon mol ratio of the aluminum in the alkyl aluminum compound and the external donor compound for example can be with For 0.1-500: 1, preferred 1-200: 1, more preferably 3-100: 1.

Mainly the theing improvement is that of the present invention employs that a kind of molecular weight distributing index is narrower and macromolecule hangover index PI_HTLarger polypropylene is used as raw materials for production, and concrete preparation process can be with same as the prior art.

Additionally, according to actual needs, the preparation method of the polypropylene non-woven fabric that the present invention is provided is additionally may included in will be poly- Before propylene and auxiliary agent melting mixing, first the polypropylene is mixed homogeneously in high speed agitator with auxiliary agent, and will be mixing equal Material after even adds extruding pelletization in double screw extruder, drying to obtain non-woven fabrics raw material, then again that the non-woven fabrics are former Material carries out melting mixing, extrusion, air-flow stretching, cooling and solidifying, lapping and reinforces, and obtains polypropylene non-woven fabric.

The species and consumption of the auxiliary agent can be the conventional selection of this area.For example, the auxiliary agent can be selected from antioxygen One or more in agent, halogen-resistant agent, light stabilizer, heat stabilizer, coloring agent, filler and Masterbatch.Additionally, with 100 weights On the basis of the polypropylene of amount part, the consumption of the auxiliary agent can be 0.05-0.3 weight portions, preferably 0.15-0.25 weight Part.

According to the present invention, according to actually used needs, the polypropylene non-woven fabric can be prepared into single-layer nonwoven, Multi-layer nonwoven fabrics can be prepared into.In addition it is also possible to prepare polypropylene non-woven fabric by the method such as melt-blown, concrete preparation method is As well known to those skilled in the art, here will not be described in great detail.

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 of Polymer Laboratories companies production combines the infrared inspection of IR5 types Survey device to determine, wherein, the chromatographic column in chromatograph of gel permeation is Plgel10 μm of MIXED-B post of 3 series connection, solvent and stream It is dynamic to be mutually 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, carries out universal calibration using PL companies production EasiCal PS-1 Narrow distribution polystyrenes standard specimens.

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 five unit group [mmmm] of isotaxy：

Due to¹³In C-NMR spectrums, for the methyl carbon area of 19.5-22.5ppm, can to provide resolution higher for chemical shift Stereoregular information, obtains a triad isotactic, 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 five unit group [mmmm] of isotaxy：

Wherein, [mm], [mr], [rr] are respectively a triad isotactic, 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）Determine under 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 is added in the sample Methylphenol antioxidant（Abbreviation BHT）.140 DEG C of dissolved samples, collection¹³C-NMR, 125 DEG C of test temperature, 10 milli of detecting head specification Rice, 90 ° of pulses, sampling time AQ are 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 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 that " 2,1 " insertion and " 1,3 " are inserted：

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 Insert for " 1,3 " 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 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 measure of TREF analytical 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 precipitation gradually be crystallized according to crystallizing power size in temperature-fall period and be deposited on post；It is stable at 35 DEG C 140 DEG C are warming up to 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 is drenched 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 analytical 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, be then cooled to 50 with the speed of 10 DEG C/min again DEG C, crystallization exotherm is recorded, the peak value of crystallization exotherm corresponding temperature 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 purchased from An He alliances 721 spectrophotometers of (Tianjin) development in science and technology company limited 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 normal 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, shake 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.

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

9th, the fracture strength and elongation at break of polypropylene non-woven fabric is tested according to method specified in GB/T3923.

10th, the abnormal smells from the patient of polypropylene non-woven fabric is measured according to method specified in SMC30156-2007, specifically, is taken 50g polypropylene non-woven fabrics are put in 1L containers, abnormal smells from the patient are passed judgment on after placing 120 minutes at 80 DEG C.Abnormal smells from the patient judgment criteria It is divided into 6 grades：1 grade：It is difficult to feel；2 grades：Can feel, but not be pungent；3 grades：Can be clearly felt that, but not be pungent；4 grades：Thorn Nose；5 grades：It is pungent very much；6 grades：Can not stand.

Embodiment 1

The embodiment is used to illustrate polypropylene non-woven fabric 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 powder are added toward reactor and is stirred Mix homogeneously, makes system be warming up to 75 DEG C of back flow reaction while stirring, the stopped reaction till it there is no longer hydrogen discharge. By the product for 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 0.015 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 kettles, 2600mL toluene and 3900mL titanium tetrachlorides are added, 80 DEG C are warming up to, 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, filter pressing 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, filter pressing, and the solid product for obtaining used into oneself Alkane（Through processed）Washing 4 times, each consumption are 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 propanes is 11.9 weights Amount %.

B, assay device：

Device adopts continuous autoclave pre-polymerization and horizontal retort gas phase series polymerizations technique.Prepolymerization reactor is jacketed cooling Vertical mixing Fu, volume are 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 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/ 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 response time is 60 minutes, will step 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 hydrogen/propylene molar ratio is 0.005 in making reaction gas phase.

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

（2）The preparation of polypropylene non-woven fabric：

By step（1）The polypropylene of obtained 100 weight portion and 0.2 weight portion four [β-（3,5- di-t-butyl -4- hydroxyls Phenyl）Propanoic acid] pentaerythritol ester（Referred to as 1010）Antioxidant adds mix homogeneously in agitator, then the material for mixing is added Enter in the feeder of WP25 double screw extruders, material is entered in twin screw via feeder, and Jing screw rods melting mixing is uniform, is squeezed Go out pelletize, dry, the temperature control of screw rod obtains non-woven fabrics raw material pellet between 170-230 DEG C in the course of processing.It is fragrant with Lay Person of outstanding talent's house Nonwovens of spunbond production line manufacture non-woven fabrics, pellet is added in single screw extrusion machine, and extruder temperature is controlled to 180- Between 230 DEG C, after the operation such as melting mixing, extrusion, air-flow stretching, cooling and solidifying, lapping and reinforcing, obtain polypropylene without Spin cloth JB1.The grammes per square metre of polypropylene non-woven fabric JB1 is 50g/m², performance is as shown in table 2.

Embodiment 2

（1）Polyacrylic preparation：

The preparation of A, 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 step 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 hydrogen/propylene molar ratio is 0.008 in making reaction gas phase.

（2）The preparation of polypropylene non-woven fabric：

Concrete grammar obtains polypropylene non-woven fabric JB2 with embodiment 1.The grammes per square metre of polypropylene non-woven fabric JB2 is 50g/ m², performance is as shown in table 2.

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.lg/ 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 response time is 60 minutes, will step 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 hydrogen/propylene molar ratio is 0.012 in making reaction gas phase.

（2）The preparation of polypropylene non-woven fabric：

Concrete grammar obtains polypropylene non-woven fabric JB3 with embodiment 1.The grammes per square metre of polypropylene non-woven fabric JB3 is 50g/ m², performance is as shown in table 2.

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/ 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 response time is 60 minutes, will step 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 hydrogen/propylene molar ratio is 0.015 in making reaction gas phase.

（2）The preparation of polypropylene non-woven fabric：

Concrete grammar obtains polypropylene non-woven fabric JB4 with embodiment 1.The grammes per square metre of polypropylene non-woven fabric JB4 is 50g/ m², performance is as shown in table 2.

Comparative example 1

The comparative example is used to illustrate reference polypropylene non-woven fabrics and preparation method thereof.

Method according to embodiment 1 carries out the preparation of polypropylene and polypropylene non-woven fabric, except for the difference that, in the polypropylene Preparation process in,（2）The reaction temperature of step is 66 DEG C, and makes hydrogen and the mol ratio of propylene in reaction gas phase be 0.025, Obtain reference polypropylene and reference polypropylene non-woven fabrics DJB1.Wherein, the performance of reference polypropylene is as shown in table 1, reference poly- third The grammes per square metre of alkene non-woven fabrics DJB1 is 50g/m², performance is as shown in table 2.

Comparative example 2

Method according to embodiment 3 carries out the preparation of polypropylene and polypropylene non-woven fabric, except for the difference that, in the polypropylene Preparation process in,（2）The reaction temperature of step is 66 DEG C, and makes hydrogen and the mol ratio of propylene in reaction gas phase be 0.05, Obtain reference polypropylene and reference polypropylene non-woven fabrics DJB2.Wherein, the performance of reference polypropylene is as shown in table 1, reference poly- third The grammes per square metre of alkene non-woven fabrics DJB2 is 50g/m², performance is as shown in table 2.

Comparative example 3

（1）Polyacrylic preparation：

B, assay device：（With embodiment 1）；

C, experimental condition：

Polypropylene is added directly in horizontal agitated vessel without prepolymerization.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/ hours and 0.058 mol/hr；The inlet amount of propylene is 30 kgs/hour, and hydrogen/propylene molar ratio is in making reaction gas phase 0.005。

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）The preparation of polypropylene non-woven fabric：

Cannot prepare.

Comparative example 4

Method according to embodiment 3 carries out the preparation of polypropylene non-woven fabric, and except for the difference that, polypropylene is adopted and refined purchased from Zhenghai Polypropylene of the trade mark of change company for H30S（Prepared using peroxide degradation, molecular weight distributing index is 4.3, high score Son hangover indices P I_HTFor 1.72）Substitute.The performance of reference polypropylene is as shown in table 1；The grammes per square metre of reference polypropylene non-woven fabrics DJB4 For 50g/m², performance is as shown in table 2.

Table 2

From the results shown in Table 2, the tensile strength and extension at break of the polypropylene non-woven fabric for being provided using the present invention Rate be superior in the non high temperature polymeric polymer propene non-woven fabrics in comparative example 1 and 2 and comparative example 4 by peroxide degradation poly- third The non-woven fabrics that alkene is prepared, it is possible thereby to illustrate, the intensity of the polypropylene non-woven fabric that the present invention is provided is higher, with excellent Mechanical property.Additionally, the polypropylene prepared using the method for the present invention is can also be seen that from embodiment 3 and the contrast of comparative example 4 The abnormal smells from the patient of non-woven fabrics well below the polypropylene non-woven fabric prepared by edman degradation Edman, therefore, can be widely used for medical treatment and food contact Deng the industry strict to odor requirements.

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 compound mode of energy is no longer separately illustrated.

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

Claims

1. a kind of polypropylene non-woven fabric, it is characterised in that polyacrylic molecular weight distributing index is in the polypropylene non-woven fabric 2.5-5.5, macromolecule hangover indices P I in molecular weight distribution width_HTMore than 1.9；Macromolecule hangover indices P I_HTBy with Lower formula is calculated：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, unit are 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 into 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, the propylene pre-polymer and propylene are polymerized.

2. polypropylene non-woven fabric according to claim 1, wherein, five unit group [mmmm] of the polyacrylic isotaxy Content be more than 85%.

3. polypropylene non-woven fabric according to claim 2, wherein, five unit group [mmmm] of the polyacrylic isotaxy Content be more than 90%.

4. polypropylene non-woven fabric according to claim 3, wherein, five unit group [mmmm] of the polyacrylic isotaxy Content be more than 93%.

5. polypropylene non-woven fabric 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；Described " not containing " does not refer to and absolutely not contains, and refers to propylene 2, and 1 insertion and 1,3 is inserted Enter content very low, less than 0.01%, beyond the Monitoring lower-cut of instrument.

6. the polypropylene non-woven fabric according to any one in claim 1-5, wherein, polyacrylic crystallization temperature Tc More than 113 DEG C.

7. polypropylene non-woven fabric according to claim 6, wherein, polyacrylic crystallization temperature Tc is more than 115 DEG C.

8. the polypropylene non-woven fabric according to any one in claim 1-5, wherein, xylene soluble in the polypropylene The content of thing is less than 4.4 weight %.

9. polypropylene non-woven fabric according to claim 8, wherein, in the polypropylene, the content of xylene soluble part is less than 2.3 weight %.

10. polypropylene non-woven fabric according to claim 9, wherein, in the polypropylene, the content of xylene soluble part is little In 1.6 weight %.

11. polypropylene non-woven fabrics according to any one in claim 1-5, wherein, the polypropylene at 230 DEG C, Melt mass flow rate MFR under the effect of 2.16kg load is 0.01-1000g/10min.

12. polypropylene non-woven fabrics according to claim 11, wherein, the polypropylene is at 230 DEG C, 2.16kg load is made Melt mass flow rate MFR with is 1-1000g/10min.

13. polypropylene non-woven fabrics according to claim 12, wherein, the polypropylene is at 230 DEG C, 2.16kg load is made Melt mass flow rate MFR with is 1-399g/10min.

14. polypropylene non-woven fabrics according to claim 13, wherein, the polypropylene is at 230 DEG C, 2.16kg load is made Melt mass flow rate MFR with is 10-100g/10min.

15. polypropylene non-woven fabrics according to claim 1, wherein, in the polyacrylic preparation process, step (1) The pre-polymerization multiple of the propylene pre-polymer for obtaining is 3-2000 gram of polymer/gram catalyst.

16. polypropylene non-woven fabrics according to claim 15, wherein, in the polyacrylic preparation process, step (1) The pre-polymerization multiple of the propylene pre-polymer for obtaining is 50-300 gram of polymer/gram catalyst.

17. polypropylene non-woven fabrics according to claim 1, wherein, the Ziegler-Natta catalyst contains solids containing titanium Catalytic component and alkyl aluminum compound and selectivity contain external donor compound.

18. polypropylene non-woven fabrics according to claim 17, wherein, the solids containing titanium catalytic component is by alkoxyl The catalytic product of magnesium compound, titanium compound and internal electron donor compound.

19. polypropylene non-woven fabrics according to claim 17, wherein, the 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”It is 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^”It is each independently the integer of 0-3, and m "+n "<4.

20. polypropylene non-woven fabrics according to claim 18, wherein, the formula such as formula II of the alkoxyl magnesium compound It is shown：

Mg(OR¹)_2-m(OR²)_mFormula II,

In formula II, R¹And R²It is identical or different, and it is each independently selected from C₁-C₈Straight or branched alkyl, 0≤m≤2.

21. polypropylene non-woven fabrics according to claim 20, wherein, the alkoxyl magnesium compound for spherical, and averagely Particle diameter D50 is 10-150 μm, and particle diameter distribution index SPAN is less than 1.1.

22. polypropylene non-woven fabrics according to any one in claim 18-21, wherein, the formula of the titanium compound As shown in formula III：

Ti(OR)_4-nX_nFormula III,

In formula III, R is C₁-C₁₄Aliphatic hydrocarbyl or aromatic hydrocarbyl, X is halogen atom, integers of the n for 0-4.

23. polypropylene non-woven fabrics according to any one in claim 18-21, wherein, the internal electron donor chemical combination Thing is diether compound of the formula as shown in formula IV：

In formula IV, R₁And R₂It is identical or different, and it is each independently selected from C₁-C₂₀The aliphatic hydrocarbyl of straight chain, branched or ring-type； 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-C₂₀Alkyl, C₃-C₂₀Cycloalkyl, C₆-C₂₀Aryl, C₇-C₂₀Alkaryl or C₇-C₂₀Aralkyl.

A kind of 24. preparation methoies of polypropylene non-woven fabric, the method are included polypropylene and auxiliary agent melting mixing, extrusion, air-flow Stretching, cooling and solidifying, lapping are simultaneously reinforced, and the polyacrylic molecular weight distributing index is 2.5-5.5, in molecular weight distribution width Macromolecule hangover indices P I_HTMore than 1.9；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；

25. preparation methoies according to claim 24, wherein, the pre-polymerization multiple of the propylene pre-polymer that step (1) is obtained is 3-2000 gram of polymer/gram catalyst.

26. preparation methoies according to claim 25, wherein, the pre-polymerization multiple of the propylene pre-polymer that step (1) is obtained is 50-300 gram of polymer/gram catalyst.

27. preparation methoies according to claim 24, wherein, the Ziegler-Natta catalyst contains solids containing titanium urges Agent component and alkyl aluminum compound and selectivity contain external donor compound.

28. preparation methoies according to claim 27, wherein, the solids containing titanium catalytic component is by alkoxyl magnesium The catalytic product of compound, titanium compound and internal electron donor compound.

29. preparation methoies according to claim 27, wherein, the external donor compound is formula such as formula I institute The organo-silicon compound for showing：

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

In formula I, R^1”And R^2”It is 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.

30. preparation methoies according to claim 28, wherein, the formula such as formula II institute of the alkoxyl magnesium compound Show：

Mg(OR¹)_2-m(OR²)_mFormula II,

31. preparation methoies according to claim 30, wherein, the alkoxyl magnesium compound is for spherical, and mean diameter D50 is 10-150 μm, and particle diameter distribution index SPAN is less than 1.1.

32. preparation methoies according to any one in claim 28-31, wherein, the formula such as formula of the titanium compound (III) shown in：

Ti(OR)_4-nX_nFormula III,

33. preparation methoies according to any one in claim 28-31, wherein, the internal electron donor compound is Diether compound of the formula as shown in formula IV：